APPARATUS TO DETECT, MEASURE AND QUANTIFY, SYSTEM, METHODS TO DETECT, TO MEASURE A CONCENTRATION OF

专利摘要:
these are systems, devices and methods for detecting agrochemical products in environments associated with agricultural equipment. certain agrochemicals that are formulated to be detected using the systems, devices and methods disclosed in this document are also described. the devices, systems and methods disclosed herein are generally configured to use spectral characteristics to detect agrochemicals in an environment associated with agricultural equipment. spectral characteristics can be analyzed in several ways to provide different types of information about agrochemicals and / or the environment.
公开号:BR112019024241A2
申请号:R112019024241-4
申请日:2018-05-17
公开日:2020-06-02
发明作者:M. Thompson Brian
申请人:Spogen Biotech Inc.；Nufarm Limited；
IPC主号:

专利说明:

“DETECT, MEASURE AND QUANTIFY APPLIANCE, SYSTEM, METHODS TO DETECT, TO MEASURE A CONCENTRATION OF A SUBSTANCE, TO EVALUATE THE CLEANING OF A CONTAINER, AND TO EVALUATE THE USE, MEASURE AND QUANTIFY, ACCESSORY, TOUCH, TANK, KIT , COMPOSITION AND COMPOSITION OR METHOD ”
JOINT RESEARCH AGREEMENT
[0001] The claimed invention was made by or on behalf of Elemental Enzymes Ag and Turf, LLC and Nufarm Americas Inc., part of a joint research agreement in effect prior to the date of the claimed invention and is the result of activities within the scope of the common research agreement.
FIELD
[0002] The present invention generally relates to systems and methods for detecting agrochemicals.
BACKGROUND
[0003] Agrochemicals, including pesticides (eg, insecticides, fungicides, herbicides, etc.). Plant growth regulators and fertilizers are widely used to improve the quality and yield of crops. Pesticides are commonly used to control weeds, pests, insects, fungi, nematodes and other diseases. Pesticides are commonly applied by spraying a solution containing pesticide on a crop. Fertilizers, used to promote plant growth, are applied in a similar way. After applying an agrochemical product solution, there is a residual amount of the agrochemical product remaining in the spray equipment, such as the spray tank, the spray nozzle (s) and any fluid ducts between the spray tank and the nozzle (s). Proper care and cleaning procedures to remove agrochemical residues from spray equipment after a spray application is important for
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2/166 proper maintenance of equipment and safety for subsequent sensitive crops that are sprayed or treated. In addition, it is necessary to identify the amount of pesticides, phytosanitary agents and products to promote the growth of plants in a mixture.
[0004] It is also important to remove pesticides or other agrochemical residues from spray equipment and any equipment used to apply, prepare, contain or transport spray solutions, or that is used to manufacture or store active ingredients or to prepare pesticide formulations to prevent crop damage resulting from unintentional transfer or cross-contamination of pesticides to crops sensitive to pesticide residue. Residual contamination in the tank and / or other spray equipment can cause significant damage to plants, even at extremely low levels of pesticide application. This contamination can come from spray solutions, transport or pesticide storage containers, cross-contamination from manufacturing or chemicals or precursor formulations of pesticides or manufacturing waste streams. Injuries caused by improper cleaning of equipment are particularly problematic for growth regulating or auxin-type herbicides, commonly used to control perennial and annual broadleaf weeds, in which case even small amounts of herbicidal residue can result in significant damage to sensitive or non-target plants and harvest plants. For example, benzoic acid herbicides, such as dicamba, are well known for their ability to damage crops when residues are applied to sensitive plants. Crop damage can also occur from other auxin-type herbicides, including, but not limited to, phenoxyacetic acids (phenoxys), such as 2,4-D, 2,4-DB, 2,4-DP (dichloroprop or acid dichloroprop), 2,4,5-T, 2,4,5-TP, MCPA, MCPB, MCPB NA, MCPB acid, MCPP (mecoprop), (+) R-2- (4-chloro-2 methylphenoxy) acid
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3/166 propionic (technical acid from Mecoprop-P), technical acid from Dichlorprop-P and Tropotox (MCPB + MCPA), Quinclorac, Quinmerac and other formulations of amine or 2,4-D ester and carboxylic acids-pyridine, as Clopiralida, Picloram, Triclopir, Aminopiralida, Am inocicliclirirlor, Halauxifen-methyl, Florpirauxifen-benzyl, Clacifos and their precursor chemicals or pesticide final products.
[0005] In addition, there is a need to reduce or control pesticide levels in fruit washing areas, post-harvest baths, and fertilizer irrigation lines, drip lines, pumps, chemigation systems, fertilization systems , and fire irrigation systems.
[0006] Agrochemicals are sometimes applied as seed coatings to cultivated seeds. A "seed treatment" refers to any substance used to coat a seed. For example, seed treatments can be an application of biological organisms, chemical ingredients, inoculants, herbicide protectors, micronutrients, plant growth regulators, seed coatings, etc. applied to a seed to suppress, control or repel pathogens, insects or other pests that attack seeds, parts of seedling plants or plants. In many cases, seed treatments include applying a pesticide to the surface of a seed as a coating designed to reduce, control or repel organisms, insects or other pests that attack seeds or seedlings grown from treated seeds. Seed treatments are commonly applied by spraying or otherwise depositing a material containing the desired ingredient or combination of ingredients in the seeds. The equipment used to apply the seed treatment to the seeds needs to be cleaned for reasons similar to the reasons why the equipment used to apply a pesticide to a field needs to be cleaned, especially when the seed treatment includes
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4/166 one or more pesticides. Even if the seed treatment does not include pesticides, however, it may be important to clean the equipment used to apply the seed coating.
[0007] The same agricultural equipment is commonly used to apply more than one type of agrochemical product in a number of different agrochemical product applications. Likewise, seed treatment or other manufacturing equipment can be used in connection with different types of agrochemical products. In a typical cleaning application and / or manufacturing equipment process, any unused pesticide product (eg, spray or seed treatment material) is drained from the tank and all hose nozzles and related equipment and disposed of accordingly. federal, state and local guidelines. The tank and fluid lines are washed with clean water. The tank can be filled with water and one or more cleaners added to the water to make a cleaning solution. The cleaning solution can be recirculated through the equipment with all spray nozzles closed by valves, which provides agitation to aid in the cleaning process. The cleaning solution can also be in the tank and related equipment. All filters, screens and sieves are normally removed and soaked. The order of the steps may vary. The steps are often repeated. It is generally recommended that the process include immersing the equipment in the cleaning solution overnight. The time required to complete this cleaning process usually ranges from 4 to 36 hours. Thus, the equipment has significant downtime each time it needs to be cleaned.
[0008] Customized spray applications on crops, which are becoming common in agricultural practices, may employ the use of more than one pesticide at the same time, for example, the application of a growth regulating herbicide, such as dicamba, combined with 2,4-D or
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5/166 a combination of herbicide mixtures combined with a fungicide or an insecticide. These combinations of agrochemicals can make equipment cleaning procedures even more problematic. Commercial cleaning products are currently available for cleaning spray tanks. Typically, the use of these cleaning products requires that the cleaning rinse water remains in the spray tank overnight with additional rinses with water that follow the cleaning process. This process is expensive, both from a time and cost perspective for the user, farmer or producer. In addition, many cleaning products available on the market are caustic, which can be harmful to the exposed operator and not considered environmentally safe or beneficial.
[0009] The present inventors have made several improvements to the systems and methods for determining a concentration and nature of an agrochemical, such as a pesticide or a final pesticide product, in an environment, which are described in detail below.
SUMMARY
[0010] One aspect of the invention is an apparatus for detecting, measuring and quantifying the amount of at least one pesticide or final pesticide product in an environment. The apparatus includes a light source and a spectrophotometric device comprising a detector positioned to receive light from the light source after the light has been transmitted through or reflected by the environment. The spectrophotometric device is configured to measure the intensity of the light received as a function of the wavelength to determine the spectral characteristics of the light received. The apparatus includes a processor configured to measure a concentration of a pesticide or final pesticide product using the spectral characteristics of the received light.
[0011] Another aspect of the invention is a system for analyzing the amount of a pesticide and / or a final pesticide product in an environment.
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6/166 system includes a processor with a data exchange interface. The processor data exchange interface is configured to receive information about a concentration of the pesticide or final product of the pesticide in the environment of another data exchange interface. The information includes a series of measurements of the concentration of the pesticide or the final product of the pesticide. The processor is configured to use information about the concentration of the pesticide or the final product of the pesticide to: predict at time t1 a first predicted rate of change in concentration using a first set of filter parameters; calculate a predicted concentration of the pesticide or final product of the pesticide at a time t2 based on the information and the rate of change predicted, where time t2 is later than time t1; comparing the predicted concentration of the pesticide or final product of the pesticide at time t2 with a measurement of the concentration of the pesticide or final product of the pesticide corresponding to time t2 to determine a difference between the predicted concentration at time t2 and the concentration measured at time t2; determining a second set of filter parameters different from the first set of filter parameters based on the difference between the predicted concentration at time t2 and the measured concentration at time t2; and calculating a predicted concentration of the pesticide or final product of the pesticide at a time t3 using the second set of filter parameters, where time t3 is different from time t1 and different from time t2.
[0012] Another aspect of the invention is a method for detecting, measuring and quantifying the amount of at least one pesticide or final pesticide product in an environment. The method includes receiving light from a light source after the light has been transmitted through or reflected by the environment. The intensity of the light received is measured as a function of the wavelength to obtain spectral characteristics of the light received. A concentration of the pesticide or final product of the pesticide is determined using the spectral characteristics of the
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7/166 light received.
[0013] Yet another aspect of the invention is an accessory for agricultural spraying equipment. The accessory includes a conduit to contain a fluid containing pesticide. A pair of windows is usually installed on opposite sides of the duct. The accessory also has a connector configured to connect the duct to at least one of an in-line filter and a spray bar.
[0014] Yet another aspect of the invention is a nozzle for applying a pesticide. The nozzle has a nozzle body and a pair of windows installed on generally opposite sides of the nozzle body.
[0015] Another aspect of the invention is a tank to contain a solution containing pesticide. The tank includes a wall that includes at least partially a space to retain the solution; and a system for determining the amount of pesticide in the solution. The system includes a light source and a spectrophotometric device, including a detector positioned to receive light from the light source after the light has been transmitted or reflected by the solution. The spectrophotometric device is configured to measure the intensity of the light received as a function of the wavelength to determine the spectral characteristics of the light received. The system includes a processor configured to measure a concentration of the pesticide or final product of the pesticide using the spectral characteristics of the received light. At least the light source and the spectrophotometric device are embedded in the wall.
[0016] Another aspect of the invention is a kit for installing a system to determine an amount of pesticide or final pesticide product in a solution contained in a piece of agricultural spraying equipment in agricultural spraying equipment. The kit includes a light source and a photodetector device, including a detector. The spectrophotometric device is configured to measure the light intensity received by the detector as a
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8/166 wavelength function to determine the spectral characteristics of the received light. The kit includes a processor configured to measure a concentration of the pesticide or final product of the pesticide using the spectral characteristics of the received light. The kit also includes a conduit to flow fluid into a space between the light source and the spectrophotometric device and a connector to connect the conduit to the agricultural spraying equipment, so that the fluid from the agricultural spraying equipment piece can flow through the conduit. . The kit has instructions for connecting the connector to the part's agricultural spray equipment.
[0017] In another aspect, the invention includes a method for measuring a concentration of a substance in an environment. The method includes receiving light from a light source after the light has been transmitted through or reflected by the environment. The intensity of the light received is measured as a function of the wavelength to obtain spectral characteristics of the light received. A concentration of the substance is determined using the spectral characteristics of the light received. The substance is selected from the group consisting of an adjuvant, a fertilizer, a growth regulator, a micronutrient, a biological control agent, a phytosanitary agent, an inoculant, a surfactant, an osmoprotector, a protector, a marker molecule, a buffering agent, an trace element, a water conditioning agent and a hard water solute.
[0018] Yet another aspect of the invention is an apparatus for measuring a concentration of a substance in an environment. The apparatus includes a light source and a spectrophotometric device, including a detector positioned to receive light from the light source after the light has been transmitted through or reflected by the environment. The spectrophotometric device is configured to measure the intensity of the light received as a function of the wavelength to determine the spectral characteristics of the light
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9/166 received. The apparatus includes a processor configured to measure a concentration of the substance using the spectral characteristics of the received light. The substance is selected from the group consisting of an adjuvant, a fertilizer, a growth regulator, a micronutrient, a biological control agent, a phytosanitary agent, an inoculant, a surfactant, an osmoprotective, a protector, a marker molecule and a hard water solute.
[0019] Another aspect of the invention is a method of evaluating the cleanliness of a returnable or reusable container. The method includes receiving light from a light source after the light has been transmitted through or reflected by a material over or flowing from the container. The intensity of the light received is measured as a function of the wavelength to obtain spectral characteristics of the light received. The concentration of a pesticide or final pesticide product is determined using the spectral characteristics of the light received.
[0020] In one aspect, an apparatus for detecting, measuring and quantifying the quantity of at least one agrochemical product in an environment comprises a light source. A spectrophotometric device comprises a detector positioned to receive light from the light source after the light has been transmitted through or reflected by said environment. The spectrophotometric device is configured to measure the intensity of the light received as a function of the wavelength to determine the spectral characteristics of the light received. A processor is configured to measure a concentration of said agrochemical product using the spectral characteristics of the received light.
[0021] In another aspect, a system for analyzing the quantity of an agrochemical product in an environment comprises a processor having a data exchange interface. The processor data exchange interface is configured to receive information about a concentration of the agrochemical product in the environment of another data exchange interface. The said
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10/166 information includes a series of measurements of the concentration of the agrochemical product. The processor is configured to use information about the concentration of the agrochemical product to: predict in time t1 a first predicted rate of change of that concentration using a first set of filter parameters; calculate a predicted concentration of the said agrochemical product at a time t2 based on said information and on the predicted rate of change, where time t2 is later than time t1; comparing said predicted concentration of said agrochemical product at time t2 with a measurement of said concentration of said agrochemical product corresponding to time t2 to determine a difference between the predicted concentration at time t2 and the concentration measured at time t2; determining a second set of filter parameters different from the first set of filter parameters based on said difference between the predicted concentration at time t2 and the measured concentration at time t2; and calculating a predicted concentration of said agrochemical product at time t3 using said second set of filter parameters, where time t3 is different from time t1 and different from time t2.
[0022] In yet another aspect, a method to detect, measure and quantify the quantity of at least one agrochemical product in an environment comprises receiving light from a light source after the light has been transmitted through or reflected by said environment. The intensity of the light received is measured as a function of the wavelength to obtain spectral characteristics of the light received. A concentration of said agrochemical product is determined using the spectral characteristics of the received light.
[0023] In one or more modalities of the method, one or more of the following steps are performed based on the determined concentration of the agrochemical product in the environment: cleaning agricultural equipment that define the environment with a cleaning agent; stop cleaning equipment
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11/166 agricultural activities that define the environment; using agricultural equipment that defines the environment with another agrochemical product; refrain from using agricultural equipment that defines the environment with another agrochemical product; discard rinsing water in agricultural equipment that defines the environment; add cleaning agent to rinse in agricultural equipment that define the environment; spraying another agrochemical product from agricultural spraying equipment that defines the environment; avoid or interrupt the spraying of an agrochemical product solution with another agrochemical agent in agricultural spray equipment that defines the environment; refrain from treating seeds with a seed treatment comprising another agrochemical using environment-defining seed treatment equipment; treating seeds with a seed treatment comprising another agrochemical using environment-defining seed treatment equipment; generate a dispatch alert indicating that a residue of the agrochemical product is present in the environment when the environment is expected to be substantially free of the agrochemical product; add a detoxifying formulation to a solution in agricultural equipment that defines the environment; generate a dispatch alert indicating that the concentration of the agrochemical product in agricultural equipment that defines the environment is in a safe zone concentration; determine compliance with crop loss insurance requirements; adjust a crop loss insurance premium rate and a crop loss insurance deductible; advancing a production process for an agrochemical product to a subsequent processing step; delay the advance of an agrochemical product production process to a subsequent processing step; determine whether you want to clean a drum that defines the environment; cleaning a re-started drum that defines the environment; and refrain from cleaning a re-taken drum that defines the environment.
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[0024] In another aspect, an accessory for agricultural spraying equipment comprises a duct for containing a fluid containing agrochemicals and a pair of windows. At least one window is formed in the conduit. At least one window is configured to transmit electromagnetic radiation through the window. A connector is configured to connect the duct to at least one of an in-line filter and a spray boom. A detector detects electromagnetic radiation transmitted through the window associated with the fluid containing the agrochemical product. The detector is configured to detect the agrochemical product based on the electromagnetic radiation that is transmitted through the window.
[0025] In yet another aspect, a nozzle for applying an agrochemical product comprises a nozzle body that defines an outlet opening through which a fluid containing agrochemical product can be dispensed. A pair of windows are installed on the generally opposite sides of the nozzle. At least one window is formed in the nozzle body. At least one window is configured to transmit electromagnetic radiation through the window. A detector detects electromagnetic radiation transmitted through the window associated with the fluid containing the agrochemical product. The detector is configured to detect the agrochemical product based on the electromagnetic radiation that is transmitted through the window.
[0026] In yet another aspect, a tank to contain a solution containing agrochemical product comprises a wall that at least partially encloses a space to retain the solution. A system for determining an amount of an agrochemical in the solution comprises a light source. A spectrophotometric device comprises a detector positioned to receive light from the light source after the light has been transmitted or reflected by said solution. The spectrophotometric device is configured to measure the intensity of the light received as a function of the length of
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13/166 wave to determine the spectral characteristics of the light received. A processor is configured to measure a concentration of said agrochemical product using the spectral characteristics of the received light. At least the light source and the photometric device are embedded in the wall.
[0027] In another aspect, a kit to install a system to determine an amount of an agrochemical in a solution contained in a piece of agricultural spraying equipment in the agricultural spraying equipment comprises a light source. A spectrophotometric device comprises a detector. The spectrophotometric device is configured to measure the intensity of the light received by the detector as a function of the wavelength to determine the spectral characteristics of the light received. A processor is configured to measure a concentration of said agrochemical product using the spectral characteristics of the received light. A conduit is configured to flow fluid in a space between the light source and the spectrophotometric device. A connector connects the conduit to the agricultural spraying equipment, so that the fluid from the agricultural spraying equipment piece can flow through the conduit. The kit contains instructions for connecting the connector to the part's agricultural spray equipment.
[0028] In yet another aspect, a method for measuring a concentration of a substance in an environment comprises receiving light from a light source after the light has been transmitted through or reflected by that environment. The intensity of the light received is measured as a function of the wavelength to obtain spectral characteristics of the light received. A concentration of the substance is measured using the spectral characteristics of the light received. The substance is selected from the group consisting of an adjuvant, a fertilizer, a growth regulator, a micronutrient, a biological control agent, a phytosanitary agent, an inoculant, a surfactant, an osmoprotective, a protector, a marker molecule and a solute
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14/166 hard water.
[0029] In yet another aspect, an apparatus for measuring a concentration of a substance in an environment comprises a source of light. A spectrophotometric device comprises a detector positioned to receive light from the light source after the light has been transmitted through or reflected by said environment. The spectrophotometric device is configured to measure the intensity of the light received as a function of the wavelength to determine the spectral characteristics of the light received. A processor is configured to measure a concentration of the substance using the spectral characteristics of the light received. The substance is selected from the group consisting of an adjuvant, a fertilizer, a growth regulator, a micronutrient, a biological control agent, a phytosanitary agent, an inoculant, a surfactant, an osmoprotective, a protector, a marker molecule and a hard water solute.
[0030] In yet another embodiment, a method of evaluating the cleanliness of a returnable or reusable container comprises receiving light from a light source after the light has been transmitted through or reflected by a material on or flowing from the container. The intensity of the light received is measured as a function of the wavelength to obtain spectral characteristics of the light received. The concentration of an agrochemical product is determined using the spectral characteristics of the light received.
[0031] In another aspect, a method for evaluating the use of an agrochemical product comprises providing a fluid that can include the agrochemical product. Receive light from a light source after the light has been transmitted through or reflected by at least a portion of the fluid. The intensity of the light received is measured as a function of the wavelength to obtain spectral characteristics of the light received. A concentration of the agrochemical product in the fluid is determined using the spectral characteristics of the light
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15/166 received.
[0032] In certain methods of the method, the method further comprises performing at least one of the following steps based on the determined concentration of the agrochemical product in the fluid: cleaning agricultural equipment in which the fluid is received with a cleaning agent; stop cleaning the agricultural equipment in which the fluid is received; use agricultural equipment in which the fluid is received with another agrochemical product; refrain from using agricultural equipment in which the fluid is received with another agrochemical product; discard rinsing water in agricultural equipment in which the fluid is received; add cleaning agent to rinse in agricultural equipment where the fluid is received; spraying another agrochemical product from agricultural spraying equipment in which the fluid is received; refrain from or stop spraying a solution of an agrochemical product with another agrochemical agent in agricultural spray equipment in which the fluid is received; refrain from treating seeds with a seed treatment comprising another agrochemical agent using seed treatment equipment in which the fluid is received; treating seeds with a seed treatment comprising another agrochemical agent using seed treatment equipment in which the fluid is received; generate a dispatch alert indicating that a residue of the agrochemical product is present in the fluid when the fluid is expected to be substantially free of the agrochemical product; add a detoxifying formulation to the fluid; generate a dispatch alert indicating that the concentration of the agrochemical product in the fluid is in a safe zone concentration; determine compliance with crop loss insurance requirements; adjust a crop loss insurance premium rate and a crop loss insurance deductible; advancing a production process for an agrochemical product to a subsequent processing step;
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16/166 delaying the advance of a production process for an agrochemical product to a subsequent processing step; determine whether to clean a resumed drum in which the fluid is received; clean a resumed drum in which the fluid is received; and refrain from cleaning a taken up drum in which the fluid is received.
[0033] In another aspect, a composition is provided. The composition comprises an agrochemical product and a marker dye or marker pigment.
[0034] In yet another aspect, a method is provided to detect the presence of an agrochemical product in a liquid. The method involves obtaining an absorbance spectrum for the liquid. The liquid came into contact with the equipment previously exposed to a composition comprising the agrochemical product and a marker dye or marker pigment. The method also comprises comparing the absorbance spectrum with a reference absorbance spectrum for the marker dye or marker pigment. The reference spectrum for the marker dye or marker pigment with maximum absorbance (Amax) at one or more wavelengths. The presence of an Amax in the absorbance spectrum for the liquid at the same wavelength or wavelengths indicates that the agrochemical is present in the liquid.
[0035] In yet another aspect, a method is provided to detect a counterfeit agricultural composition. The method comprises obtaining an absorbance spectrum from an agricultural composition suspected of falsification and comparing the absorbance spectrum obtained for the agricultural composition suspected of falsification with a reference absorbance spectrum for a genuine agricultural composition. The genuine agricultural composition comprises an agrochemical product and a marker dye or marker pigment. The reference spectrum has a maximum absorbance
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17/166 (Amax) for the dye or pigment in one or more wavelengths. The absence of an Amax in the absorbance spectrum for the agricultural composition suspected of falsification at the same wavelength or wavelengths indicates that the agricultural composition suspected of falsification is a falsified composition.
[0036] Other aspects will be partly evident and partly highlighted below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Figure 1 is a schematic diagram that illustrates a modality of a system for detecting agrochemical products;
[0038] Figure 2 is a schematic diagram that illustrates a modality of agricultural equipment for spraying a solution of agrochemical product and to which the detection system can be operationally connected;
[0039] Figure 3 is a schematic illustration of an arrangement of the detection system in which a photodetector device and a light source are arranged adjacent to a fenestrated conduit;
[0040] Figure 4 is a schematic illustration of another arrangement of the detection system in which the optical fibers operationally connect the photodetector device and the light source to the fenestrated conduit;
[0041] Figure 5 is a schematic illustration of another arrangement of the detection system in which the photodetector device and the light source are operationally connected to a flow cell;
[0042] Figure 6 is a schematic illustration of another arrangement of the detection system comprising a protective coating;
[0043] Figure 7 is a schematic illustration of another arrangement of the detection system comprising a processor and a power supply;
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[0044] Figure 8 is a schematic illustration of another arrangement of the detection system comprising a screen;
[0045] Figure 9 is a schematic illustration of another arrangement of the detection system comprising mounting brackets;
[0046] Figure 10 is a schematic illustration of another arrangement of the detection system in which the fenestrated conduit can be connected fluidly to a plurality of fluid sources;
[0047] Figure 11 is a schematic illustration of another arrangement of the detection system in which the fenestrated conduit is fluidly connected to a filter;
[0048] Figure 12 is a schematic illustration of another arrangement of the detection system in which a fluid line extends from a spray bar to the detection system;
[0049] Figure 13 is a schematic illustration of another arrangement of the detection system in which the detection system is mounted directly on the spray boom;
[0050] Figure 14 is a schematic illustration of another arrangement of the detection system in which a flow cell attached to the spray boom operationally connects the detection system to the spray boom;
[0051] Figure 15 is a schematic illustration of another arrangement of the detection system in which the detection system is mounted directly on a spray nozzle;
[0052] Figure 16 is a schematic illustration of another arrangement of the detection system in which the detection system is operationally connected to a passage immediately upstream of the spray nozzle;
[0053] Figure 17 is a schematic illustration of another arrangement
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19/166 of the detection system in which the detection system is operationally connected to a recirculation duct downstream of the spray nozzle;
[0054] Figure 18 is a schematic illustration of another arrangement of the detection system in which the detection system is received directly in a tank;
[0055] Figure 19 is a perspective of a modality of the detection system;
[0056] Figure 20 is a graph showing the absorption detected in a defined wavelength range of samples of 2,4-D, dicamba, MCPA (amine), MCPB, mecoprop and dichloroprop;
[0057] Figure 21 is a graph showing the absorption detected in a defined wavelength range of dicamba samples in different concentrations;
[0058] Figure 22 is a graph showing the absorption detected in a defined wavelength range of 2,4-D samples in different concentrations;
[0059] Figure 23 is a graph that illustrates a modality of a standard curve that relates the concentration of dicamba to the spectral characteristics of the type that can be measured by the detection system;
[0060] Figure 24 is a graph that illustrates a modality of a standard curve that relates the concentration of 2,4-D with spectral characteristics of the type that can be measured by the detection system;
[0061] Figure 25A is a graph showing the absorption detected in a defined wavelength range of formulated MCPA samples (ARGITONE®) in different concentrations;
[0062] Figure 25B is a graph showing the absorption detected in a defined wavelength range of MCPB samples in different concentrations;
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[0063] Figure 25C is a graph that shows the absorption detected in a defined wavelength range of mecoprop samples in different concentrations;
[0064] Figure 25D is a graph showing the absorption detected in a defined wavelength range of dichlorprop-P samples in different concentrations;
[0065] Figure 25E is a graph showing the absorption detected in a defined wavelength range of mecoprop-P samples in different concentrations;
[0066] Figure 25F is a graph showing the absorption detected in a defined wavelength range of dichlorprop samples in different concentrations;
[0067] Figure 26A is a graph showing the absorption detected in a defined wavelength range of samples of clopyralide in different concentrations;
[0068] Figure 26B is a graph showing the absorption detected in a defined wavelength range of samples of formulated fluroxypyr (fluroxypyr ALLIGARE) in different concentrations;
[0069] Figure 26C is a graph showing the absorption detected in a defined wavelength range of samples of picloram in different concentrations;
[0070] Figure 26D is a graph showing the absorption detected in a defined wavelength range of samples of triclopyr in different concentrations;
[0071] Figure 27A is a graph showing the absorption detected in a defined wavelength range of formulated dicamba (CLASH ™) and 2,4-D (WEEDAR®) samples;
[0072] Figure 27B is a graph showing the detected absorption
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21/166 in a defined wavelength range of formulated dicamba (CLASH ™) and glyphosate (ROUNDUP POWERMAX®) samples;
[0073] Figure 27C is a graph showing the absorption detected in a defined wavelength range of formulated dicamba samples (XTENDIMAX® VAPORGRIP®), formulated methyl methulfurone (MANOR) and a combination thereof;
[0074] Figure 27D is a graph showing the absorption detected in a defined wavelength range of samples from a combination of MCPB and formulated dicamba (XTENDIMAX® VAPORGRIP®) in different concentrations;
[0075] Figure 27E is a graph that shows the absorption detected in a defined wavelength range of samples from a combination of formulated dicamba (XTENDIMAX® VAPORGRIP®) and mecoprop in different concentrations;
[0076] Figure 27F is a graph showing the absorption detected in a defined wavelength range of formulated 2,4-D samples (WEEDAR® 64) in different concentrations;
[0077] Figure 28A is a graph showing the absorption detected in a defined wavelength range of RHIZONLINK® samples in different concentrations;
[0078] Figure 28B is a graph showing the absorption detected in a defined wavelength range of samples of a nonionic surfactant (ALLIGARE SURFACE ™) in different concentrations;
[0079] Figure 28C is a graph showing the absorption detected in a defined wavelength range of CAPTAN® fungicide samples in different concentrations;
[0080] Figure 28D is a graph showing the absorption detected in a defined wavelength range of alpha-cypermethrin samples
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22/166 (ASTOUND® DUO);
[0081] Figure 29 is a graph showing the absorption detected in a defined wavelength range of samples of a product based on microbial spores, Bacillus thuringiensis (Bt), in different concentrations;
[0082] Figure 30A is a graph showing the absorption detected in a defined wavelength range of samples of dichlorosalicylic acid (DCSA) in different concentrations;
[0083] Figure 30B is a graph showing the absorption detected in a defined wavelength range of samples of 2-chloroanisole in different concentrations;
[0084] Figure 30C is a graph showing the absorption detected in a defined wavelength range of samples of 3-chloroanisole in different concentrations;
[0085] Figure 30D is a graph showing the absorption detected in a defined wavelength range of 2,5-dichloroanisole samples in different concentrations;
[0086] Figure 31A is a graph showing the absorption detected in a defined wavelength range of a dicamba sample;
[0087] Figure 31B is a graph showing the absorption detected in a defined wavelength range of a sample of glufosinate contaminated with trace amounts of dicamba;
[0088] Figure 31C is a graph showing the absorption detected in a defined wavelength range of a sample of glufosinate;
[0089] Figure 31D is a graph showing the absorption detected in a defined wavelength range of a sample of glufosinate contaminated with trace amounts of imidaclopride;
[0090] Figure 31E is a graph showing the detected absorption
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23/166 in a defined wavelength range of an imidacloprid sample;
[0091] Figure 31F is a graph showing the absorption detected in a defined wavelength range of a sample of azoxystrobin contaminated with trace amounts of imidacloprid;
[0092] Figures 32A to 32H provide illustrative spectra of UVVIS showing the spectral characteristics of the formulated dicamba (CLASH ™ Amax 230 nm, 280 nm; Figure 32A); Formulated 2,4-D (WEEDAR® 64; Amax 230 nm, 280 nm; Figure 32B); a yellow marker dye (Amax 425 nm; Figure 32C); a red spectral marker dye (Amax 530 nm; Figure 32D); a mixture of the yellow marker dye and the formulated dicamba (Figure 32E); a mixture of the red marker dye and the formulated 2,4-D (Figure 32F); and mixtures containing 1: 1 (Figure 32G) or 2: 1 (Figure 32H) concentration ratios of the formulated dicamba mixed with the yellow marker dye and the red marker dye mixed with the formulated 2,4-D;
[0093] Figure 33A provides illustrative spectra of IIV-VIS for a series of dilutions of dicamba formulated to reduce volatility (XTENDIMAX® VAPORGRIP®) mixed with a red-orange marker dye (Amax approximately 625 nm), in various dilutions; and
[0094] Figure 33B provides a standard curve generated using the data provided in Figure 33A correlating the average absorbance of the red-orange marker dye with the dicamba concentration. The concentration of dicamba in solution was highly correlated with the absorbance of the spectral dye.
[0095] Corresponding reference characters indicate corresponding parts throughout the drawings.
DETAILED DESCRIPTION
[0096] This disclosure describes systems, devices and
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24/166 methods to detect agrochemical products in environments associated with agricultural equipment. In addition, the present disclosure describes certain agrochemicals that are formulated to be detected using the systems, devices and methods disclosed in this document. As explained below, the devices, systems and methods disclosed herein are generally configured to use spectral characteristics to detect agrochemicals in an environment associated with agricultural equipment. Spectral characteristics can be analyzed in a variety of ways to provide different types of information about agrochemicals and / or the environment.
DEFINITIONS
[0097] The following definitions are provided to assist in understanding the detailed description.
[0098] The "2,4-dichlorophenoxyacetic acid" also known as "2,4-D" is an organic compound that acts as a systemic herbicide that selectively kills most broadleaf weeds. 2,4-D is a herbicide that comes in various chemical forms, comprising salts, esters and acid forms and is often mixed with other herbicides. The toxicity of 2,4-D depends on its form.
[0099] "Agricultural equipment" includes "agricultural spraying equipment", "manufacturing equipment" and other machinery, passages, devices, storage containers and structures used in an agricultural environment that may come in contact with an agrochemical product. In addition, agricultural equipment includes machines, passages, devices, storage containers and structures used in the manufacture of an agrochemical or other agricultural product.
[0100] “Agricultural spraying equipment” includes, but is not limited to, a tank, a storage tank, a bulk tank, a
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25/166 spray tank, a nursing tank, a rinse tank, a tank drain, a seed treatment machine, a boom, a boom boom, a boom boom, a boom platform, a container, a drum, a pitcher, a receptacle, a bowl, a chamber, a nozzle, a nozzle screen, a screen filter, a nozzle filter, a nozzle fitting, a nozzle body, a screen, a sieve, a valve, a pipe, a pump, a wick cleaner, a line, a pipe, a hose, a hose connection and a sprayer associated with the equipment. Agricultural spraying equipment also includes seed treatment systems, soil injection equipment, irrigation and chemigation systems, fertigation systems, suspended spray lines, solenoids, filters, pumps, transport and storage equipment.
[0101] "Agrochemical product" includes any chemical or biological agent used for agricultural purposes, used in the production of an agricultural product (for example, a precursor) or any by-product of it (for example, a final product). Agrochemical products include any pesticide (eg, herbicides, insecticides, fungicides, bactericides, nematicides, virucides etc.) or final pesticide product, biological products, adjuvants, fertilizers, inoculants, growth regulators, surfactants, osmoprotectors, protection agents and seed treatment agents.
[0102] The term "auxin herbicide", as used herein, refers to any herbicide structurally similar to a naturally occurring auxin. Auxin herbicides normally exert their herbicidal activity by mimicking the plant's natural indole-3-acetic acid (IAA) hormone or other naturally occurring auxin, producing rapid uncontrolled growth and killing the plant.
[0103] “Biofertilizers”, as used in this document, refers to
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26/166 refers to a subcategory of biostimulants that are useful to increase the efficiency of nutrient use and open new routes for nutrient acquisition by plants, for example, plant growth promoting microbes.
[0104] A “cross contaminant”, as used in this document, refers to a harmful substance that passes involuntarily and indirectly from one surface material to another, as can occur with spraying or other forms of contamination in contact with a piece of agricultural equipment.
[0105] "Detoxifying", "detoxifying" or "detoxifying", as used here, refer to any modification to a pesticidal product that reduces the amount or effect of the pesticidal compound. A reduced pesticide effect includes any decrease in the amount of residual pesticide that remains on a surface material to be detoxified. Detoxification can be performed on any surface material, including the surfaces of agricultural equipment used in spraying applications and the surfaces of equipment used in the manufacture of pesticide production.
[0106] "Dicamba" refers to 3,6-dichloro-o-anisic acid or 3,6-dichloro-2-methoxy benzoic acid and its related acids and salts. Dicamba salts include, but are not limited to: isopropylamine, diglycoamine, dimethylamine, potassium and sodium. "Dicamba" can also refer to a "dicamba metabolite" or a "dicamba derivative" that includes a substituted benzoic acid and its biologically acceptable salts. The “dicamba metabolite” and the “dicamba derivative” can have herbicidal activity.
[0107] “Drift”, as used in this document, refers to the physical movement of spray particles resulting from the application of pesticides by the wind or inversion after the particles leave a spray and before reaching the intended target. Drift occurs
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27/166 mainly when spraying applications occur in unfavorable climatic conditions, but generally occurs when wind conditions occur during the application of a pesticide. The amount of drift can also be affected by characteristics such as the application technique and the physical characteristics of the equipment used, such as the size of a spray nozzle. In general, equipment that generates smaller droplets and application techniques that require the droplets to travel longer distances to reach the intended target tend to increase the amount of drift.
[0108] "Fluid" means any substance that is fluid, such as a liquid, a gas or a fluidizable solid, such as granular material or powder.
[0109] A "growth regulating herbicide", as used herein, is also referred to as an auxin-type herbicide. Growth regulating herbicides are generally formulated as amine salts or low volatility esters and are found in the following groups: phenoxy herbicides, benzoic acid herbicides, pyridine herbicides and quinoline herbicides and include different chemical classes, such as phenoxycarboxylic acids, acids benzoic, pyridine-carboxylic acids, aromatic carboxymethyl derivatives and quinolinecarboxylic acids. Growth regulating herbicides should also include auxin derivatives, including auxin, IAA, IBA and other plant growth hormones and plant growth hormone derivatives.
[0110] A "hard water solute", as used here, refers to minerals in "hard water". The mineral content in hard water generally consists of calcium and magnesium ions, however, in some geographical areas, iron, aluminum and manganese can also be present at high levels. Hard water solute (s) is formed when water penetrates through deposits of limestone or chalk, composed largely of calcium and magnesium carbonates, but may also include chlorides, bicarbonates (HCO3-) and
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28/166 carbonates (CO3-2) and other ions derived from carbon dioxide.
[0111] The term "insect growth regulator" (IGR) refers to a chemical that inhibits or modifies the life cycle of an insect, for example compounds such as benzoylurea pesticides. Insect growth regulators should also include feed inhibitors, deterrents and other insecticidal assets.
[0112] “Manufacturing equipment”, as used in this document, refers to any piece of equipment, apparatus (for example, tanks, mixers, filling lines, packaging equipment) or any accessory (for example, hose, pipe ) used in the production of a precursor, intermediate or final pesticide product.
[0113] The term "neonicotinoid", as used herein, refers to a systemic agricultural insecticide similar to nicotine. Certain studies have found a link between the use of neonicotinoids and declining bee populations.
[0114] A "non-target plant" as used in this document refers to a plant that is not intended to be treated with a specific pesticide or to have that pesticide applied to it. A non-target plant may refer to a plant that is sensitive to injury by the pesticide and may also refer to a non-GM plant that is not resistant to one or more herbicides or other pesticides.
[0115] The term “osmolarity” or “osmotic concentration”, as used here, refers to the measurement of solute concentration, defined as the number of solute osmoles (osmol / Osm) per liter (I) of solution (osmol / l or Osm / I).
[0116] The term “final pesticide product”, as used here, refers to one or more products that result due to a chemical breakdown (conversion) reaction of a pesticide. For example, a common end product that
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29/166 results in the degradation or breakdown reactions of dicamba is 3,6-dichloro2-hydroxybenzoic acid (3,6-DCSA).
[0117] The term “pH”, as used here, is a measure of the acidity or alkalinity of an aqueous solution. It is approximately the negative of the logarithm for base 10 of the molar concentration, measured in units of mol per liter, of hydrogen ions. A pH value is a number that ranges from 0 to 14.
[0118] A “plant biostimulant”, as used in this document, is any substance or microorganism applied to plants with the aim of increasing nutritional efficiency, tolerance to abiotic stress and / or the quality characteristics of the crop, regardless of its nutrient content, for example, plant, seaweed or algae extracts.
[0119] The phrase "plant part", as used here, refers to a part of the plant and can include a cell, a leaf, a stem, a flower, a floral organ, a fruit, pollen, a vegetable, a tuber, a bulb, a root ball, a root broth, a root or a seed.
[0120] The phrase “precursor chemistry”, as used here, refers to a chemical used to make a pesticide, as well as impurities in a pesticide.
[0121] The term “rinse water”, as used in this document, refers to rinse water or cleaning solution that may contain diluted concentrations of pesticides, residual concentrations of one or more pesticides, precursor chemicals or pesticide end products resulting from cleaning or detoxifying pesticide residues in agricultural or manufacturing equipment, for example, the solution that results from cleaning a tank, a storage tank, a bulk tank, a spray tank, a rinse tank or any combination of the same.
[0122] A “safe zone” is a concentration of pesticides or final pesticide products contained in the rinse water or that remain
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30/166 in agricultural spray equipment that can be applied to a plant or environment and does not cause injury or damage to the plant or the environment. The safe zone for a pesticide is a concentration low enough that, during a spray or exchange with another pesticide, the remaining low level of pesticide residue remaining in the tank, nozzles, pipes, etc. cannot cause damage to a plant, a non-target plant, a sensitive plant, a plant field, a pollinator, a waterway or a natural environment that are at risk of being exposed to the pesticide, such as by cross contamination, drift, etc. In some cases, a safe zone can be determined with respect to a single pesticide and / or the final product of the pesticide. In other cases, a safe zone can be determined in a way that represents possible cumulative effects and / or interactions of various pesticides and final pesticide products.
[0123] A “seed treatment” refers to a substance used to coat a seed. For example, seed treatments can be an application of biological organisms, chemical ingredients, inoculants, herbicide protectors, micronutrients, plant growth regulators, germination enhancers or suppressants, seed coatings, etc., as provided to a seed to promote the growth of a seedling / plant and / or suppress, control or repel pathogens, insects or other pests that attack seeds, seedlings or plants. The specific use of “pesticide seed treatment”, as used in this document, refers to an application of a pesticide on the surface of a seed as a coating designed to reduce, control or repel organisms, insects or other disease pests that attack seeds or seedlings grown from treated seed. Seed treatment that would require removal while cleaning pesticide seed treatment machines refers to the removal of a pesticide or several pesticides.
[0124] “Seed treatment equipment”, as here
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31/166 used, refers to devices for applying a seed treatment to a seed. Seed treatment equipment may include, but is not limited to: injection systems, sprayers or other dispensers, seed flow monitors, pumps, seed belts and a treatment, collection or mixing chamber, compartment, basin, reservoir or tank. This equipment is used, for example, to supply a single or several products contained in a paste, a coating or a seed encrustant in a continuous and single application or simultaneously with several products.
[0125] The term "spectrophotometric device", "photodetector device", as used herein, refers to a device capable of measuring the intensity of electromagnetic radiation in at least part of the electromagnetic radiation spectrum, for example, as transmitted through, reflected or emitted by certain substances. For example, a "spectrophotometric device" can provide a quantitative measure of a material's reflection or transmission properties as a function of wavelength in at least a portion of the electromagnetic spectrum. The portion of the spectrum that a spectrophotometric device measures may include, for example, the visible, emitted fluorescent, ultraviolet and / or infrared portions of the spectrum. The spectrophotometric device can also include a spectrophotometer, a photodiode or a matrix of photodiodes, a photosensor, a photodetector and can also include a laser device that emits light through an optical amplification process based on simulated electromagnetic radiation emission. The spectrophotometric device can also be a microelectromechanical system (MEMS) or a nanoelectromechanical system (NEMS).
[0126] The phrases “reduce enough”, “remove enough”, “detoxify enough” or “clean enough” refer to processes in
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32/166 which the amount of a pesticide or the effect of the pesticide is reduced / decreased in the rinse water remaining in pesticide application equipment or manufacturing equipment at a concentration that does not cause damage to a plant, a field of plants, a part of the plant, soil, waterway or natural environment.
[0127] The word “tank” refers to a container suitable for containing pesticide solutions and includes the following: a tank, a storage tank, a bulk tank, a spray tank, a nursing tank, a tank for rinsing and a manufacturing vessel.
[0128] As used here, the term “marker dye” refers to any natural or synthetic chemical compound that, when present in a solution, has one or more absorbance maximums (Amax) in the ultraviolet (UV) or visible range of the electromagnetic spectrum and can be detected using a spectrophotometric device. The term “marker pigment” refers to any natural or synthetic chemical compound that, when present in a suspension, has one or more absorbance maximums (Amax) in the ultraviolet (UV) or visible range of the electromagnetic spectrum and can be detected using a spectrophotometric device. When present in a liquid (for example, when dissolved or suspended in a liquid), marker dyes and pigments can be used to detect and / or quantify the amount of another chemical compound (for example, a pesticide or other agrochemical) present in the liquid.
[0129] A "user device" or "user device" refers to any device that a user can choose to use as an interface and includes, without limitation, a computer, an iPad, a l-watch, a tablet, a telephone, a data logger, computer software, computer hardware, a diagnostic receiver, a data mitigation system, a two-way exchange interface, a data portal, a device
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33/166 data capture, a cloud, a cable, a satellite system, a monitor, a data repository, a digital video browser, an application, a native application, a hybrid application, a web application, a web browser, remote sensing device, boom spray applicator control unit and / or industrial process control system.
[0130] "Volatility" refers to the movement of a gaseous form of a pesticide after the pesticide has been deposited on an intended target as typically a liquid. After deposition, the pesticide can change from a liquid to a gaseous form and the gaseous form can leave the target with wind currents and inversion layers. The volatility of a pesticide is influenced by many factors, including vapor pressure, concentration and rate of transport to the leaf or soil surface. Other factors that influence volatility include air, leaf or soil temperature; the water content of the leaf or soil surface; and the speed of air movement above the leaf or soil surface.
[0131] A “waterway”, as used in this document, refers to any body of water and may include: streams, rivers, pools, ponds, lakes, irrigation ditches, channels, estuaries, dams, streams and surface aquifers or underground, water treatment plants, manufacturing waste streams, drains, pipes and holding tanks.
[0132] "Algorithm", as used here, describes a mathematical procedure or formula using a finite number of steps to identify, measure and quantify a pesticide or a final pesticide product in solution. The algorithm can be a single algorithm, an adjustment algorithm, multiple algorithms, chemometric (learning) algorithms or combinations thereof as described in the present invention and can be used for measurement at a single point in time or simultaneous identification and measurement of the concentration of a pesticide or mixture of pesticides in real time.
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[0133] "Window (s)", as used herein, can be any solid or transparent material that allows light transmission.
DETECTION SYSTEM FOR AGRICULTURAL PRODUCTS
[0134] One embodiment of a system 11 of the present invention is illustrated in Figure 1. System 11 includes a photodetector device 13 including one or more detectors 15 positioned to detect light (in general, electromagnetic radiation) after the light interacts with an object or area that potentially has one or more agrochemical products associated with it. For example, light can be detected after being transmitted, reflected or emitted by the object or substances in the area. In the example illustrated in Figure 2, a series of detectors 15 are configured to receive light from a flow cell 17 that receives fluid that can contain an agrochemical, such as a spray solution to be applied to a seed or crop or a solution of cleaning used to clean pesticide residue equipment. The detectors 15 are thus positioned to detect the light that has been transmitted through and / or reflected by the material in the flow cell 17. The light can be natural ambient light. Alternatively, one or more light sources (not shown) can be positioned to direct light towards the object or area that potentially contains a pesticide or final pesticide product. Detectors 15 are suitably spaced apart (for example, to form a set of detectors). For example, each detector 15 can be positioned in a different location to measure the concentration of a pesticide, pesticide precursor chemical, or final pesticide product in several different locations, such as several locations that may be of interest in equipment used to apply pesticides, store pesticides, manufacture pesticides or apply a seed treatment to the seeds.
AGRICULTURAL EQUIPMENT
[0135] In one or more modalities, the detection system 11 is
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35/166 used to detect an agrochemical product in an environment associated with agricultural equipment. For example, detection system 11 can be used to detect an agrochemical product in an environment associated with field equipment (for example, agricultural spraying equipment) as described in more detail below. In addition, the detection system 11 can be used to detect an agrochemical product in an environment associated with a processing facility in which an agrochemical product or other agricultural product is manufactured.
SPRAYING EQUIPMENT
[0136] Referring to Figure 2, a modality of agricultural spraying equipment (broadly, agricultural equipment) with which the detection system 11 can be used is generally designated under reference number 101. Agricultural spraying equipment 101 is generally configured, in one or more modalities, to apply a solution containing one or more agrochemicals to a field or to crops growing in a field. Spray equipment 101, which can be referred to as a sprayer, spray system, or more generally as a system for applying pesticides or other chemicals, includes a tank 103 to receive a solution 105 containing one or more pesticides or other agrochemicals, one or more spray devices 107, a plumbing system 109 connecting the tank to the spray devices and a pump 111 operable to pump the solution through the tank plumbing system to the spray devices. The spraying equipment 101 also includes a number of valves 115 in the plumbing system 109 operable to control the flow of the pesticide solution 105 through the plumbing system. One or more screens 123, 131 are also included in the plumbing system 109 to filter debris from pesticide solution 105 or prevent debris from falling into tank 103. The
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36/166 screens or other filters can be important because debris in pesticide solution 105 can clog nozzles 119 in spray devices 107 and thus interfere with the ability of spray devices to produce spray evenly, as needed to ensure uniform application of the pesticide solution to the target of pesticide application.
[0137] The spray system 101 illustrated in Figure 3 is just one example of a spray system with which the systems and methods of the present invention can be used. It is understood that the spray system configuration can vary widely from what is illustrated in Figure 3. For example, the spray system can be a chemical induction system that uses the venturi effect to attract one or more pesticides and / or others chemicals for the spray stream at a location downstream of the pump. However, the system 101 illustrated in Figure 3 will now be described in more detail to provide detailed examples of how the system 11 illustrated in Figure 2 can be positioned in relation to the equipment. The tank 103 of the spray system 101 can be any conventional spray tank. It suitably has a lid 123 covering an opening at the top of tank 103 through which water or other materials used to make pesticide solution 105 can be added to the tank. A screen 125 adequately covers the opening to limit the opportunity for debris to fall into tank 103. A shut-off valve 127 at the bottom of tank 103 controls drainage from the tank. Plumbing system 109 directs fluid from shut-off valve 127 to pump 111. As shown in Figure 3, a screen 131 or other filter is installed in the plumbing system between tank 103 and pump 111 to prevent any debris in the tank reach the pump. It is understood that a similar screen could be installed in tank 103 over the drain in addition to, or instead of, screen 131.
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[0138] Pesticides can settle to the bottom of the spray tank 103 and, if left in the tank, can dry and harden on the tank walls, as well as any accessories or connections connected to the tank. Pesticide residues can also accumulate and sometimes absorb in or over hoses or other fluid lines in the plumbing system 109. Residues can also accumulate due to repeated spraying coats followed by drying on the device (s) spray 107, pump 111, on any of the valves 115, screens 117, inside the top of the spray tank (for example, on the cap 123 or screen 125 on the top of the tank) and around any deflectors that may be in the tank or on uneven surfaces within the tanks caused by deflectors, hydraulic installations, agitation units, damaged or cracked hoses, etc. This residue can be an important source of contamination. System 11 is configured to detect these types of waste.
[0139] Instrument 13 shown in Figure 1 is suitably mounted directly on agricultural spray equipment 101 or other agricultural equipment. For example, flow cell 17 in Figure 1 can be installed in one of the fluid lines of plumbing system 109 or in tank 103. Alternatively, instrument 13 can be mounted on a portable device (not shown) and moved by a user to an environment of interest (for example, the surface of a spray equipment piece 101 or an area adjacent to the spray equipment) for evaluation by the handheld device of the amount of pesticide and / or final product of the pesticide at that location. For example, system 11 may include a cuvette (not shown) configured so that it can be inserted by a user into tank 103 for manual sampling of the tank's contents to measure the amount of pesticide or final pesticide product in the solution or water of
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38/166 rinsing the tank. More generally, instrument 13 (or one of more than its detectors 15) can be mounted (substantially permanently or temporarily) in position to detect light after interacting with any of the following pieces of spray equipment: tank 103 or its contents, the spraying devices 107, the piping system 109, the pump 111, any of the valves 115, 127, any of the screens 117 in the pipeline 109 or the screens 125, 131 in the tank, any of the nozzles 119 , a spray coming out of nozzles 121, a cap 123 in tank 103 or any other unidentified components of the spray equipment.
SPECIFIC DATA TRANSMISSION
[0140] In one or more embodiments, the system 11 can include one or more radiation guides, for example, a light guide such as one or more optical fibers 19, which can be configured to carry light or other radiation from the object or area of interest for one or more of the detectors 15. (The radiation guides can also be configured to transmit radiation from a radiation source (for example, a light source) to an object of interest or flow cell in certain modalities). Optical fibers or other radiation guides can facilitate the positioning of detectors 15 at a distance from the object or area of interest, for example, in a more protected area or in an area that is more easily accessible. For example, it may be easier to position an optical fiber 19 in a tight space on equipment 101 than to position detector (s) 15 in the same space. In certain embodiments, optical fibers 19 comprise solarization resistant optical fibers (SROF). Ultraviolet radiation, such as that present in sunlight, has a tendency to degrade optical fibers, resulting in greater absorption of light in the fiber that occurs over time. Over time, the gradual increase in light absorption by the optical fiber alters the spectral characteristics
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39/166 measurements of the light transmitted through the fiber. Solarization-resistant optical fibers are made of materials that resist this type of UV degradation. In yet another embodiment, instrument 13 includes one or more spectral filters 21 adapted to filter the radiation over one or more spectral bandwidths. The spectral filter (or filters) 21 can be adapted to eliminate interference from light or radiation sources that are not associated with the object or area of interest. Spectral filters 21 are suitably electronic filters that can be modified during use (for example, in response to changing conditions), as will be described in more detail below.
[0141] In certain embodiments, system 11 may comprise a spectral light interface (SLI) 23 configured to transmit filtered spectral data to a data exchange interface 25 for outputting data to another device, such as a personal computer, tablet, smart phone or other mobile device. In the embodiment illustrated in Figure 1, the data exchange interface 25 includes a wireless communication device 27, a data processing system 29, data storage 31 and a communication interface 33. The data exchange interface can have other configurations in other modalities. The illustrated data exchange interface 25 suitably includes systems that can be used together or alternatively to provide the user with several options for linking the photodetector device 13 to the user's device (s). For example, wireless communication device 27 provides the option to send data wirelessly to a remote PC or other computer, tablet computer, smart phone, remote sensing device, or other mobile device. Data processing system 29 provides the option for system 11 itself to perform various computing functions, which will be discussed in more detail below. It is understood, however, that these computing functions can also additionally or alternatively be performed on one or more external devices than the
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40/166 user connects to the system 11.0 data storage 31 provides the option to store data collected by the system on the data exchange interface 25 (for example, for permanent storage and / or for downloading to a device later). The communication interface 33 provides the option for a user to exchange information by connecting the user's device to the communication interface 33. For example, the communication interface can suitably be a USB port or another standard interface with options compatible with ISOBUS (International Organization for Standardization, International Organization for Standardization, ISO). It is also understood that system 11 can be implemented as an independent system, in which case all processing would be carried out within the system without communication with any external devices.
RADIATION CONNECTIONS
[0142] System 11 is configured to be operationally connected to agricultural equipment, such as agricultural spraying equipment 101, seed treatment equipment or pesticide manufacturing equipment, so that spectrophotometric device 13 can detect light or other radiation afterwards interacting with a material received in agricultural equipment that may contain an agrochemical product. Several different arrangements that facilitate an operational connection between system 11 and agricultural equipment will be described in detail below. However, it will be understood that an agrochemical product detection system can be connected to a piece of agricultural equipment in other ways in other ways.
FENESTRATED FLUID PASSAGE
[0143] With reference to Figure 3, in one or more modalities, the detection device 13 is operationally connected to a piece of agricultural equipment, being positioned adjacent to a passage
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41/166 fenestrated 35 (broadly, a fenestrated structure). For example, passage 35 may comprise a pipe, tube, conduit, bucket, nozzle, etc. to receive a flowing fluid or a generally static fluid. Passage 35 comprises at least one window 37 which is transparent to radiation having a wavelength in a range of interest to detect one or more agrochemicals in the fluid. Suitably, the detection device 13 is operationally aligned with the window 37 to detect spectral characteristics of the fluid based on the radiation transmitted through the window. In the illustrated embodiment, passage 35 comprises a conduit with first and second windows 37 on diametrically opposite sides of the conduit. The windows 37 are registered with each other to pass the radiation from an external source 39 to the flow cell, through the fluid received in the flow cell, to the detection device 15. In the illustrated embodiment, the radiation source 39 comprises a powered light source, such as one or more halogen lamps, an LED, an LED array, one or more deuterium lamps, one or more xenon lamps, combinations thereof, etc. In certain embodiments, the radiation source 39 may comprise ambient light. The illustrated light source 39 is mounted adjacent to one of the windows 37, so that the light from the light source passes through the window. The photodetector device 13 is mounted adjacent to the opposite window, in order to detect the light that leaves the space to contain the fluid. Thus, the photodetector device 13 is positioned so that it can detect light from the light source after the light interacts with the materials in the conduit 35.
[0144] The transparent windows 37, as illustrated in Figure 3, can be installed on opposite sides of several different fluid passages in agricultural spraying equipment, seed treatment equipment or pesticide manufacturing equipment to facilitate the use of the system 11 .
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CONNECTED BY FIBER OPTICAL CABLES
[0145] It is not necessary to mount the light source 39 or the photodetector device 13 adjacent to any window. In some cases, it may be desirable to use one or more fiber optic cables (for example, solarization resistant fiber optic cables) to transmit light between a window and a remote location, where it may be more desirable to mount the light source and / or detection device 13. With reference to Figure 4, in one or more embodiments, the light source 39 is positioned at a remote location and one or more optical fibers 19 (or another radiation guide) are positioned to transmit light from the source. light 39 for window 37. In Figure 4, the detection device 13 is also located in a remote location and one or more additional optical fibers 19 are positioned to transmit light from window 37 after interacting with the material in conduit 35 to the photodetector device.
FLOW CELL ATTACHED TO THE CONDUCT
[0146] Referring to Figure 5, in certain embodiments, a substantially transparent flow cell 17 can be spliced in passageway 35. For example, in one or more embodiments, passageway 35 comprises a conduit for agricultural equipment and the cell flow meter 17 is attached to the conduit, so that the fluid flowing through the agricultural equipment flows directly through the flow cell 17. The light source 39 is mounted adjacent to one side of the flow cell 17 and the photodetector device 13 it is mounted adjacent to the opposite side of the flow cell 17. Thus, the light from the light source 39 can be detected by the photodetector device 13 after the light has interacted with the material in the flow cell.
[0147] A flow cell as illustrated in Figure 5 can be joined to several different fluid passages in agricultural spraying equipment, seed treatment equipment or equipment for manufacturing agrochemicals to facilitate the use of the system 11.
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ASSEMBLY OF THE SYSTEM ON AGRICULTURAL EQUIPMENT
[0148] In certain embodiments, a portion or all of the agrochemical product detection system 11 can be mounted directly on agricultural equipment. Certain components that can be used to facilitate the assembly of parts of the agrochemical product detection system in agricultural equipment are described in more detail below. It will be understood that the agrochemical product detection system can be mounted on agricultural equipment in other ways in other modalities.
PROTECTION COATING
[0149] Agricultural spraying equipment, seed treatment equipment and equipment for the manufacture of agrochemical products are commonly used in environments and / or have attributes that can damage sensitive optical and electronic equipment. Thus, when the photodetector device 13 or other electronic components of the agrochemical product detection system are mounted directly on agricultural equipment, in some cases, it may be desirable to mount some or all of the system components within a protective coating or cover 41 Figure 6 illustrates a modality of a protective coating 41 that involves a light source 39 and the photodetector device 13. There are several ways to organize one or more components of system 11 into a protective coating 41, while still allowing the photodetector device 13 detects light after the light interacts with a material to be analyzed. In Figure 7, for example, a conduit 35 extends through the liner 41 between an inlet and an outlet in the liner to transport fluid to be analyzed through the liner. In the illustrated embodiment, conduit 35 is straight and the inlet and outlet are on opposite sides of the liner. However, it is understood that the locations of the entrances and exits may be different from that illustrated, if desired. The light source 39 and the photodetector device 13 are
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44/166 mounted within the liner 41 on opposite sides of the conduit 35. As illustrated, transparent windows 37 are installed in the conduit 35 and the light source 39 and the photodetector device 13 are positioned adjacent to the windows. Thus, the components within the coating 41 in Figure 6 correspond to the components of the agrochemical product detection system 11, as illustrated in Figure 3, but it is understood that the coating can include other component arrangements in other embodiments.
[0150] Coating 41 is suitably water resistant, shock resistant, heat resistant and / or resistant to chemicals. The liner 41 can be water resistant by constructing the liner so that it is sealed against water ingress. The coating 41 can be shock resistant by selecting a durable material to form the coating and / or using vibration damping assemblies to mount the spectrophotometric device 13, light source and any other sensitive components of the system to the coating. The coating 41 can be heat resistant using a material that has a low thermal conductivity to form the coating and / or by adding thermal insulation to the coating. Coating 41 can be resistant to chemicals using a material selected for its inert chemical properties, such as a chemical resistant polymer. Those skilled in the art will be able to select materials suitable for chemical resistance to pesticides and related chemicals. In one or more embodiments, the liner 41 includes a lower portion and an upper portion (broadly, first and second portions) configured to be selectively closed and a seal that is configured to seal the interfaces between the lower portion and the upper portion to prevent dirt, dust or other contaminants to enter the coating.
ASSEMBLY WITH ADDITIONAL COMPONENTS
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[0151] One or more additional components can be mounted on the agricultural equipment, together with the photodetector device 13 and the light source 28. For example, in Figure 7, system 11 includes a microprocessor 29 that is connected to the photodetector device 13 for analyze signals from it (for example, according to one or more of the algorithms described below). The microprocessor is properly configured to collect data from the photodetector device and transmit, process or process and transmit the data to the end user or other intermediate device. Microprocessor 29 can also contain transmission hardware, such as hardware for any of the following communications: wireless connection, Bluetooth, IR, cellular communication, LAN, USB, firewire or other wired or wireless connection with options compatible with ISOBUS (International Organization Standardization, ISO). In addition, a battery or other power supply 43 is properly mounted on the equipment (for example, to supply the light source as in Figure 8). The battery or other power supply 43 can be rechargeable, single use or multiple uses. The energy can be direct or alternating current and can be transported from external power sources, optionally including spray platform power and other agricultural equipment. Although the battery or power supply 43 is illustrated in Figure 7 as supplying power to the light source only, it is understood that the battery or other power source can supply power to any combination of the light source, spectrophotometric device, microprocessor and other system components 11 that can use energy. Although microprocessor 29 and battery 43 are shown to be mounted externally to the protective coating 41, it should be understood that they can be received within the protective coating with the photodetector device 13 in certain embodiments.
[0152] Figure 8 shows another example that is similar to Figure
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7, but on which a monitor 45 is mounted on the agricultural equipment together with the battery or other energy source. The screen 45 is suitably mounted on agricultural spraying equipment, such as in the cab of a spraying platform or mounted elsewhere or internally on a spraying platform. Screen 45 can be connected to other components of system 11 via a wired or wireless connection. Monitor 45 can optionally be or include the monitor of a tablet, phone, laptop or other portable device configured to communicate with system 11. In Figure 8, a processor, such as microprocessor 29, can also be mounted on the equipment, or if desired, a remote processor can be used (for example, using a wireless connection to the spectrophotometric device 13 and / or the screen).
[0153] If desired, microprocessor 29, screen 45 and / or battery 43 or another power supply can be closed, or at least partially closed, in the cover shown in Figure 7
ASSEMBLY SYSTEMS
[0154] System 11 adequately includes an assembly system for mounting system components on agricultural equipment. With reference to Figure 9, in one embodiment, the mounting system includes a set of supports 47 or other suitable supports having at least one of the following characteristics: the ability to isolate the assembled component (s) from vibrations ; the ability to form a mechanical interface with a corresponding piece of equipment on which the system 11 or a component of the system is to be mounted; water resistance; heat resistance; chemical resistance to pesticides and final pesticide products; and combinations thereof. The mounting system can be sold separately from system 11 as a mounting kit. For example, different mounting kits can be created to mount system 11 in
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47/166 different specific pieces of agricultural spraying equipment, seed treatment equipment or pesticide manufacturing equipment. Alternatively, the assembly system can be sold with system 11. It is also understood that system 11 can be sold without any assembly system without departing from the scope of the invention.
FLUID CONNECTIONS
[0155] In certain modalities, the agrochemical product detection system 11 is directly connected fluidly to a piece of agricultural equipment. In one or more embodiments, the agrochemical product detection system 11 is configured to receive a fluid sample associated with agricultural equipment that is delivered separately to the agrochemical product detection system. The agrochemical product detection system 11 can be fluidly coupled to agricultural equipment in any suitable way. Certain modalities of fluid connections between system 11 and agricultural equipment are described below. It is understood that other ways of fluidly connecting the system to agricultural equipment can be used in other modalities.
CONNECTION WITH VARIOUS SOURCES OF FLUID
[0156] In one or more modalities, system 11 is fluidly coupled to agricultural equipment to receive fluids from several different sources (for example, drains from several different tanks, etc.). Referring to Figure 10, system 11 is mounted on a fluidic system downstream from two or more different sources S1, S2. For example, a star connection 51 can be used to fluidly couple system 11 to two different sources S1, S2. Several 51 star connections and / or a collector can be used to fluidly couple the system to more than two different sources. If desired, the star connection (s) 51 or manifold can be replaced with a suitable valve or set of valves to prevent fluid flow
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48/166 between the sources. For example, star connection 51 in Figure 10 can be suitably replaced by a multi-way valve (two or more), which can be a manual valve or controlled by an actuator, such as a solenoid for automated valve control (for example , by the microprocessor).
[0157] In an application of Figure 10, the first source S1 is a tank of clean water and the second source S2 is a spray tank or other structure containing agrochemicals. This can be advantageous because system 11 can be configured to periodically switch from the source of agrochemical product S2 to the source of clean water S1 to obtain measurements in the dark and / or in white that can be beneficial in removing noise from spectral measurements. Alternatively, the first source S1 can be the boom of a spray platform and the second source S2 can be the spray tank of the spray platform to allow comparative readings between the fluid in the tank and the fluid in the boom. Other fluid sources can also be connected to the agrochemical product detection system 11 in other modalities.
FILTERED CONNECTION
[0158] In one or more modalities, system 11 includes a connector to connect the system to an in-line filter or sieve 131 in a passage of agricultural equipment. Referring to Figure 11, in certain embodiments, system 11 includes a standard connector 153 that is attached or that can be attached to a filter / sieve or other similar in-line component of agricultural equipment. The connector is suitably a standard hose connector for a line that ranges in size from% inch to 2 inch (about 0.6 cm to about 5 cm). In certain embodiments, passage 35 of the agrochemical product detection system 11 itself may include an in-line filter (not shown).
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ABOVE OR AT THE END OF THE SPRAY BAR
[0159] With reference to Figures 12 to 14, in certain embodiments, the system 11 can be connected fluidly to agricultural spraying equipment at a connection point on or at the end of a spray boom. As is known to those skilled in the art, a spray bar can comprise a collector (e.g., pipe) to simultaneously apply a pesticide or other chemical to a crop from several different spray nozzles, spray spheres or emitters distributed to the along the length of the collector.
[0160] Figure 12 illustrates an embodiment in which the system 11 is fluidly coupled to an end downstream of the spray boom 107, for example, downstream of the spray nozzles 119. In other embodiments, the system 11 can be fluidly coupled to an upstream end of the spray boom or to a middle segment of the spray boom without departing from the scope of the invention. In the embodiment shown in Figure 12, however, a conduit 35 carries fluid from the end of the spray boom to system 11. In one or more embodiments, conduit 35 has an outlet that is configured to discharge excess fluid from the spray boom. spraying after it flows through the agrochemicals detection system. In certain embodiments, the outlet of the conduit 35 is configured to recirculate the fluid passing through the system 11 back to a spray tank, a spray pump or a recirculation system used to prevent sedimentation in the spray tank.
[0161] Figure 13 shows an embodiment in which the system 11 is fluidly coupled to the spray boom 107 upstream of an end cap downstream 108 thereof. In the illustrated embodiment, the system 11 is fluidly coupled to the spray boom downstream of the spray nozzle.
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50/166 spray plus downstream 119 (for example, a spray ball, an emitter); but in other embodiments, the system is fluidly coupled to the spray boom at a connection point upstream of one or more of the nozzles. In one or more embodiments, the system 11 is mechanically mounted directly on the spray boom 107, so that the windows 37 allow radiation as light to be transmitted from within the spray boom to the photodetector device 13.
[0162] Figure 14 is similar to Figure 13, except that in the arrangement shown in Figure 14, a flow cell 17 was joined directly to the spray boom 107. Flow cell 17 fluidly couples the agrochemical product detection system 11 to boom 107 and, in the illustrated embodiment, at least a portion of the system is supported directly on the boom boom. Again, although system 11 is mounted between the last nozzle, spray ball, or emitter 119 and end cap 108 in Figure 14, flow cell 17 is understood and the rest of the system can be mounted anywhere along the spray boom length.
AT THE NOZZLE OR OTHER OUTPUT
[0163] Referring to Figure 15, in certain embodiments, the system 11 is fluidly coupled to agricultural spray equipment or other agricultural equipment at a connection point on a spray nozzle 119 or other fluid outlet. The outlet can be a nozzle, spray ball, emitter or other device configured to apply an agrochemical to crops, seeds or other materials in a process facility. In the illustrated embodiment, at least a portion of the agrochemical product detection system 11 is supported directly on the nozzle 119. For example, at least a portion of the agrochemical product detection system can be integrally formed on the nozzle in certain embodiments. In other embodiments, a passage can divert fluid from nozzle 119 into the system
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51/166 supported elsewhere. In the illustrated embodiment, the transparent windows 37 are positioned on opposite sides of the nozzle 37 upstream and adjacent to the outlet (or outlets). The light source 39 is positioned adjacent to one of the windows 37 and the photodetector device 13 is positioned adjacent to the opposite window, so that the spectrophotometer device can detect the light emitted by the source after interacting with any material between the windows. That is, the windows 37 allow radiation like light to be transmitted from inside the nozzle 119 to the photodetector device 13.
[0164] Figure 16 illustrates a modality that is similar to Figure 15, except that system 11 is fluidly connected to agricultural equipment at a connection point located slightly upstream of the body, forming the nozzle, spray ball or emitter 119. For example, system 11 is fluidly coupled to a passage that is fluidly coupled to the nozzle, spray ball or emitter 119, such as a passage that extends between a spray bar and the nozzle, spray ball spray or emitter. In the illustrated embodiment, at least a portion of the agrochemical product detection system 11 is supported directly in the passage extending from the nozzle 119. In other embodiments, another passage can divert the fluid to the system 11 supported elsewhere.
[0165] Figure 17 illustrates another mode in which system 11 is fluidly connected to agricultural equipment at a connection point that is downstream of an outlet of nozzle 119. In this mode, system 11 includes a discharge conduit 35 that is positioned to capture at least part of the material being dispensed from the spray nozzle, spray ball, emitter or other agrochemical product outlet 119. In the illustrated embodiment, at least a portion of the agrochemical product detection system 11 is supported directly in the discharge 35. In other modalities, another passage can divert the fluid to the system
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52/166 supported elsewhere. The conduit 35 itself could have an outlet opening at a downstream end through which the agrochemical is configured to be discharged to a desired location. In certain embodiments, conduit 35 is configured to supply the fluid to a spray tank, spray pump or recirculation system. In one or more embodiments, the spray nozzle, spray ball, emitter or other outlet 119 comprises a simulated sprayer or a simulated outlet that does not actually apply agrochemicals, but is in all other respects the same as the devices that apply the agrochemical product. For example, a simulated spray nozzle 119 can be installed on a spray boom 107 along with actual spray nozzles, so that system 11 can collect data from the simulated spray nozzle that is representative of what is being dispensed from the spray nozzles. spraying. Alternatively, conduit 35 can be positioned to sample a small portion of the material applied by an actual spray nozzle, spray ball, emitter or other application device 119 (for example, in the spray path emitted from a spray nozzle or real spray ball) to collect data from a real pesticide application device.
NO OR ABOUT THE TANK
[0166] Referring to Figure 18, in certain embodiments, the system can also be received inside a tank 103 or other structure to contain or transport a fluid. Tank 103 can be a spray tank or a storage or transport tank. Whether one or more components of system 11 can be enclosed in a water resistant or waterproof coating 41. In certain embodiments, at least a portion of system 11 can be supported in a probe that can be inserted into the fluid stored in a tank or flowing through a passage.
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Alternatively, parts of the system 11 can be constructed on the wall of the tank or passageway to protect them from fluid content. As another alternative, system 11 can be mounted externally on tank 103 and a conduit can be provided to transport fluid to the system so that it can be analyzed. In one embodiment, system 11 is included as part of a kit for mounting the system in a tank. Kits for mounting at least a portion of the system 11 in other locations of agricultural equipment and / or fluid connection of the system to a source of agrochemical product at other connection points can also be used in other modalities.
EXAMPLE SYSTEM
[0167] Referring to Figure 19, a modality of an agrochemical product detection system is generally indicated in reference number 11. The illustrated components of system 11 are received in a protective coating 41 that has a transparent cover, so that the components are visible to a user. In other embodiments, compartment 41 is opaque. As explained above, the cabinet may comprise a protective coating (for example, reinforced) that is configured to protect the system from vibrations, high / low temperatures, aggressive chemicals and the like. In addition, as explained above, compartment 41 can be mounted directly on agricultural equipment by means of supports or the like.
[0168] The agrochemical product detection system 11 includes a passage that extends through the liner 41 of at least one fluid inlet 61.62 to at least one fluid outlet 63. In the illustrated embodiment, the passage comprises first and second inlets of fluid 61.62. The first fluid inlet 61 is configured to fluidly connect the passage to a source of agrochemical product associated with agricultural equipment (for example, a tank, a spray bar, a flue, a
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54/166 nozzle, etc., as explained above). The second fluid inlet is configured to fluidly connect system 11 to a clean water source. Passage 11 includes at least one valve associated with a star fitting 51 (for example, a manifold) that is configured to selectively connect each of the inlets 61, 62 to a conduit 35 of the passage extending from the star fitting to the outlet 63. A system 11 processor can be configured to control the valve associated with star fitting 51 in certain embodiments. System 11 can selectively deliver clean water from inlet 62 through the passageway when dark and white spectral readings are desired and can selectively deliver a fluid that can contain agrochemicals through the passageway when detection of agrochemicals is desired. Other embodiments may have other passage configurations without departing from the scope of the invention.
[0169] The illustrated system 11 includes a photodetector 13 and a light source 39 (broadly, a radiation source) which are arranged on opposite sides of the conduit 35. The conduit 35 is configured so that the light source 39 releases light (broadly, radiation; for example, visible light and ultraviolet light) through the conduit to the photodetector 13 and the photodetector receives the light after it has interacted with a substance in the conduit. For example, in certain embodiments, conduit 35 comprises windows that are aligned with the light 39 and the photodetector 13, as explained above, to allow the passage of light from the light source to the photodetector. In other embodiments, a flow cell is spliced in the conduit 35 at a location aligned with the light source 39 and the photodetector 13. The photodetector 13 is configured to detect spectral characteristics of the fluid after receiving the light from the conduit. As explained below, a system 11 processor (not shown) or another processor is configured to analyze spectral data to detect the agrochemical.
[0170] Photodetector 13 can be combined with connections without
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55/166 wired, cellular, Bluetooth, wired, optical or other to provide raw or processed spectral data to a phone, tablet, monitor, computer, memory or monitor of integrated systems for display or registration to the end user. In certain embodiments, analytical processes for evaluating spectral data can be performed on detector 13 or system 11 processor through embedded programs. In one or more modalities, raw or pre-processed data can be sent to a second device for processing the data at a remote location to the system 11 and, in some modalities, a remote location to the agricultural equipment. These processing devices can have their own displays, batteries, rugged cases and connections (such as USB, firewire, ports) to enhance the device's ability to be used in the field.
DETECTION DEVICES
[0171] As stated above, system 11 can use a photodetector device 13 comprising one or more photodetectors 15 to detect spectral characteristics of a substance in which detection of agrochemicals is desired. Any suitable type of photodetector and photodetector device can be used within the scope of the invention. For example, in one or more embodiments, the photodetector device 13 comprises a spectrometer that is configured to detect absorbance, reflectance or transmission at least in the ultraviolet (UV) and visible light (VIS) spectrum. In certain embodiments, the photodetector is configured to detect spectral characteristics in other wavelength bands (for example, infrared, etc.). Other types of photodetectors can also be used as described in more detail below.
MICROELECTROMECHANICAL SYSTEM MEASUREMENT DETECTOR
[0172] In one or more modalities, the photodetector device 13
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56/166 comprises a microelectromechanical system (MEMS) with spectrophotometric capabilities. For example, a spectrophotometric MEMS 13 can be placed in the line of (for example, in fluid communication with) a liquid containing static or flowing agrochemicals to allow detection of agrochemicals. The MEMS 13 device (or devices) can be a chip (MEMS-SPX, Knowles Electronics, LLC), a probe (DIP TIP ™, World Precision Instruments) or other MEMs device for photodetection. In one embodiment, the MEMS 13 device received in a flow cell 17 (for example, a stainless steel flow cell, such as a stainless steel flow cell with a clearance of 1 cm) and allows free movement of liquid through flow cell. A MEMS device can be configured to detect spectral characteristics in UV, infrared, visible or a combination of these light bands to detect a wide variety of agrochemicals.
[0173] The MEMS 13 device can be mounted or fluidly connected to agricultural equipment in any of the configurations described above. In addition, the MEMS 13 device can be placed as a chip or probe, etc., inside any individual nozzle or several nozzles within agricultural equipment. The MEMS 13 detector can be used for various agricultural equipment, including nursing tanks, bulk tanks, portable sprayers, spraying platforms, tractors, nozzles, boom lines, overhead irrigation systems, in-line irrigation systems and spraying aircraft in cultures. In addition, the MEMS device can also be mounted on seed treatment equipment or pesticide manufacturing equipment.
PHOTODIODES
[0174] In one or more embodiments, photodetectors 15 may comprise one or more photodiodes (broadly, semiconductors)
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57/166 (specially made of silicon, quartz, crystalline materials, any photovoltaic IIV / VIS filter glass to provide a wide range of spectral absorbance). Suitably, each photodiode 15 is configured to convert light (or other electromagnetic radiation) into an electric current generated when photons are absorbed into the photodiode. In certain embodiments, each photodiode 15 is provided with a distinct separation of color bands or spectral bands defined with narrow selectivity. Photodiode 15 or the array of photodiodes (two or more photodiodes) are placed inside the apparatus 13 and can generate or transmit a signal (which can be increased by an amplifier and transistor (s) placed to provide increased output or amplification of the spectral signal ) representing spectral characteristics in the range of ultraviolet (UV), visible (VIS) and near infrared (IR) wavelengths. Suitable photodiodes 15 include monochrome and polychromatic photodiodes that have defined and customizable spectral wavelength bands. The positioning of a single or multiple set of photodiodes 15 can be used with narrow and / or wide band filters to filter light or background noise, providing a customizable high-resolution wavelength format. A matrix of photodiodes allows a wide spectral range of wavelength (nm) to be detected simultaneously at different intervals and depends on the number of photodiodes, as well as on the different properties and location of the photodiodes. Photodiodes 15 can be connected or equipped with optical filters, built-in lenses or other devices that improve spectral transmission. Photodiodes 15 may vary in surface area. The photodiode device 13 can be used as a single device or as two or more devices together to detect, measure and quantify an agrochemical product that has a spectral trace that is identifiable in UV, VIS or other wavelength ranges. For example, the photodiode device 13 can convert the characteristics
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58/166 spectral of a substance that can contain an agrochemical product in a measurable electrical output signal (for example, spectral traces captured at 230 nm, 250 nm and 280 nm converted to electrical signals). The at least one photodiode, two to three photodiodes or several photodiodes arranged together are properly configured to detect a fingerprint of an agrochemical product or unique chemical signature.
[0175] The photodiode (or photodiodes) 13 can be incorporated into a photodetector device 13 and then be mounted on agricultural equipment or fluidly connected to agricultural equipment in any suitable way, as in any way described above with reference to Figures 3 to 19 Photodiode 13 can be used as a single element in which the photodiode can be operated independently or in a matrix format comprising two or more photodiodes. The quality of the spectral trace data produced by one or more photodiodes (or other detectors) can, in certain modalities, be improved by using lenses or other optics that can collect an ideal amount of optical energy. In certain embodiments, photodiodes (or other detectors) use bandwidth filters that provide complete separation of the spectral bandwidth (s) to distinguish between signature absorbance or spectral fingerprint for each diagnostic compound or chemistry. A general array of photodiodes in any one of Figures 4 to 19 can include an amplifier that amplifies an output signal including spectral characteristic data. Modulation of the amplified output signal can be performed using a transistor. In addition, the output of the amplified signal can be captured and displayed for quick detection in real time or transferred remotely. The band formation of the photodiode detector is carried out using filtering materials, such as colored glass, interference filters or dichroic filters. The combinations of the aforementioned filtering techniques can be combined to shape the radiation that strikes
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59/166 on the surface of the photodiode, such as using a long-pass edge filter or dichroic mirror to separate visible and infrared light. Light with wavelengths less than 700 nm is reflected 90 degrees from incident light and NIR light with wavelengths greater than 700 nm passes through the filter. Additional cutting of the photodiode output signals can be achieved using narrowband interference filters or colored glass placed in front of the photodetectors that use a beam splitter to divide the incident light into two different components. Here, the incident light is divided into several equal beams, directed to detectors with filters (Figure 1). The directionality of the light received by the photodiode or matrix of photodiodes, as described in Figures 3 to 19, is not limited and can be illuminated from above, from below or at any angle of incidence provided to the photodiode or photodetector device. Photodiodes or photodiodes placed in a matrix on the device can be segregated by a doping or depletion zone (type p, type n), a layer to distinguish the electrical impulses that act as spacers and used to isolate each photodiode from each other or format not doped (PIN diode).
[0176] In certain modalities, photodiodes that can be used as a single photodiode or a photodiode array with multiple sensors (two or more) and selected for distinct and defined measurement of color range selectivity have narrowband measurement capabilities and broadband. Different optics are provided to filter the background wavelengths, which can have customizable wavelength limits. Other suitable photodiodes include monochromatic or polychromatic diodes, with color bands of absorbance (nm) in the cyan, red, magenta, green, yellow and blue spectra. The multicolored photodiode can detect wavelengths of light ranging from the minimum UV (200 nm) to wavelengths above 1,700 nm. The spectral absorbance ranges can be wide from 200 to 700 nm; 400 to 700 nm; 700
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60/166 to 1,200 nm, for short-wave infrared (1,700 nm) or spectral characteristics of different wavelength absorbance for: 230 nm, 250 nm, 280 nm, 425 nm 435 nm, 455 nm, 465 nm, 485 nm , 515 nm, 525 nm, 535 nm, 555 nm, 558 nm, 575 nm, 610 nm, 615 nm, 660 nm, 661 nm, 675 nm, 720 nm, 810 nm, 835 nm, 850 nm, providing high resolution bandwidth over a wide spectral range (200 to 1,700 nm) with a band filter width of less than or approximately equal to +/- 5 nm.
PROCESSING AND ANALYSIS OF SPECTRAL CHARACTERISTICS
[0177] System 11 is suitably associated with a processor that analyzes spectral data to detect and, in some modalities, measure and quantify the amount of an agrochemical in the flow cell 17 or another environment from which the detectors 15 receive light. With reference to Figure 1, in one embodiment, the processor may reside in the data exchange interface 25. In certain embodiments, the processor may be another processor internal to the system 11. In some embodiments, the processor may be located on a remote device to system 11, such as a mobile device (for example, a phone, a tablet, etc.) or a computer (for example, a laptop or a desktop). More than one processor in one or more locations (for example, internal to system 11 and external to the system) can also be used in certain modalities.
[0178] Any suitable way of analyzing the spectral characteristics detected by the photodetector 15 to detect and / or measure an agrochemical product can be used. For example, in one or more modalities, the processor is configured to use a radiation absorbance ratio at two wavelengths by the object or area of interest to assess the concentration of one or more agrochemicals.
[0179] In one or more modes, the processor is configured to analyze spectral data to measure and quantify the quantity of various
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61/166 agrochemical products simultaneously. For example, different detectors 15 can have different filters 21 to isolate bandwidths that are pertinent to several different agrochemicals.
[0180] In some cases, a single absorbance reading may be sufficient for the analysis of a substance. An example in which a single absorbance reading would be sufficient is if the overall absorbance at a defined wavelength is below a minimum limit, indicating that there is no detectable pesticide present or that a safe zone has already been reached. In addition, a single absorbance spectrum may be sufficient in some cases, if calibrated against a non-absorbent background wavelength and predictive software.
[0181] In other cases, a comparison of the spectrum obtained using more than one wavelength can be used to identify an agrochemical. Absorbance ratios at main wavelengths, such as 276 nm at 230 nm and 285 nm at 230 nm, can be used to identify an agrochemical product or to determine a concentration of agrochemical product in certain modalities. More sophisticated algorithms (for example, learning algorithms) or spectrum recognition software can also be used to identify pesticides and other agrochemicals.
[0182] An embodiment of a method for detecting a concentration of an agrochemical product will now be described.
USE OF A STANDARD CURVE TO EVALUATE THE CONCENTRATION OF AGRICULTURAL PRODUCTS
[0183] In this modality, a standard curve for a given agrochemical product is obtained by relating the concentration of the agrochemical product to the spectral data. For example, a standard curve can be obtained by relating the concentration of agrochemicals to a ratio of
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62/166 absorbance of two different wavelengths. With reference to Figure 20, which shows an example of the absorption spectrum for several different pesticides, it can be seen that these pesticides exhibit two peaks in the absorption spectrum - one around 216 to 245 nm, usually centered around 230 nm and the other around 270 to 295 nm and generally around 280 nm.
[0184] The peaks in the absorption spectrum provide good candidates for establishing a ratio that can correlate with the concentration of the particular pesticide. Figures 21 and 22 show the spectral characteristics of a solution containing pesticide in different concentrations of the pesticide. Figure 21 shows the spectral absorbance of five different concentrations of dicamba, and Figure 22 shows the spectral absorbance of 2,4-D. An equation can be determined by describing the standard curve that correlates spectral characteristics with the concentration of pesticide. Then, the field measurements taken by system 11 can be connected to the equation to determine the concentration.
[0185] This standard curve or equation can be generated by empirical data using system 11. Alternatively, the standard curve, equation or related information can be obtained from a manufacturer or other data provider about the specific pesticide or pesticide of interest. . The standard curve or related information can be stored in the data exchange interface 25.
[0186] Specific examples of the implementation of this algorithm will be provided in the following paragraphs, first by reference to dicamba and then by reference to 2,4-D. It is understood that the methods described in the two examples can be adapted for use with other agrochemicals.
EXAMPLE 1 OF SPECTRAL ANALYSIS - GENERATION OF A STANDARD CURVE FOR DICAMBA
[0187] A commercial dicamba formulation (CLASH ™) was used
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63/166 to generate a standard curve based on spectral absorbance data for dicamba in concentrations ranging from 1 mg / l to 1,000 mg / l. Empirical data showing spectral characteristics at the various concentrations are illustrated in Figure 21 (Amax 230, Amax 276). Samples of the dicamba solution were pipetted (200 pl) each onto a UV-Star® microplate (GEINER BIO-ONE). Spectral traces in a wavelength range from 200 nm to 400 nm (+/- 3 nm) were collected for each of the samples of dicamba solution in variable concentration using a BioTek SYNERGY HTX plate reader (BioTek Instrument Inc.) . The results are shown in Figure 21. Figure 23 shows the standard curve determined for dicamba. To generate the standard curve, an empirically derived absorbance ratio (276 nm: 230 nm) was plotted as a function of varying dicamba concentrations. Data for known dicamba concentrations were used to make the standard curve, plotting the concentration on the x-axis and the absorbance ratio at the wavelengths of 276 nm: 230 nm and on the y-axis. As the value of the absorbance rate 276 nm: 230 nm increases, the concentration of dicamba in the solution increases. The initial concentration of dicamba in the tank and subsequent concentration measurements throughout the detox and / or cleaning procedure can be calculated using the predictive equation generated by the standard curve 'y = 0.0007x + 0.0469', where y is the absorbance ratio for 276 nm: 230 nm, 0.0007 is the correction factor or the slope of the best-fit line, 0.0469 is a general correction factor or y-intercept (where the line touches the y axis) , eg as solved in the equation provides a measure of dicamba concentration. The value of the linear regression of R2 = 0.9962 is the predicted measure of the correlation or relationship between the peak absorbance rate (y-axis) and the dicamba concentration (x-axis).
SPECTRAL ANALYSIS EXAMPLE 2 - STANDARD CURVE GENERATION FOR 2-4D
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[0188] A commercial formulation of 2,4-D (WEEDAR® 64) was used to generate a standard curve based on spectral absorbance data for 2,4-D at concentrations in the range of 25 mg / l to 400 mg / Ell . The empirical data showing spectral characteristics at the various concentrations are illustrated in Figure 22 (Amax 230, Amax 285). The 2,4-D solutions were pipetted (200 pl) each onto a UV-Star® microplate (GEINER BIO-ONE). Spectral traces in a wavelength range from 200 nm to 400 nm (+/- 3 nm) were collected for each of the 2,4-D solutions in variable concentration using a BioTek SYNERGY HTX plate reader (BioTek Instrument Inc. ). Figure 24 shows a standard curve for 2,4-D that was plotted from the test results. In the illustrated standard curve, an absorbance ratio (285 nm: 230 nm) is plotted as a function of 2,4-D concentrations. Empirical data for various known concentrations of 2,4-D were used to make the standard curve, plotting the concentration of 2,4-D on the x-axis and the absorbance ratio (285 nm: 230 nm) on the y-axis. As the value of the absorbance rate of 285 nm: 230 nm increases, the concentration of 2,4-D also increases. The initial concentration of 2,4-D in the tank and subsequent concentration measurements throughout the detoxification and / or cleaning procedure can be calculated using the predictive equation generated by the standard curve 'y = 0.002x + 0.2232', where y is a measure of the maximum absorbance ratio (285 nm: 230 nm), 0.002 is the correction factor or the slope of the best fit line, 0.2232 is provided as a general correction factor or y-intercept (where the line touches the y-axis and x, as solved in the equation, provides a predictive measure of 2,4-D concentration. The linear regression value of R2 = 0.9963 is the predicted measure of the correlation or relationship between the peak absorbance rate (y-axis) and the 2.4D concentration (x-axis). In an absolute correlated relationship, valve R2 is equal to 1.0; so again the regression value for this example indicates a
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65/166 strong correlation.
NOISE REDUCTION FILTERS
[0189] One or more filters can be used to reduce the effects of spectral noise. The noise reduction filter (s) is suitably a data processing algorithm, such as a computer program run by the processor. A noise reduction filter can have a linear or non-linear input / output ratio. The selection of the filter parameters is carried out properly in real time, with the filter coefficients being determined using a current input sample. Alternatively, the selection of the filter parameters can be performed using a previously stored input signal sample. The adjustment of the parameters of a filter is suitably based on an evaluation of the quality of the input signals in the filter. For example, the filter is suitably a linear filter. For a linear filter, the filter can have a finite or infinite impulse response. Alternatively, the filter can be a non-linear filter. The selection of the filter parameters is carried out properly in real time, with the filter parameters being determined using current input samples. Alternatively, the filter parameters can be calculated using a temporary storage of recent input samples. In addition, the selection of filter parameters can be based on more than one signal quality indicator. In addition, the selection of the filter parameters can be based on the output of an algorithm that combines several signal quality indicators. The noise reduction filter (s) of the present invention can be used to receive input signals corresponding to detected optical energies of a plurality of wavelengths. The filter (s) can be used in combination to determine the concentration of pesticides when the received signals correspond to detected optical energies of a plurality of wavelengths. The filters are properly configured to
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66/166 reduce background noise. For example, a dark measurement can be made (for example, with the light source turned off) to assess the current background noise level. Alternatively, or in addition, a valve may be actuated (for example, by the processor) periodically to cause pure water to flow through the system 11 to assess a current background noise level.
MONITORING AND DISPATCH ALERTS
[0190] System 11 is suitably configured to quantify concentrations of one or more agrochemicals periodically or substantially continuously (for example, during a predetermined monitoring period or during a cleaning process). Thus, system 11 is properly configured to monitor the concentration of one or more agrochemicals over time. System 11 is also properly configured to compare the current concentrations of agrochemicals with the stored data (for example, data stored in the data exchange interface 25) to determine when one or more events of interest have occurred. For example, the processor is properly configured to determine one or more of the following:
[0191] (a) when a desired concentration of the agrochemical product (s) is reached in an environment (for example, in a tank);
[0192] (b) whether an agrochemical product formulation still meets the shelf life requirements (for example, a sufficient portion of the pesticide has not yet fallen into a final pesticide product);
[0193] (c) the amount of an agrochemical product, such as a pesticide or final product, that remains in the equipment after spraying or treating a crop;
[0194] (d) the quantity of agrochemical products, such as a pesticide or final product that remains in equipment that was used to apply a seed treatment to the seeds;
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[0195] (e) the amount of agrochemical product, such as a pesticide or final product that remains in the equipment after it has been used to manufacture an agrochemical product;
[0196] (f) the possibility that an agrochemical product such as a pesticide has been sufficiently detoxified or removed from agricultural equipment and / or associated accessories;
[0197] (g) the possibility that an agrochemical product such as a pesticide has been sufficiently detoxified or removed from seed treatment equipment and / or associated accessories;
[0198] (h) the possibility that an agrochemical product such as a pesticide has been sufficiently detoxified or removed from pesticide manufacturing equipment and / or associated accessories and / or
[0199] (i) the possibility that an agrochemical product such as a pesticide has been sufficiently removed from a rinse water and the remaining levels in a rinse water are considered in the safe zone or in a zone that does not cause damage to plants or the environment;
[0200] (j), the possibility of an agrochemical product such as a pesticide having been mixed correctly or used in the correct concentration, or the uniformity of a solution;
[0201] (k) the quantity of an agrochemical product, such as a pesticide or final product that remains in containers or pesticide storage equipment;
[0202] (I) the amount of pesticide precursor chemistry during manufacture or contained in the finished pesticide product; or
[0203] (m) a combination of them.
[0204] System 11 is properly configured to provide dispatch alerts or alarms to a user (for example, using the data exchange interface 25 to communicate with any of the
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68/166 user devices) at any predetermined time to report the concentration of an agrochemical product such as a pesticide or final pesticide product (s) in the environment (equipment). These alerts can be provided by system 11 at any time interval or as a continuous reading in real time. These dispatch alerts provide the user with information about the concentration of pesticides or pesticide residues in or on agricultural equipment or other equipment. This can be particularly useful during the manufacture of an agrochemical, such as a pesticide, during the application of a seed treatment, or when cleaning any type of equipment that involves pesticides, such as during the detoxification or cleaning of an agrochemical, such as a pesticide from agricultural equipment, for example, tanks and bars associated with spraying platforms. The dispatch alert may be in the form of a warning to the user during cleaning procedures that the equipment contains levels of agrochemicals (for example, pesticides) that are not safe for plants, the environment or for other uses. Thus, system 11 can help to reduce or prevent harmful effects that occur by applying a not sufficiently low amount of pesticide or other agrochemical to a plant, a non-target plant or a field of plants, as would occur if the rinse water is not yet has reached the “safe zone” or a suitably low level of agrochemical product that will not cause injury.
[0205] In certain embodiments, the concentration data can be correlated with the flow rate data for an agrochemical product, so that the system is configured to determine an application rate of the agrochemical product in real time. For example, it may be desirable to provide a real-time indication of the application rate of one or more fertilizers, pesticides or other agrochemicals as it is being sprayed on seeds, plants or fields or dispensed in a
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69/166 processing facility. The application rate can be determined as a function of the measured flow rate of a fluid containing the agrochemical product and a determined concentration of the agrochemical product (s) in the fluid. Alerts can be sent if the given application rate deviates from an expected or desired application rate.
PREDICTIVE ESTIMATES AND SKILLS
[0206] In one or more modalities, system 11 can be configured to perform predictive analyzes. For example, system 11 can be configured to provide an estimate of the time remaining before a specified event occurs. In one embodiment, one or more agrochemicals, such as pesticides or final pesticide products that remain in a spray tank, bar, lines, nozzles or other accessories associated with a spray platform or other agricultural equipment can be identified and the processor can use this information to estimate the time needed to reduce the amount of agrochemicals in the equipment to safe or desirable levels. Likewise, to provide another example, system 11 can be configured to use information about the amount of agrochemicals in agricultural equipment to estimate when a reduction level of agrochemicals (for example, through a cleaning solution) will be achieved in a rinse water, so that it is safe to dispose of the rinse water. System 11 is properly configured to provide any estimates determined by the system to the user in the form of dispatch alerts (for example, using the data exchange interface 25 to communicate with any of the user's devices).
[0207] This system 11 is suitably configured to estimate future and / or past concentrations of agrochemical products, based on predictions calculated using an estimation algorithm. At
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70/166 information related to the rate of removal, deterioration or generation of one or more agrochemicals can be stored (for example, in the data exchange interface 25). This information can be generated from empirical data and / or provided by a supplier, such as a manufacturer or other source of information. The information may include information about natural decay and / or generation rates, as well as information about any relevant chemical or biological processes (for example, cleaning agents) that may be involved. Information pertinent to various pesticides and / or final pesticide products can vary from one chemical or chemical combination to the next. In addition, the relevant models (for example, exponential decay, linear generation or other more complex models) that describe the process (s) that produce changes in the concentration level (s) may vary depending on the products chemicals, biological agents, and / or process (s) involved. The algorithm used by system 11 can be adjusted based on the pesticide (s) or final product (s) of pesticide being measured, as well as any other pertinent facts or circumstances, to improve the accuracy of predictions using the algorithm.
[0208] In some cases, the time required for a pesticide to become a final pesticide product and / or a cleaning solution to reduce the concentration of a pesticide or final pesticide product can vary depending on various conditions. System 11 appropriately includes one or more additional detectors (not shown) configured to measure a variable that affects the change in a pesticide or final pesticide product over time. For example, additional detectors are properly configured to measure one or more of the following: temperature, pH, osmolarity and / or concentration of another substance, such as adjuvant, fertilizer, growth regulator, micronutrient, a control agent
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71/166 biological, a phytosanitary agent, an inoculant, a marker molecule, a surfactant and / or a solute in hard water. The data from these additional detectors can be used to improve predictions for future and / or past concentration levels of any pesticide and / or pesticide end product or other agrochemicals. Data from these additional detectors can also be used to improve the measurement accuracy of the current concentration level (s) in cases where the parameter monitored by the additional sensor (s) affects the spectral characteristics of the light detected by the system 11.
[0209] Therefore, system 11 is properly configured to perform at least one of the following:
[0210] (a) estimate an agrochemical product, such as a concentration of pesticide or final pesticide product at a time t2 based on at least one measurement of the concentration of said pesticide or final pesticide product taken at time t1, where t1 is not equal to t2;
[0211] (b) estimate a concentration of agrochemicals, such as a concentration of pesticides at time t3, based on at least two measurements of the concentration of said pesticide taken at time t1 and time t2, where t2> t1 and the change in the concentration of time t1 to time t2 represents a reduction of the pesticide in the environment;
[0212] (c) estimate a concentration of the final pesticide product at a time t3 based on at least two measurements of the concentration of that final pesticide product, taken at time t1 and time t2, where t2> t1 and a change in concentration from time t1 to time t2 represents an accumulation of the final pesticide product in the environment;
[0213] (d) estimate a concentration of agrochemicals, such as a concentration of pesticides, based on at least two measurements of the concentration of pesticides performed at time t1 and time t2, where t2>
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72/166 t1 and the change in concentration from time t1 to time t2 represents an accumulation of the pesticide in the environment;
[0214] (e) estimate a concentration of the final pesticide product based on at least two measurements of the concentration of the final pesticide product taken at time t1 and time t2, where t2> t1 and the change in concentration of time t1 for time t2 it represents a reduction of the pesticide or final product of the pesticide in the environment;
[0215] (f) estimate a concentration of agrochemicals such as a pesticide or concentration of final pesticide product based on a predetermined standard curve or library;
[0216] (g) estimating a concentration of agrochemical product, such as a pesticide or a concentration of the final product based on a comparison with a background absorbance value with a wavelength different from the wavelength (s) used to identify the pesticide or the final pesticide product;
[0217] (h) estimate a concentration of agrochemical product, such as a concentration of pesticide or final product of pesticide, based on an absorbance ratio obtained;
[0218] (i) determine the composition of an agrochemical product and / or identify final products of agrochemical products in a sample;
[0219] (j) estimate the absence of an agrochemical or type of agrochemical product present in a given sample; and
[0220] (k) combinations thereof.
[0221] In an example of an algorithm that system 11 can use to predict concentration levels, the forecasting algorithm is initialized with two initial concentration measurements to estimate a dosage generation or a dosage decay rate. The rate of dosage generation as part of the algorithm can be applied to a process to manufacture products
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73/166 agrochemicals in a tank or vessel and reach a desired final concentration of the agrochemical product and / or confirm a validity requirement for the concentration range of the agrochemical product for quality assurance. The dosage decay rate as part of the algorithm can be applied to a process to detoxify or remove agrochemical products from agricultural equipment or others used in the manufacture, transportation or storage of agrochemical products. A logic block in the algorithm receives the first and second initial concentration measurements from two different times and estimates the rate of generation or decay of the agrochemical.
[0222] Once the initial concentration level of the agrochemical product is determined, a predictive rate of the generation or decay rate for the concentration of agrochemical products is determined for subsequent measurements. Thus, predictive concentrations of agrochemicals are based on estimates of generation rates or decay of concentrations in the environment at the first initial measurement at time (t1) compared to the second initial measurement at time (t2) and subsequent measurement times ( t3 + tn). This predictive rate of generation or rate of decay is properly updated and refined after the initial forecast with additional data provided by the concentration measurements made in the subsequent measurement times (t3 + tn). The measured concentration and the expected concentration of the agrochemicals for subsequent measurement times (t3 + tn) are compared to determine discrepancies between the measurements made by the detector (s) and then adjustments are made to the system for adjustment changes in environmental parameters and measurement errors. System 11 properly includes a filter that is provided with initial information, including the covariance of the measurement error and estimates of the initial parameters and associated errors. This information is used to calculate a filter gain matrix. System 11 adequately adjusts substantially
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74/166 continuously the parameters or attributes of the light to minimize (or eliminate) errors due to uncertainties in the system and errors in measurements. This can be done through “dark” measurements without supplied light or a blank measurement of clean water to eliminate noise or the background of a sample. In this way, the algorithm (or algorithms) predicts the concentrations for the next subsequent measurement and the accumulated or reduced concentration of the agrochemical product, adding the concentration for each increment of time, so that the total concentration at the end of the measurement time is predicted and can be compared with the predetermined desired final concentration level.
[0223] For example, using the magnitude of the discrepancy between estimated and measured concentrations, system 11 further adjusts the parameters or attributes of the light, to increase the accuracy of subsequent forecasts of the concentration of the agrochemical product in the environment. After each adjustment, the system predicts the next measured concentration. The error between the concentration estimates and the measured data is determined and multiplied by the filter's gain matrix to update the estimate and the estimated error. Several measurements are taken and the system 11 calculates an estimate of the error in the measurement, calculates an estimate of the error in the environment and, using the filter and a filter gain, adjusts the filter time constant according to the errors, to estimate the rate generation or deterioration of pesticides in the environment. When calculating the rate of generation or decay in the environment, system 11 performs the next projected integrations of concentration of agrochemical products for a predetermined period of time and, knowing the limits associated with the high and low extremities of the detection of agrochemical products, the system warns whether the pesticide concentration has sufficiently achieved the predetermined concentration target in an environment.
[0224] The detection of the identity and concentration of the agrochemical product can be carried out using a single algorithm, an
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75/166 adjustment, various algorithms, chemometric (learning) algorithms or combinations of these. The wavelength (s) used can be adjusted based on the agrochemical and light parameters. In addition, single or selective light sources or filters can be used to eliminate noise or background and increase resolution.
[0225] The error and the updated parameters are used as input to a model to predict the error and other parameters projected in the next instance. As confidence in the accuracy of the parameters increases with each iteration, the values of the filter gain matrix decrease, decreasing the influence of the measurement data on the update of the parameters and the associated error. The filter is used to remove errors and improve the prediction of the concentration of the agrochemical product at a given time and the total dosage at the end of the measurement period. The next predicted concentrations are added cumulatively to obtain an accumulated concentration average. System 11 further predicts the total concentration at the end of the measurement period.
[0226] The spectral bandwidth transmitted by the detector (s) 15, the percentage of transmission through or by the object or area of interest and the logarithmic range of the sample absorption and, alternatively, a percentage of the reflectance measurement are properly used collectively to develop the algorithm. Spectrophotometric methods were developed to measure the transmittance or reflectance of pesticides in solutions in varying ranges of concentration and used to develop the algorithm of the invention. The peak absorbance diffusivity of agrochemical product from 200 to 2,500 nm can be used to detect any agrochemical product as described in the modalities of the invention. Specific pesticides and classes of pesticides were used to develop the algorithm. They have been detected and quantified using various control standards and
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76/166 calibration to identify the wavelengths for the peak absorbance of the photometric determination.
[0227] In another example of an algorithm that System 11 can use, the algorithm determines from a single absorbance reading whether any detectable algorithm is present and / or whether a safe zone has been reached or not by comparing the overall absorbance in a wavelength set to a threshold level or using predictions based on a calibration of the single absorbance reading against a non-absorbent background wavelength.
[0228] A single algorithm, an adjustment algorithm, several algorithms, chemometric (learning) algorithms or combinations of these can be used to simultaneously measure the concentrations of one or more agrochemicals and one or more inert marker dyes (discussed below) used in combinations with agrochemicals.
[0229] An algorithm for detecting multiple mixtures of pesticides using pattern recognition combined with chemometric approaches is described. A chemomethical approach applies pattern recognition techniques and can be used to provide spectral traces in real time that provide a spectral signature or fingerprint of a unique agrochemical product. In certain modalities, chemometric algorithms are applied with a method to simultaneously identify and measure the concentration of multiple agrochemicals in an aqueous sample. Continuous and simultaneous measurements are taken and used to quantify the concentrations of multiple mixtures of agrochemical product, determining the absorbance or emission spectrum of the agrochemical components in an aqueous solution (s) in a spectral range and applying the chemomechanical algorithm (s) a analyzing resources in the spectral traces. The analysis of the chemometric algorithm allows characteristics
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77/166 qualitative and quantitative spectral spectra of the individual agrochemical traits, allowing both the identification and the quantitative determination of the concentration of the agrochemical product (s) in a mixture. The application of chemometric algorithms is useful for measuring more than one or more agrochemicals in an aqueous solution in the 200 to 800 nm wavelength range (or other higher wavelength ranges) and includes several samples and calibration measurements using approaches based on pattern recognition. The narrow band spectra can be designed for collection at different wavelength bandwidths to distinguish between the different signatures associated with an individual agrochemical product. The calibrated standards are used initially in the development of the algorithm to minimize any effect of background interference contributed by constituents other than agrochemicals in the sample mixture.
[0230] Therefore, system 11 is properly configured to use the algorithms described here to accurately estimate the amount of agrochemical residue that is currently in a tank at the time of the initial measurement (tO). This is useful for confirming the concentration of an agrochemical product during a manufacturing process to determine whether the correct or desired final concentration has been achieved or to determine the estimated useful life of an agrochemical product solution. This is also useful for determining the concentration of pesticide remaining in the tank at the beginning of the detoxification or removal process (t1) and at (t2) when the removal process is complete.
AGRICULTURAL PRODUCTS AND OTHER PARAMETERS THAT THE SYSTEM CAN DETECT
[0231] System 11 described above can be used to detect, measure and quantify any of the agrochemical products described here,
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78/166 including: a herbicide, a fungicide, an insecticide, an insect growth regulator, a biocontrol agent, a bactericide, a nematicide, an acaricide and a virucide, a fertilizer or any combination thereof.
HERBICIDES
[0232] For example, system 11 can be used to determine the amount of a herbicide that exists in agricultural equipment or remains on surfaces contaminated with residual herbicides. A list of herbicides that can be detected and monitored by system 11 includes, but is not limited to: acetochlor, acifluorfen and its sodium salt, aclonifene, acrolein (2-propenal), alachlor, alloxidine, ametrine, amicarbazone, amidosulfurone, aminopiral , aminocyclopyrachlor, amitrol, ammonium sulfamate, anilophos, asulam, atrazine and s-metoachlor atrazine, azimsulfurone, beflubutamide, benazoline, benazolin-ethyl, bencarbazone, benfluraline, benfuresate, bensulfurone-benzentha, benzene, benzene, benzene benzazine, benzodiazepine, benzazine, benzine, benzine, benzine bispiribac and its sodium salt, bromacila, bromobutide, bromophenoxy, bromoxynil, bromoxynyl octanoate, butachloro, butafenacil, butamiphos, butralin, butroxidime, 4-butylate, 4-butylate -methylphenoxy) butylentrone, cafenstrol, carbazine, cafenstrol-ethyl, catechin, clomethoxyfen, chlorambene, chlorobromurone, chlorflurenol-methyl, chloridazone, chlorimurone-ethyl, chlorotolurone, chlorpro fame, 2chlorophenoxyacetic acid, chlorsulfurone, chlortalidamethyl, chlortamide, cinidonethyl, cinmethyline, kinesulfurone, clethodim, clodinafoppropargil, clomazone, clomeprope, clopyralide, chlorpyridide, clopyralid-olamine, 2-chloramine-4-chloramine -chloro-2-fluoro-5 - '(1-methyl-2-propynyl) oxy-phenyl' (3-fluorobenzoyl) amino'carbonyl'-1 -cyclohexene-1-carboxylate) ”', clopyralide, cumilurone, cyanazine, cycloate, cyclosulfamurone, cycloxydim, cyhalofop-butyl, 2,4-D, 2,4-D and their butotyl, butyl, isoctyl and isopropyl esters and their salts
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79/166 dimethylammonium, diolamine and trolamine, daimurone, dalapone, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, demedipham, demetrine, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts , dicamba, dichlorophenoxyacetic acid, dimethyl amine salt of 2.4 doclorophenoxyacetic acid, 2,4-dichlorophenol, dichlobenyl, dichlorprope, dichlorprope-P, diclofop-methyl, diclosulam, difenzoquat methylsulfate, diflufen, diflufen; dimetachlor, dimetamethrin, dimethenamide, dimethenamide-P, dimethypine, dimethylamine salt (CMPP-P DMA), dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamide, diquat dibromine, dithiopir, diurone, DNOC, endocar, EPTC , etalfluralina, ethametsulfurone, etametsulfuron-methyl, etofumesate, ethoxyfen, ethoxysulfurone, etobenzanide, phenoxaprop-ethyl, phenoxaprop-P-ethyl, fentrazamide, phenurone, phenurone-TCA, flamprop-methyl, framprop-M-isopropyl, flamprop-M-isopropyl pM-methyl, flazasulfurone, florasulam, fluazifop-butyl, fluazifop-Pbutile, flucarbazone, flucetosulfurone, fluloraline, flufenacet, flufenpire, flufenpirethyl, flumetsulame, flumiclorac-pentyl, flumicloracetyl, flumioxurine, flumioxurol, fluometergol, fluometergol flurenolbutyl, fluridone, flurochloridone, fluroxypyr, fluroxypyr 1 -methylptilester, flurtamone, flutiacet-methyl, fomesafen, fomesafen sodium salt, foramsulfurone, phosamine-ammonium, guizalop, glufosinate, glufosinate-ammonium, glufosinate-ammonium, and glufosinate-ammonium, , potassium, sodium (including sesquisodium) and trimesium (also called sulfosate, halosulfurone, halosulfuroxymethyl, haloxifopetothyl, haloxifop-methyl, hexazinone, HOK-201 (N- (2,4-difluorophenyl) -1,5-dihydro-N - (1methylethyl) -5-oxo-1 - '(tetrahydro-2-pyranylmethyl-4H-1,2,4-triazol-4-carboxamide), 2-hydroxyphenoxyacetic acid, 4-hydroxyphenoxyacetic acid, imazamethabenzmethyl, imazamox, imazapico, imazapira, imaz aquine, imazaquin-ammonium, imazetapyr, imazetapyr-ammonium, imazosulfurone, indanophane, iodosulfurone, iodosulfurone-methyl, ioxynyl, ioxinyl octanoate, ioxinyl-sodium, isoproturone,
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80/166 isourone, isoxaben, isoxaflutol, pyrosulfotide, lactophen, lenacil, linuron, maleic hydrazide, MCPA and their salts (eg MCPA to dimethylammonium, MCPA to potassium and MCPA to sodium), esters (eg MCPA to 2- ethylhexyl, MCPA to butotyl) and thioesters (eg, MCPA to thioethyl), MCPB and its salts (eg, MCPB-sodium) and esters (eg, MCPB-ethyl), MCPB acids, MCPB + MCPA (trropotox ), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfurone-methyl, mesotrione, metam sodium, metamifop, metamitrone, metribuzin, metazachlor, metabenzothiazurone, methylarsonic acid and its calcium, monoammonium, monosodium and disodium, methyldromone, methyldromone, methyldromone, methyldromone, methyldromone, methyldromone, methyldromone, methyldromone, methyldromone, methyldromone, methyldromone, methyldromone, methyldromone, methydromone. metolachlor, S-metolachlor, metosulam, methoxyurone, metribuzin, metsulfurone, metsulfuron-methyl, mycosulfurone, molinate, monolinurone, naproanilide, napropamide, naptalam, neburone, nicosulfurone, norflurazon, oxorin, oxaloxane, paraquat dichloride, pebbled, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, petoxiamide, fenmedifane, piclorame, pinclorame-potassium, picolinafen, pinoxadene, piperofos, pretilachone, primosulfone, primisuron, primisulfone, primisuron, primisuron, primisulfone, primisulfone, primisulfone , promethrin, propachlor, propanyl, propaquizafop, propazine, propachlor, propanyl, propaquizafop, propazine, propam, propisochlor, propoxycarbazone, (R) 2 (4-chloro-2-methoxyphenol) propionic acid, propitamide, prosulfocarb, prosulfurone, prosulfurone, protoporfirinone PPO), piraclonil, pyroflufen-ethyl, pyroxassulfone, pyrazulfotol, pyrazogyl, pyrazolinate, pyrazoxifene, pyazosulfurone-ethyl, pyroxasulfone, pyribenzoxime, pyributicarb, pyridate, pyriftalide, pyriminobacmethyl, pyrimisulfan, pyrimisulfan, pyrimbacyracin, pyrimbacyracin, pyrimbacyracin, pyrimethoxy, pyrimethoxyl, pyrimethoxyl, pyrimethoxyl, pyrimethanol , quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-Ptefuril, rimsulfurone, safluenacil, seto xidime, sidurone, simazine, symmetrine, sulcotrione, sulfentrazone, sulfosulfurone, sulfometuron-methyl, sulfosulfurone,
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2,3,6-TBA, TCA, sodium TCA, tebutam, tebutiurone, tefuriltrione, tembotrione, tepraloxidime, terbacil, terbumeton, terbutilazine, terbutrin, tenilcllora, tiazopire, tiencurbazone, tifensulfuron-methyl, thiobazone, thiobazone tri-alate, tribenurone, trebernuron-methyl, tifelsulfurone, trasulfdurone, traziflame, triclopire, triclopyr-butotyl, triclopyrtriethylammonium, tridifane, trietazine, trifloxysulfurone, trifluralin, triflusulfuron-trone and triflusulfuron-methyl.
The system 11 described herein can be used to selectively determine the amount of any herbicide in the broad classes of herbicides identified in Table 1.
TABLE 1: CLASSES OF HERBICIDES COMMONLY USED
Classesbroad Control HerbicidesExample Pests Anilides / Anilines Acetochlor alachlor asulam benfluralin butachlor diethyl difilufenicano dimetenamide flamprop metazachlormetolachlor pendimethalin pretilachlor propachlor propanyl trifluralin Aromatic acids cloramben aminopiralid dicamba clopiralid picloram piritiobac quinclorac quinmerac Arsenic copper acid arsenatecacodyl DSMA MSMA Organophosphors Bensulide bialafos etefon phosaminaglufosinate glyphosate piperophos Phenoxy 2,4-D 2,4-DB dichlorprop dichlorprop-
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Classesbroad Control HerbicidesExample Pestsp mecoprop-r mecoprop-p clomeprop fenopropMCPA MCPB 2,4,5-T Pyridines Ditiopir fluroxypyr imazapyr tiazopir triclopyr halauxifene methyl florpirauxifen-benzyl Quaternary Diquat MPP Paraquat Triazines ametrine atrazine cyanazine hexazinone promethazine promethin simazine symmetrine terbuthylazine terbuthylin Urea Chlortolurone DCMll metsulfuronamethyl monolinurone tebutiurone Others 3-AT aminocyclopyrachlor bromoxynil clomazone DCBN dinoseb juglone mesotrione metazol metam sodium metamitrone metribuzin flucarbazone sulfentrazone
[0233] In other applications, the system 11 described here can be used to determine the amount of a growth regulating herbicide that exists in agricultural equipment or remains on surfaces contaminated with residues of a growth regulating herbicide. Growth regulating herbicides, also referred to as auxin-type herbicides, are generally formulated as amine salts or low volatility esters. Detoxifying formulations can be used to detoxify any growth regulating herbicide in the following groups: phenoxy herbicides, benzoic acid herbicides, pyridine herbicides and quinoline herbicides. Growth regulating or regulating herbicides
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83/166 growth, which include different chemical classes, such as phenoxycarboxylic acids, benzoic acids, pyridine-carboxylic acids, aromatic carboxymethyl derivatives and quinolinecarboxylic acids, in which the essential structural requirement for its activity is a strong negative charge on the carboxyl group of dissociated molecule. Auxin herbicides are herbicides widely used in lawns, crops, fallows, grass management, especially for domestic use and on golf courses, forest management, bush management in non-cropped areas and for aquatic weed control . The general categories of synthetic herbicides representative of auxin, auxin type or growth regulator include, but are not limited to, phenoxyacetic acids (phenoxys), such as 2,4-D, 2,4-DB, 2,4-DP (dichlorprop or dichlorprop acid), 2,4,5-T, 2,4,5-TP, MCPA, MCPB, MCPB NA, MCPB acid, MCPP (mecoprop), (+) R-2- (4-chloro-2- methylphenoxy) propionic (Mecoprop-P technical acid), dichlorprop-P and Tropotox technical acid (MCPB + MCPA) and other 2,4-D amines or esters, benzoic acids, such as dicamba, and pyridine-carboxylic acids, such as Clopyralide, Picloram, Triclopyr, Aminopiralid and Aminocyclopyrachlor. Such herbicide compositions and a list of commercially available herbicides that contain the growth regulating herbicides, dicamba and 2,4-D and can be detected, measured and quantified using the apparatus of the present invention are provided in Table 2.
TABLE 2: HERBICIDE COMPOSITIONS CONTAINING DICAMBA AND 2,4-D CURRENTLY AVAILABLE COMMERCIALLY
Active ingredients
Dicamba
2,4-D
2,4-D, dimethylamine salt; Dicamba, dimethylamine salt
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Active ingredients
Dicamba, dimethylamine salt
Atrazine; Dicamba, potassium salt
2,4-D, glyphosate
Dicamba, glyphosate
2,4-D, 2-ethylhexyl ester; 2,4-DP-p, 2-ethylhexyl ester;
Dicamba
Dicamba, sodium salt; Diflufenzopyr-sodium; Nicosulfurone
Dicamba, diglycolamine salt
Dicamba; MCPA, 2-ethylhexyl ester; Triclopyr, butoxyethyl ester
Dicamba, sodium salt; Diflufenzopyr-sodium
Dicamba, dimethylamine salt; MCPA, dimethylamine salt;
Triclopir, trimethylamine Salt
2,4-D; Dicamba
Dicamba, sodium salt; Primisulfurone-methyl
2,4-D, 2-ethylhexyl ester; Dicamba
Carfentrazone-ethyl; Dicamba; MCPA, 2-ethylhexyl ester; acid
MCPP-p
2,4-D, dimethylamine salt; Dicamba; MCPP, dimethylamine salt
Dicamba, diglycolamine salt; Fluroxypyr, 1-methylheptyl ester
2,4-D, dimethylamine salt; Dicamba, dimethylamine salt;
Quinclorac; Sulfentrazone
Dicamba, sodium salt; Rimsulfron
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Active ingredients
2,4-D, 2-ethylhexyl ester; Carfentrazone-ethyl; Dicamba, MCPP-p acid
2,4-D, dimethylamine salt; Dicamba, dimethylamine salt; MCPPp, dimethylamine salt; Sulfentrazone
2,4-D, dimethylamine salt; Dicamba, dimethylamine salt; MCPPp, dimethylamine salt;
2,4-D, dimethylamine salt; Dicamba, dimethylamine salt; MCPPp, dimethylamine salt; MSMA
2,4-D, triisopropanolamine salt; Dicamba; Picloram, triisopropanolamine salt
Dicamba, sodium salt; Halosulfurone-methyl
Aminocyclopyrachlor
[0234] System 11 described here is useful for detecting, measuring and quantifying auxin-like herbicides. Exemplary auxin herbicides include 2,4-dichlorophenoxyacetic acid (2,4-D), 4- (2,4-dichlorophenoxy) butanoic acid (2,4-DB), dichloroprop, dichloroprop-p, (4-chloro-2 - methylphenoxy) acetic acid (MCPA), 4- (4-chloro-2-methylphenoxy) butanoic acid (MCPB), mecoprop, mecoprop-p, dicamba, picloram, fluroxypyr, chloramben, clopioralide, aminopiralid, triclopir, quinmerac and quinclorac, salts, acids or esters of any of these herbicides and mixtures thereof acceptable in agriculture.
INSECTICIDES
[0235] In still other applications, the system 11 described can be used to determine the amount of insecticide in an environment. For example, system 11 is suitable for detecting, measuring and quantifying an insecticide or a combination of insecticides, which include, but are not limited to: abamectin,
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86/166 acephate, acetamiprid, amidoflumet, avermectin, azadiractin, azinphos-methyl, bifentrin, biphenazate, buprofezin, carbofuran, cartap, chlorfenapyr, chlorfluazurone, chlorpyrifos, chlorpyrifin-methyl, chliphifl-chlorofluorine, chlorotin-chloride , lambda-cyhalothrin, cypermitrine, cyromazine, deltamethrin, diafentiurone, diazinone, dieldrin, diflubenzurone, dimeflutrin, dimethoate, dinotefuran, diofenolane, emamectin, endosulfone, sphenol-renate, flaminvalidate, etiprol, flaminate, phenoxy, phenoxy, phenoxy , tau-flavinate, flufenerin, flufenoxurone, fonofos, halofenozina, hexaflumorona, hydramethilnona, imidaclopride, indoxacarb, isofenfos, lufenurone, malation, metaflumizone, metallidene, metamofen, methymethoxy, methyrone, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy , novalurone, noviflumurone, oxamil, paration, paration-methyl, permethrin, phorate, fosalone, fosmet, fosfamidone, pirimicarb, profenofos, proflutrina, pimetrozina, puraflupore, pyrethrin, pyridalil, pyriprol, pyriproxifene, rotenone, ryanodine, spinosad, spirodiclofen, spiromesifene, spirotetrama, tetrahydrofluoride, tyrofluoride, sulfoxafl, tetrachlorvinfos, thiacloprid, thiamethoxam, thiodicarb, thiosulfatapodium, tralometrine, triazamate, trichlorone and trioflumorone.
FUNGICIDES
[0236] Fungicides such as acibenzolar, aldimorph, amisulbrom, azaconazole, azoxystrobin, benalaxyl, benomile, bentiavalicarb, bentiavalicarb-isopropyl, binomial, biphenyl, bitertanol, blasticidine-S, Bordeaux mixture (niacin, sulphate) , bupirimate, butiobate, carboxine, carpropamide, captafol, captan, carbendazim, chloroneb, chlorothalonil, clozolinate, clotrimazole, copper oxychloride, copper salts, such as copper sulfate and copper hydroxide, ciazofamide, ciflunamide, cumoxanil, cyprazol, cypramine, cyprazol, cyprazol, cyproxylil diclofluanide, diclocimet, diclomezine,
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87/166 dichloran, dietofencarb, diphenoconazole, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, discostrobin, ditianon, dodemorf, dodine, econazol, etaconazole, edifenfos, epoxiconazole, phenolamide, ethaboxam, ethaboxam, ethaboxam, ethaboxam, ethaboxam, ethaboxam, ethaboxam, , fencaramid, fenfuram, fenexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorf, fentina acetate, fentina hydroxide, ferbam, ferfurazoate, ferimzone, fluazinam, fludioxonil, flumetover, fluopicolide, fluoxastrobin, flquinconazole, flquinconazole , folpet, fosetil-aluminio, fuberidazole, furalaxil, furametapir, hexaconazole, himexazol, guazatine, imazalil, imibenconazole, iminoctadine, iodicarb, ipconazole, iprobenfos, iprodione, iprovalicarb, methanol, isoprazole, isoconazole, isoconazole, , mapanipirin, mefenoxam, mepronil, metalaxyl, metconazole, methasulfocarb, metiram, metominostrobin / phenominostrobin, mepanipir im, metrafenone, miconazole, myclobutanil, neo-asozine (ferric methanearsonate), nuarimol, octilinone, ofurace, orisastrobin, oxadixil, oxolinic acid, oxpoconazole, oxycarboxine, paclobutrazol, penconazole, pencicuride, pencicuron, pencicurone, pentopyran picoxistrobin, polyoxin, probenazole, prochloraz, procimidone, propamocarb, propamocarb-hydrochloride, propiconazole, propineb, proquinazid, protioconazole, piraclostrobin, priazofos, pyrifenox, pirimethanil, pirifenox, pyrolnitrine, quironoline, quironol, pyrolone streptomycin, sulfur, tebuconazole, tecrazene, keyboardoftalam, tecnazene, tetraconazole, thiabendazole, tifluzamide, thiofanate, thiophanate-methyl, take out, thiadinyl, tolclofos-methyl, tolifluanid, triadimefon, triadimide, triadimide, triadimide, triadimide, triadimide , triticonazole, uniconazole, validamycin, vinclozolin, zineb, ziram, and zoxamide; nematocytes such as aldicarb, oxamyl and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, cinometionat, chlorobenzylate, cyhexatin, dicofol, dienochlor, ethoxazole, phenazaquin, oxide
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88/166 fenbutatin, fenpropatrin, fenpyroximate, hexitiazox, propargite, pyridabene and tebufenpirad; and biological agents or biologically active compounds.
[0237] In other applications, the system 11 described here can be used to determine the amount of a class of neonicotinoid insecticides in an environment, including: neonicotinoid insecticides, pyriproxifene or diamide. Neonicotinoids specifically comprise a class of systemic agricultural insecticides that are neuroactive or selectively neurotoxic chemicals similar to nicotine. The neonicotinoid family includes acetamipride, clothianidin, imidacloprid, nitenpyram, nitiazine, thiacloprid and thiamethoxam. The use of neonicotinoid insecticides has grown recently, as they are selected for use preferentially to many organophosphate and carbamate insecticides. The neonicotinoid family includes acetamipride, clothianidin, imidacloprid, nitenpyram, nitiazine, thiacloprid and thiamethoxam.
[0238] In still other applications, the system 11 described here can be used to determine the amount of an insect growth regulator (IGR), such as: benzoylurea, hilmilin, diflubenzurone and triflumurone, which can inhibit the development in varying stages of the mosquito life cycle.
[0239] In other practical applications, the system 11 described here can be used to determine the amount of a biologically active compound or biological control agent that can be used as insecticides, such as: abamectin, acephate, acetamipride, amidoflumet, avermectin, azadiractin , azinfos-methyl, bifentrina, binfenazato, buprofezin, carbofuran, chlorfenapir, chlorfluazurone, chlorpyrifos, chlorpyrifos-methyl, chromafenozida, clotianidin, cyfluthrin, dihydrochloride, beta-cyflorethin, diaphrine, diaphrine, diaphrine, diaphragm, diaphragm , dimethoate, diophenolan, emamectin, endosulfan, sphenolerate, etiprol fenoticarb,
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89/166 fenoxicarb, fenpropatrin, fenvalerato, fipronil, flonicamid, flucitrinato, taufluvalinato, flufenerim, flufenoxurone, fonofos, halofenozida, hexaflumurona, imidaclopride, indoxacarb, isofenfos, metoforidos, metho, methoxy, methoxy, methoxy, methoxy, methoxy, methoxy , methoxyfenozide, nitiazin, novalurone, noviflumurone, oxamil, paration, parationmethyl, permethrin, phorate, fosalone, fosmet, fosphamidon, pirimicarb, profenofos, pimetrozine, pyridalil, pyriproxifen, rotenone, spinosade, tyrosphonefephrine, tyresphyridine, tyrone, spyridine , tetrachlorvinfos, thiacloprid, thiamethoxam, tiodicarb, thiosultap-sodium, tralometrina, triclorfon and triflumuron; fungicides such as acibenzolar, azoxystrobin, benomile, blasticidin-S, Bordeuax mixture (tribasic copper sulfate), bromuconazole, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, ciflufenilide, cyimoxanilide, cyimoxanilide, cyimoxamine , (5) -3,5-dichloro-N (3-chloro-1-ethyl-1-methyl-2-oxopropyl) -4-methylbenzamide, diclocimet, diclomezine, dichloran, diphenoconazole, (5) -3,5- dihydro-5-methyl-2- (methylthio) -5-phenyl-3- (phenylamino) -4H-imidazol-4-one, dimetomorf, dimoxystrobin, diniconazole, diniconazoleM, dodino, edifenfos, epoxiconazole, famoxadone, phenamidone, fenarimol, fenbuconazole, fencaramide, fenpiclonil, fenpropidina, fenpropimorfo, fentina acetate, fentina hydroxide, fluazinam, fludioxonil, flumetover, flumorfflumorlina, fluoxastrobina, fluquinconazola, flusilazol, flushilin, flushilin, flushilin, flushilin, flushilin, fluoroacetamol, iprobenfos, iprodione, isoprothiolane, casugamycin, cresoxim-methyl, mancoz eb, maneb, mefenoxam, mepronil, metalaxyl, metconazole, metominostrobin / phenominostrobin, metrafenone, myclobutanil, neo-asozine (ferric methane-arsonate), nicobifene, orisastrobin, oxadixyl, penconazol, pencicuram, propenazole, propenazole, propenazole, propenazole protioconazole, pyrifenox, pyraclostrobin, pyrimethanil, piroquilon, quinoxyphene, spiroxamine, sulfur, tebuconazole, tetraconazole, thiabendazole, tifluzamide, thiophanate-methyl, take,
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90/166 thiadinyl, triadimefon, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin and vinclozolin; nematicides such as aldicarb, oxamyl and fenamiphos; bactericides like streptomycin.
BACTERICIDES OR BACTERIOCIDES
[0240] In addition, system 11 described here is suitable for detecting, measuring and quantifying a bactericide or bacteriocide. Commonly used bactericides are disinfectants, antiseptics or antibiotics, such as 8-hydroxyquinoline sulphate, bronopol, copper hydroxide, cresol, dichlorophene, dipyrthion, dodicin, phenaminosulf, formaldehyde, hexachlorophene, casugarcin, nitrapirin, octycin, estritin, oxytetrazine, oxytetrazine, oxytetrazine, oxytetrazine, oxytetrazine, oxytetrazine, oxytetrazine, oxytetrazine, oxytetrazine. keyboardoftalam and thiomersal.
NEMATICIDES
[0241] The system 11 described in this document is also properly configured to detect, measure and quantify nematicides, as toxic to broad spectrum nematicides that act systematically and have high volatility or other properties that promote migration through the soil. Commonly used nematicides are generally classified into broad classes of: avermectin, botany, carbamate, oxime carbamate, fumigant, organophosphate, organophosphate, phosphonothioate nematicides. Unclassified nematicides refer to acetoprol, benclothiaz, chloropicrin, dazomet, DBCP, DCIP, fluazaindolizine, fluensulfone, furfural, metam, methyl isothiocyanate, thioxazafene and xylenols.
VIRUCIDES
[0242] System 11 described here is also suitable for determining the amount of virucides in an environment, such as disinfectants or surface detergents, especially detoxifying disinfectants containing iodophores or phenolic compounds. Other virucides that can be detected, measured and quantified by system 11 include: Cyanovirin
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N, Griffithsin, Scytovirin, NVC-422, Virkon Disinfectant / Cleaner P.W.S. Virucide (for veterinary use), Zidovudine, Zonrox bleach, other bleaches, lysol, wetting agents, alcohols and solvents.
ACARICIDES
[0243] In other applications, system 11 is configured to determine the amount of acaricides, such as: permethrin, antibiotic miticides, carbamate miticides, formamidine miticides, dicofol and a variety of commercially available systemic and non-systemic miticides: abamectin, acequinocil, biphenazate, biphenazate, chlorfenapyr, clofentezine, ciflumetofen, cypermethrin, dicofol, ethoxazole, phenazaquin, phenpyoxime, hexitiazox, imidacloprid, pyridabene, spiromesifene and spirotetra.
BIOLOGICAL
[0244] In other applications, system 11 is configured to detect bacterial, viral or fungal organisms for use in or with the promotion of plant, pesticide or biopesticide growth. In addition, biological products can also be detected and quantified. Examples include: Streptomyces acidiscabies non-viable MBI-005 RL-110, systemic herbicide MBI-010, California autographa nucleopolihedrovirus strain FV11, Spodoptera littoralis nucleopolihedrovirus, MBI-601 Muscador albus strain SA-13, MBI-0 extract piper longum, MBI-206 Burkholderia spp. strain A396, S. Frugiperda baculovirus, strain B50 of Brevibacillus parabrevis, lactone Acyl-homoserine, Bacillus pumilus, Bacillus thuringiensis, strain PRAA4-1T of Chromobacterium subtsugae, oxalic acid dihydrate, Trichoderma spp. 5339 or ANT-03, Stringolactones, strains 14940 or 14941 of Aureobasidium pullalans, strain ACM941 of Clonostachys rosea, Malaleuca alternifolia, Bacillus amyloliquefacians, Bacillus firmus, Bacillus subtilis, Pasteuria nishiwazae Pn1, extract from Knotweed. F727, Flavobacterium spp., Strain H492,
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FINAL PRODUCTS OF PESTICIDES
[0245] System 11 can also be configured to detect, measure and quantify a final pesticide product that is produced when the pesticide or herbicide is detoxified or degraded into its less toxic end products (for example, in cases where chemicals break down reagents due to natural processes or interaction with cleaning or detox products). The peak absorbance of the decomposition or the final products can be applied to the algorithms described here to determine when a pesticide, for example, a herbicide has reached the desired concentration. In general, the concentration (s) (measured and expected) for the final pesticide product (s) is inversely related to the concentration (s) of the ) pesticide (s) and can alternatively be used to determine when a pesticide has been removed or detoxified enough to levels considered in the safe zone and not causing damage to a plant, a plant field, a part of the plant, a waterway or a natural environment.
[0246] Comparisons of dicamba concentrations and generation or accumulation of final dicamba product were analyzed using system 11 in parallel with samples analyzed by liquid chromatography coupled with mass spectroscopy (LC / MS / MS) to determine the decomposition of dicamba or concentration final product over time. Liquid chromatography (LC) combined with mass spectroscopy (MS) analyzes showed a removal of the dicamba molecule, a commonly used systemic herbicide (C8H6CI2O3) also referred to as 3,6-dichloro-2-methoxybenzoic acid accompanied by an increase in your product, DCSA or 3.6 dichlorosalicylic acid; 3,6-dichloro-2-hydroxybenzoic acid.
[0247] This is just an example of a specific combination
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93/166 of a pesticide and a final pesticide product. It is understood that other pesticides and final pesticide products will have similar relationships and that the system's detection of a change in the concentration of one or more final pesticide products can be used as a proxy for an inverse change in the corresponding pesticide.
OTHER AGRICULTURAL PARAMETERS
[0248] In addition to determining the amount of pesticides or final pesticide products in an environment, the system 11 described here may include additional detectors (as described above in connection with the system in Figure 2) configured to measure a plurality of other parameters in the environment. For example, system 11 can be used to measure parameters, including: temperature, pH, osmolarity, hard water components, water conditioning agents or pH modifiers and / or concentration of adjuvant, fertilizer, growth regulator, a micronutrient, a biological control agent, a phytosanitary agent, an inoculant, a marker molecule, a surfactant, an osmoprotector, a protector, diesel, oils, viscosity modifiers and / or a solute in hard water.
ADJUVANTS
[0249] For example, system 11 is properly configured to determine the amount of one or more agriculturally acceptable adjuvants or vehicles that are included in a spray application and can be applied together with or without a pesticide. Adjuvants can also include agricultural acceptable carriers. The agricultural acceptable carrier can be any vehicle suitable for agricultural use. For example, acceptable vehicles suitable for agriculture include, but are not limited to, dispersants, surfactants, additives, water, thickeners, anti-caking agents, waste decomposition, composting formulations, granular applications, diatomaceous earth, oils, dyes, stabilizers,
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94/166 preservatives, polymers, coatings and combinations thereof. The additive can comprise an oil, a gum, a resin, a clay, a polyoxyethylene glycol, a terpene, a viscous organic, a fatty acid ester, a sulfated alcohol, an alkyl sulfonate, a petroleum sulfonate, an alcohol sulfate, a sodium alkylbutane diamate, a sodium thiobutane dioate polyester, a benzene acetonitrile derivative, a proteinaceous material (for example, a dairy product, wheat flour, soybean meal, blood, albumin, gelatin or a combination thereof) or a combination of them. The thickener can include, but is not limited to, a long chain polyethylene glycol alkyl sulfonate, a polyoxyethylene oleate or a combination thereof. The surfactant can be a heavy petroleum oil, a heavy petroleum distillate, a polyol fatty acid ester, a polyethoxylated fatty acid ester, an aryl alkyl polyoxyethylene glycol, an alkyl amine acetate, an alkyl aryl sulfonate, a poly-alcohol water, analkyl phosphate or a combination thereof. The anti-caking agent can be a sodium salt, a diatomaceous earth with calcium carbonate or a combination thereof. For example, the sodium salt can include a sodium salt of monomethyl naphthalenesulfonate, a sodium salt of dimethyl naphthalenesulfonate, a sodium sulfite, a sodium sulfate or a combination thereof. Suitable agricultural acceptable carriers include vermiculite, charcoal, sugar factory carbonation sludge, rice husk, carboxymethylcellulose, peat, perlite, fine sand, calcium carbonate, flour, alum, starch, talc, polyvinylpyrrolidone, peanut shell or a combination of them.
FERTILIZERS AND INOCULANTS
[0250] In addition, the system 11 described here can be configured to determine the concentration of a fertilizer in an environment that is used in applications with or without pesticide. System 11 can be used to detect a “fertilizer” (for example, a liquid fertilizer), a “fertilizer material from
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95/166 micronutrients ”(for example, boric acid, a borate, a boron frit, copper sulfate, a copper frit, a copper chelate, a sodium tetraborate decahydrate, an iron sulfate, an iron oxide , iron and ammonium sulfate, an iron frit, an iron chelate, a manganese sulphate, a manganese oxide, a manganese chelate, a manganese chloride, a manganese frit, a sodium molybdate, acid molybdic, a zinc sulfate, a zinc oxide, a zinc carbonate, a zinc frit, zinc phosphate, a zinc chelate or a combination thereof), an insecticide (for example, an organophosphate, a carbamate, a pyrethroid, an acaricide, an alkyl phthalate, boric acid, borate, fluoride, sulfur, haloaromatic substituted urea, hydrocarbon ester, bio-based insecticide or a combination thereof), herbicide (eg, chlorophenoxy compound, nitrophenolic compound, nitrocresolic, a dipyridyl compound, an acetamide, an acid the aliphatic, an anilide, a benzamide, a benzoic acid, a benzoic acid derivative, anisic acid, an anisic acid derivative, a benzonitrile, benzothiadiazinone dioxide, a thiocarbamate, a carbamate, a carbanylate, chloropyridinyl, a cycle derivative -hexenone, a cyclohexenone derivative, a dinitroaminobenzene derivative, a fluordinitrotoluidine compound, isoxazolidinone, nicotinic acid, isopropylamine, isopropylamine derivatives, oxadiazolinone, phosphate, phthalate, picolinic acid compound, triazine, urine, triazine, triazine, triazine endotal, sodium chlorate or a combination thereof), fungicide (for example, a substituted benzene, a thiocarbamate, an ethylene bis dithiocarbamate, a thiophthalmitamide, a copper compound, an organomercury compound, an organotin compound, a compound of cadmium, anilazine, benomyl, cyclohexamide, dodine, etridiazole, iprodione, metlaxyl, triforin or a combination thereof), a molluscicide, an algaecide, an alteration o in plant growth, a bacterial inoculant (for example, a bacterial inoculant of the genus Rhizobium, an inoculant
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96/166 bacterial of the genus Bradyrhizobium, a bacterial inoculant of the genus Mesorhizobium, a bacterial inoculant of the genus Azorhizobium, a bacterial inoculant of the genus Allorhizobium, a bacterial inoculant of the genus Sinorhizobium, a bacterial inoculant of the ge Kluyvera, a bacterial inoculant of the Az genus a bacterial inoculant of the genus Pseudomonas, a bacterial inoculant of the genus Azospirillium, a bacterial inoculant of the genus Bacillus, a bacterial inoculant of the genus Streptomyces, a bacterial inoculant of the genus Patreenibibes, a bacterial inoculant of the genus Paracoccus, a bacterial inoculant of the genus Enterobacter, a bacterial inoculant of the genus Alcaligenes, a bacterial inoculant of the genus Mycobacterium, a bacterial inoculant of the genus Trichoderma, a bacterial inoculant of the genus Gliocladium, a bacterial inoculant of the genus Glomus, a bacterial inoculant of the genus Klebsiella or a combination thereof, a fungal inoculant (for example, a fungal inoculant from the family Glomeraceae, a fungal inoculant from the family Claroidoglomeraceae, a fungal inoculant from the family Gigasporaceae, a fungal inoculant from the family Acaulosporaceae, a fungal inoculant from the family Saccul osporaceae, a fungal inoculant from the family fungus of the family Pacidsporaceae, a fungal inoculant of the family Diversisporaceae, a fungal inoculant of the family Paraglomeraceae, a fungal inoculant of the family Archaeosporaceae, a fungal inoculant of the family Geosiphonacea, a fungal inoculant of the family Ambisporacea, and a funnant innocent fungal inoculant of the Dentiscultataceae family, a fungal inoculant of the Racocetraceae family, a fungal inoculant of the phylum Basidiom ycota, a fungal inoculant of the phylum Ascomycota, a fungal inoculant of the phylum Zygomycota, or a combination thereof. The fertilizer may include, but is not limited to, ammonium sulfate, ammonium nitrate, ammonium sulfate nitrate,
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97/166 ammonium chloride, ammonium bisulfate, ammonium polysulfide, ammonium thiosulfate, aqueous ammonia, anhydrous ammonia, ammonium polyphosphate, aluminum sulfate, calcium nitrate, calcium ammonium nitrate, calcium sulfate, calcined magnesite, limestone calcitic, calcium oxide, calcium nitrate, dolomitic limestone, hydrated lime, calcium carbonate, diamonium phosphate, monoammonium phosphate, magnesium nitrate, magnesium sulphate, potassium nitrate, potassium chloride, potassium and magnesium sulphate, potassium sulphate, sodium nitrates, magnesian limestone, magnesia, urea, urea-formaldehydes, urea and ammonium nitrate, urea and ammonium sulphate, sulfur-coated urea, polymer-coated urea, diurea isobutylidene, K2SO4-2MgSO4, kainite, silvinite, kieserite, Epsom salts, elemental sulfur, marl, ground oyster shells, fish meal, oil cakes, fish manure, blood bran, rock phosphate, super phosphates, slag, bone meal, wood ash, manure, bat guano, peat, compost, green sand, cottonseed meal, cottonseed meal, feather meal, crab meal, fish emulsion, humic acid or a combination thereof. The plant's fertilizer or biostimulant can also include extracts of plants, algae and seaweed.
GROWTH REGULATORS
[0251] System 11 described here can be configured to determine the amounts of plant growth regulator (s) or plant growth stimulator compound (s) that are included in a spray application and can be applied together with or without a pesticide. Plant growth regulators include, but are not limited to: a cytokinin or acytokinin derivative, cytokinin or cytokinin derivative may comprise kinetin, cis-zeatin, trans-zeatin, 6-benzylaminopurine, dihydroxizeatin, N6- (D2 -isopentenyl) adenine, ribosylzeatin, N6- (D2-isopentenyl) adenosine, 2-methylthio-cis-ribosylzeatin, cis-ribosylzeatin, trans-ribosylzeatin, 2methylthio-trans-ribosilzeatin, ribosilzeatin-5-monosphosphine, 5-monosphosphine,
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N6-dimethylaminopurine, deoxizeatin 2'-riboside, 4-hydroxy-3-methyl-trans-2butenylaminopurine, ortho-topoline, meta-topoline, benzyladenine, orthomethyltopoline, meta-methyltopoline or a combination thereof. Where the plant growth-stimulating compound comprises an auxin or auxin derivative, the auxin or auxin derivative may comprise an active auxin, an inactive auxin, a conjugated auxin, a naturally occurring auxin or a synthetic auxin, or combinations of the same. Where the plant growth stimulating compound includes an auxin or auxin derivative, the auxin or auxin derivative may include indole-3-acetic acid, indole-3-pyruvic acid, indole-3-acetaldoxime, indole-3-acetamide, indole -3acetonitrile, indole-3-ethanol, indole-3-pyruvate, indole-3-acetaldomaxima, indole-3-butyric acid, a phenylacetic acid, 4-chloroindol-3-acetic acid, polyglutamic acid, trinexpac, a conjugate with glucose auxin, or combinations thereof.
SURFACES
[0252] The system 11 described can also be configured to detect and measure concentrations of one or more surfactants. Surfactants are usually amphiphilic organic compounds, which means that they contain hydrophobic groups (their tails) and hydrophilic groups (their heads). Therefore, a surfactant contains a water-insoluble (or oil-soluble) component and a water-soluble component. Fluorotensive agents have fluorocarbon chains. Siloxane surfactants have siloxane chains. Many important surfactants include a polyether chain that ends in a highly polar anionic group. Polyether groups often comprise ethoxylated sequences (similar to polyethylene oxide) inserted to increase the hydrophilic character of a surfactant. On the other hand, polypropylene oxides can be inserted to increase the lipophilic character of a surfactant. Most commonly, surfactants are classified according to the polar head group as: non-ionic, anionic, cationic or
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99/166 amphoteric. A nonionic surfactant does not have groups loaded on its head. The head of an ionic surfactant carries a positive or negative net charge. If the charge is negative, the surfactant is more specifically called anionic; if the charge is positive, it is called cationic. If a surfactant contains a head with two groups of opposite charges, it is called zwitterionic. Commonly used carboxylate surfactants, which are the most common surfactants, include: alkyl carboxylates (soaps), such as sodium stearate. More specialized species include sodium lauryl sarcosinate and fluorostensives based on carboxylate, such as perfluorononanoate, perfluorooctanoate (PFOA or PFO). The anionic surfactants commonly used contain anionic functional groups in your head, such as sulfate, sulfonate, phosphate and carboxylates. Prominent alkyl sulphates include ammonium lauryl sulphate, sodium lauryl sulphate (sodium dodecyl sulphate, SLS or SDS) and sodium lauryl sulphate-related alkyl ether sulphates (sodium lauryl ether sulphate or SLES) and sodium myrosulphate. Others include: docusate (sodium dioctyl sulfosuccinate), perfluorooctane sulfonate (PFOS), perfluorobutanesulfonate, alkyl aryl ether phosphates and alkyl ether phosphates. Commonly used cationic surfactants include: octenidine dihydrochloride and other permanently charged quaternary ammonium salts: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyl amethyldiettium chloride , dioctadecyldimethylammonium bromide (DODAB). Zwitterionic (amphoteric) surfactants are also commonly used and cationic and anionic centers are linked to the same molecule. The cationic part is based on primary, secondary or tertiary amines or quaternary ammonium cations. The anionic part can be more variable and include sulphonates, as in sulcenes CHAPS (3 - '(3-colamidopropyl) dimethylammonio'-lpropanesulfonate) and cocamidopropyl-hydroxysultaine. Betaines like
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100/166 cocamidopropyl betaine has a carboxylate with ammonium. The most common biological zwitterionic surfactants have a phosphate anion with an amine or ammonium, such as phosphatidylserine phospholipids, phosphatidylethanolamine, phosphatidylcholine and sphingomyelin. Non-ionic surfactants, many of which contain long-chain alcohols. Among these, fatty alcohols, cetyl alcohol, stearyl alcohol and cetostearyl alcohol (predominantly consisting of cetyl and stearyl alcohols) and oleyl alcohol stand out. Commonly used nonionic surfactants include: trisloxanes, polyethylene glycol (C2nH4n + 2On + 1), diethylene glycol (C4H10O3), polyoxyethylene glycol (Brij) alkyl ethers: CH3- (CH2) 10-16 (O-C2H4) 1- 25-OH, octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ethers: CH3- (CH2) 10-16- (O-C3H6) 1-25OH, glycoside alkyl ethers: CH3- (CH2) 10-16 - (O-glucoside) 1-3-OH, decyl glucoside, lauryl glycoside, octyl glycoside, polyoxyethylene glycol ethers: octylphenol: C8H17- (C6H4) - (O-C2H4) 1-25-OH, Triton X-100, polyoxyethylene glycol alkylphenol ethers: C9H19- (C6H4) - (O-C2H4) 1-25-OH, nonoxynol-9, glycerol alkyl esters, glyceryl laurate, polyoxyethylene glycol sorbitan alkyl esters: polysorbate, alkyl esters of sorbitan: cocamide ida MEA, cocamide DEA, dodecyldimethylamine oxide, block copolymers of polyethylene glycol and polypropylene glycol: poloxamers, polyethoxylated tallow amine (PO AND THE). Furthermore, in ionic surfactants, the counter-ion can be: monatomic / inorganic: cations: metals: alkali metal, alkaline earth metal, transition metal, anions: halides: chloride (Cl—), bromide (Br-), iodide (I-), polyatomic / organic cations: ammonium, pyridinium, triethanolamine (TEA), anions: tosyl, trifluoromethanesulfonates and methyl sulfate.
OSMOPROTECTORS
[0253] System 11 described here can also be configured to measure one or more osmoprotectors. Osmoprotectors include a variety
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101/166 of classes of compounds, such as sugars (sucrose and trehalose), amino acids: glutamine, proline and alanine, charged amino acids, such as glutamate, Bglutamate, glutamate betaine, polyols (glycerol, arabitol and inositol) and heterosides (glycosylglycerol and mannosucrose) . They include a variety of classes of compounds: sugars and derivatives, amino acids and derivatives and polyols and derivatives. They include solutes, such as betaine or ectoin. Betaine glycine or trimethylglycine is a preferred osmoprotectant. Among common sugar osmoprotectors, sucrose and trehalose are accumulated by microorganisms in response to salt stress. Some of the unusual osmoprotective sugars include gentiobiosis, melibiosis, maltose, turanosis, raffinose, stachyose, verbascose, altrose, palatinose and cellobiosis, which are often reported in plants. These can also be catabolized to increase the accumulation of other osmoprotectors. Some of the sugar alcohols (polyols) include glycerol, inositol, mannitol, sorbitol, arabitol and maltitol. Osmoprotection pathways have potential applications in transferring halotolerance to commercially important crops. Commonly used osmoprotectors also include: glycosylglycerol, dimethylsulfoniopropionate, glutamine, glutamine amides, proline, N-acetylated diamino acids, ectoins and betaine glycine.
PROTECTORS
[0254] System 11 described in this document can be configured to provide quantities and forecasts for protector concentrations. The common protectors are summarized and selected from the list of: 1,8-naphthalic anhydride, naphthalene-1,8-dicarboxylic anhydride, N diclormide, Ndialyl-2,2-dichloroacetamide, Cloquintocet, Ciometrinil (Z) -cyanomethoxy-imino (phenyl) acetonitrile, Oxabetrinyl (Z) -1,3-dioxolan-2-ylmethoxy-imino- (phenyl) acetonitrile, Fenchlorazol, Flurazol benzyl-2-chloro-4-trifluoromethyl-1,3-thiazol-5-carboxylate, Fenclorim 4,6-Dichloro-2-phenylpyrimidine, Benoxacor (RS) -4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine and Fluxofenim 4-chloro-2,2,2
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102/166 trifluoroacetophenone 0-1,3-dioxolan-2-ylmethyloxime. A formulation comprising protective agents can be applied to crops (e.g., cereal crops such as corn, rice, wheat and sorghum) against pre-emergent thiocarbamate and chloroacetanilide herbicides or for post-emergence herbicides in broadleaf crops. Additional protectors include: 1,8-naphthalic anhydride, naphthalene-1,8-dicarboxylic anhydride, N, N-dialyl2,2-dichloroacetamide, cyanomethyl (Z) -cyanomethoxy-imino (phenyl) acetonitrile, oxabetrinyl (Z) - 1,3-dioxolan-2-ylmethoxyimino- (phenyl) acetonitrile, Flurazol benzyl-2chloro-4-trifluoromethyl-1,3-thiazol-5-carboxylate, Fenclorim 4,6-dichloro-2phenyl Ipirin idine, Benoxacor (RS) - 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4benzoxazine, Fluxofenim 4-chloro-2,2,2-trifluoroacetophenoneO-1,3-dioxolan-2ylmethyloxime and Mefenpir, MG-191.
HARD WATER SOLUTIONS
[0255] System 11 can also be configured to measure the composition and percentage of solutes in hard water. Hard water contains high levels of calcium (Ca), magnesium (Mg), sodium (Na) and / or iron (Fe), aluminum (Al) and zinc (Zn). Hard water solutes comprising Al, Ca, Mg, Na, Fe and Zn cations (positively charged ions) bind to negatively charged herbicide molecules. Often, the association between herbicides and these cations makes the herbicide ineffective. Hard water also affects glyphosate. Al, Ca, Mg, Fe, Na or Zn could form a complex with glyphosate adversely affecting its activity to bind the target enzyme in the plant. If glyphosate cannot bind to the enzyme, it will not provide the proper activity necessary for weed control. The mineral content in water generally consists of calcium and magnesium ions, however, in some geographical areas, iron, aluminum and manganese can also be present at high levels. Hard water solutes are formed when water penetrates through lime and chalk deposits, composed largely of calcium and magnesium carbonates, but
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103/166 may also include chlorides, bicarbonates (HCO3-) and carbonates (CO3-2) and other ions derived from carbon dioxide. Thus, the benefit of being able to determine hard water solutes using system 11 before applying a pesticide application and adjusting the amount of pesticide for effective control is an essential benefit that can be obtained using system 11.
METHODS OF USE OF THE AGRICULTURAL PRODUCT DETECTION SYSTEM
[0256] One embodiment of a method of the present invention includes using the system 11 described above to monitor the concentration (s) of one or more pesticides or final pesticide products (broadly, agrochemicals) during a cleaning process , preparing a detoxifying solution or equipment used for processes involving pesticides, such as agricultural equipment 101 described in detail above, other agricultural equipment, seed treatment equipment or pesticide manufacturing equipment.
[0257] For example, detector (s) 15 and / or optical fiber (s) 19 are operatively connected to the equipment to receive light from an object or area of interest. The light received by the detector (s) is filtered by the spectral filter (s) 21. The spectral characteristics of the light are analyzed by system 11 to determine the concentration (s) of one or more more pesticides, final pesticide products or other agricultural parameters, such as those described above. For example, a ratio of the spectral intensity to absorbance peaks corresponding to a pesticide, pesticide end product or other chemical of interest is used appropriately to determine the concentration level. Information on the measured concentration level (s) is produced properly (for example, on a user's device), such as using the data exchange interface 25 to connect system 11 to the user's device and transmit the information to the user's device.
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[0258] For example, the step of connecting the detector (s) 15 to the agricultural equipment may include the step of mounting the detector (s) or the optical fiber (17) to the equipment adjacent to the (s) object (s) or area (s) in the equipment of interest. In certain embodiments, the step of connecting the detector (s) to agricultural equipment includes the step of moving a portable detector to a location of interest, such as manually immersing the portable unit in a solution contained in tank 103. In one or more In addition, the step of connecting the detector (s) to the agricultural equipment comprises fluidly connecting the system 11 to the agricultural equipment, so that the fluid from the agricultural equipment flows through a conduit or flow cell of the system from the which the detector (s) are configured to receive electromagnetic radiation.
[0259] In one embodiment, the method includes making a single measurement of the concentration level (S) of one or more pesticides, final pesticide products or other agrochemicals described here at a specified time. In another embodiment, the method includes monitoring the concentration levels of one or more pesticides, final pesticide products or other agrochemicals described here over a number of moments, in a substantially continuous or non-continuous manner (for example, periodic or intermittent) .
[0260] The method optionally includes the step of using system 11 described above to estimate or predict the concentration of a pesticide, final pesticide product or other agrochemical product of interest in the future, using a first measurement at time t1 and a second measurement at time t2. Alternatively, or in addition, the method optionally includes the step of estimating an amount of time remaining until a specified event related to the measured concentration levels occurs. For example, the method includes properly estimating a time remaining before the level of one or
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105/166 more agrochemicals have been sufficiently reduced below a threshold level that defines a safe zone. This can be determined by measuring the level of the agrochemical product directly or by monitoring the level of a final product of the agrochemical product and using an inverse relationship between the level of the pesticide and the level of the final product of the pesticide.
[0261] The method optionally includes sending one or more alerts to a user or user device. For example, the data exchange interface 25 properly sends an alert when (a) the predicted cumulative concentration of one or more agrochemicals is equal to or approaches the predetermined dosage limit or (b) the predicted reduced concentration of one or more agrochemical products is equal to or decreases below a predetermined dose limit corresponding to a safe zone.
[0262] In one embodiment, the method includes cleaning agricultural or other equipment, washing it with water. Alternatively, or in addition, the method optionally includes the addition of one or more cleaning or detoxifying agents to facilitate the cleaning process. For example, an agricultural detoxifying formulation can be used individually or combined with one or more cleaning agents to facilitate reducing the concentration of at least one growth regulating herbicide selected from the group comprising: a phenoxy herbicide, a benzoic acid herbicide, a pyridine herbicide, a class of quinoline herbicide or any combination thereof. Alternatively, or in addition, the method optionally also includes the use of an agricultural detoxifying formulation individually or combined with one or more cleaning agents to reduce the concentration of at least one herbicide comprising: dicamba, 2,4-D, dichorprop, dichlorprop- p, mecoprop, mecoprop-p, MCPB, MCPA or any combination thereof.
[0263] The method optionally includes determining how much of a
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106/166 agricultural detoxifying formulation is necessary to sufficiently remove an agrochemical residue or agrochemical product remaining in agricultural equipment. For example, system 11 adequately recommends a formulation amount to a user (for example, in the form of an aqueous solution, a spray adjuvant, a diluent, a powder, a resin, a coating, a powder, a lubricant, a paste, a water-dispersible gel, a medium, a granule or a tablet) to add to detoxify or clean enough: a tank, a storage tank, a bulk tank, a spray tank, a nursing tank, a rinsing tank, a seed treatment machine, bar, bar sprayer, spray platform, spray ball, emitter, container, drum, jug, receptacle, basin, chamber, nozzle, valve, solenoid, pump filter, tube , line, tube, hose, hose fitting and a spray associated with the equipment based on an initial measurement before the cleaning process starts.
[0264] The method optionally includes testing post-harvest dips, post-harvest treatment water, batch equipment and other equipment for finished agricultural products that may come in contact with pesticides, for which it would be advantageous to detect the identity, presence, and levels of pesticides that may be present.
[0265] Having described the method in general terms, several specific examples of applications of the methods and, more generally, system 11 will now be described.
APPLICATION EXAMPLE 1 - CLEANING AGRICULTURAL EQUIPMENT
[0266] In one embodiment, system 11 and the methods described in this document can be applied to the cleaning of agricultural equipment. The procedure required to properly clean agricultural equipment, for example, a spray tank, depends on several factors, including the
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107/166 composition of the spray tank, the pesticides used and the sensitivity of a crop to which the tank solution will be applied after a tank cleaning.
[0267] Referring to Figure 2, standard cleaning begins with draining any pesticide solution from tank 103 after application is complete. Tank 103 is typically filled and washed with clean water. A commercial cleaner or another is added to tank 103 to form a cleaning solution. The cleaning solution is recirculated through the passage with the spray nozzles 119 closed. The cleaning solution is left to stand in tank 103 (for example, overnight). At several points, an agitator 141 can be activated to stir the contents of the tank 103. All filters, screens and sieves 123, 131 are removed and soaked in a cleaning solution (for example, overnight). The rinse water containing the cleaning solution is drained from tank 103 and disposed of in accordance with applicable regulations. Tank 103 is again washed with clean water, which is recirculated through the equipment. The resulting rinse water is drained. Several steps are repeated as needed.
[0268] In accordance with the methods of the present invention, system 11 described above is used to detect, measure and / or quantify the amount of one or more pesticides, final pesticide products or other chemicals involved in the cleaning process in a or more points during the process. For example, any of the steps can be repeated until system 11 indicates a limit for moving to the next step in the cleaning process. System 11 can also be used at the end of the cleaning process to verify that the equipment is clean enough. At any time during the process, system 11 can be used to determine the level (s) of pesticides, final pesticide products or other chemicals to assess how cleaning is progressing and make necessary adjustments, such as adding
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108/166 more cleaning agent, repeat one or more cleaning steps or move on to the next step in the process. Shipment alerts are optionally sent to the user's device to notify when the main steps are completed or when intervention can be desired.
[0269] Commercial tank cleaners are available and recommended in many product brands. They fall into several major categories that help remove oil and water-soluble pesticides. They can also be classified as surfactants, hijackers and solubilizers. Suitable cleaning agents include: ammonia plus water, ammonia plus detergent, ammonia plus detergent and water, ammonia or commercial tank cleaner plus water, sodium hydroxide, sodium tripolyphosphate, kerosene or diesel, followed by ammonia and water, alkaline detergents and other detergents and water, sodium hypochlorite (chlorine-based bleach), fuel oil or kerosene, hydrogen peroxide plus metal ions, sulfonylurea salt and ethanolamine, sodium bicarbonate plus kerosene plus liquid detergent, liquid detergent, water or any mixture of these and described in more detail in Table 3. Any or combination of cleaning agents can be used in one or more modalities of a tank cleaning method.
TABLE 3: COMMONLY USED TANK CLEANING AGENTS
Tank cleaning agents ammonia + water commercial tank cleaner or ammonia + water ammonia + detergent ammonia + detergent + water sodium hydroxide
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Tank cleaning agents sodium tripolyphosphate alkaline detergent kerosene or diesel followed by ammonia + detergent water (sodium tri-phosphate detergent) + chlorine bleach water (sodium hypochlorite) fuel oil or kerosene hydrogen peroxide and salt metal ions water-soluble sulfonylurea and ethanolamine sodium bicarbonate + kerosene + liquid detergent liquid detergent surfactants
Water
[0270] Normally, detoxifying many spray equipment herbicides requires the use of ammonia or approved tank cleaners. Table 4 provides recommended cleaning solutions and cleaning procedures, depending on the choice of pesticide for use in spray tanks.
TABLE 4: CLEANING SOLUTIONS AND CLEANING PROCEDURES FOR USE WITH DIFFERENT PESTICIDE FORMULATIONS IN A SPRAY TANK
Pesticide Formulation Cleaning Solution Instructions 2,4-D amine, Ammonia + Shaking,
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Pesticide Formulation Cleaning Solution Instructions Dicamba detergent wash and let rest overnight, wash and rinse 2,4-D ester Baking soda + kerosene + liquid detergent Rinse inside the tank and wash the sprayer. Let stand for 2 hours, wash and rinse. Sulphonylurea,Chlorine, Sulphonamides,Imidazolinones, Triazolopyrimidines, Sulfonylamino-carbonyl triazolinones Ammonia + detergent + water Shake and let restovernight, wash and rinse. Other herbicides, insecticides Fungicides Liquid detergent Shake, wash and rinse
[0271] Although tank cleaning methods have been described in this section as being used for tanks containing a pesticide, it should be understood that the methods can also be used with tanks containing other agrochemicals.
APPLICATION EXAMPLE 2 - CLEANING OF SEED TREATMENT EQUIPMENT
[0272] In one or more modalities, the systems and methods
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111/166 described in this document can be applied to the cleaning of seed treatment equipment. Seed treatments with agrochemicals, such as pesticides, inoculants, herbicide protectors, micronutrients, plant growth regulators, seed coatings and dyes, are commonly applied to seeds using treatment machines (in general, agricultural equipment).
[0273] In certain embodiments, system 11 is used to determine the concentrations of pesticides in substances received on or in the seed treatment equipment when the seed treatment equipment is being cleaned. Commercial seed keepers (in general, seed treatment equipment) are designed to apply precisely measured amounts of pesticides to a given seed weight. There are three main types of commercial seed treaters: commercial powder treater, semi-fluid treater and direct treater (including nebulizer treater). Volumetric seed treatment equipment is commonly used to treat canola, cotton, soybeans, sugar beet, sunflower, vegetables and wheat seeds. Commonly treated seeds also include: corn sorghum, oats, rye, barley, corn, pine and most vegetable seeds. Pesticides applied as seed treatments often include fungicides and insecticides. Seed treatment materials are usually applied to a seed as dust, paste, powder or liquid. Common equipment used for seed treatment may include, but is not necessarily limited to, a drum handler, a commercial batch handler, a downstream batch handler, a continuous batch treatment system, a supply tank and / or several other tanks. Seed treatment equipment may also comprise: a tank agitator, a metering pump, a drain plug, a drain plug valve, a
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112/166 valve set, etc. Seed treatments are usually provided to the seed with additional agents, such as pesticide carriers, binders, adhesives that can make removing seed treatments from equipment problematic and complicated.
[0274] The detector (s) 15 and / or optical fibers 17 of the system 11 are properly assembled or maintained in one or more locations, so that the detectors can receive light from an object or area of interest. System 11 can be used when cleaning seed treatment equipment in ways substantially similar to the way it is used to facilitate the cleaning of agricultural equipment. Systems and methods can reduce the time required to maintain and clean equipment between seed treatment applications, thereby reducing the time that equipment is idle. The methods also help to eliminate cross-contamination that can occur between batches of different types of seeds that may require different treatments. If the seed treatment equipment has been inactive for a period of time, the sediment at the bottom of the equipment can be particularly difficult to clean and may present an increased risk of cross contamination. Thus, in certain embodiments, one or more of the detectors 15 and / or optical fibers 17 are suitably positioned to receive light from the bottom of a tank, drum attendant or other equipment on which the sediment may have accumulated. The methods described describe a safe, compatible, efficient and time-effective means for sufficient removal of a seed treatment from seed treatment machines and any other associated application equipment used to treat seeds.
[0275] Although methods of cleaning seed treatment equipment have been described in this section as being used for pesticide detection, it should be understood that the methods can also
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113/166 be used for other agrochemicals.
APPLICATION EXAMPLE 3 - INJURY REDUCTION IN CROPS
[0276] In one or more modalities, the agrochemical product detection system 11 can be applied to reduce the risk of injury to the crop. When a pesticide composition is sprayed from a tank or other vessel, a residual amount of the active pesticidal agent normally remains in the agricultural tank or vessel. This pesticide residue, if left untreated, can pose a significant problem for farmers, growers or custom operators by accidentally damaging crops and other desirable plants located near the sprayed fields or growing in areas bordering on a sprayed field. As a result, special precautions must be taken to prepare spray tanks (nursing tanks, etc.) and vases for later use after pesticide application. This problem is particularly serious for growth regulating or auxin-type herbicides, such as dicamba, where even small amounts of herbicide residues can result in significant damage to sensitive plants.
[0277] Unintentional injuries to crops may occur, especially in non-target species, if the spray tanks used in pesticide applications have not been properly cleaned. In particular, injuries can occur if pesticide residues accumulate and / or crystallize in the application equipment (tanks, lines, barriers and nozzles) before applying subsequent pesticides (herbicides, etc.) to a crop. Injuries caused by contamination of the sprayer can occur up to several months after using the sprayer, if it has not been cleaned properly before applying pesticides (dicamba, etc.). Spray sumps and pumps, spray tank surfaces, inside the upper part of the
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114/166 spray tank and around deflectors, hydraulic installations, agitation units, hoses, screens and filters must also be cleaned or replaced frequently, as they can be an important source of contamination.
[0278] Dicamba, a herbicide with benzoic acid, can be applied to leaves or soil and is used to control annual and perennial broadleaf weeds in grain and pasture crops, and is also used to control shrubs and ferns in pastures . It is commonly used to eradicate broadleaf weeds before and after they sprout. Dicamba is also used in combination with a phenoxyalkanoic acid or other herbicides to control weeds in pastures, varied terrain and non-cultivated areas (fences, roads and waste areas). Dicamba is typically formulated as a wettable solution, suspension or granules and can be applied by land-based equipment, such as a spray platform with a spray bar or spray tank, or by air. Dicamba, for example, causes significant damage to plants, even at extremely low levels of application. The remaining dicamba levels in the tank drain have been reported to be approximately 5%, with percentages greater than 5% at the nozzles of the total concentration used for spray application. Most dicot plants are sensitive to dicamba treatment. For example, sensitive plants can show herbicide damage with pronounced symptoms after spraying dicamba, even at the low level of 0.017 kg / ha, with the severity of symptoms increasing by 0.28 kg / ha and 0.56 kg / ha, application levels normally used for weed control in agriculture. However, sensitive dicot plants like tobacco can exhibit distinct symptoms of injury, even at treatment levels with dicamba as low as 0.001 to 0.01 g / ha. Soy will be sensitive to dicamba concentrations as low as
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115/166 mg / l. Many farmers discard the remaining dicamba in a tank or the rinse water from dicamba after cleaning a tank in the field. The release of dicamba in the environment through the elimination of a rinse water that contains dicamba can be found in the soil and surface waters (waterways), which can represent a concern for the life of terrestrial and aquatic plants.
[0279] Phenoxyacetic acids can also cause damage to crops. Specific examples for the use of phenoxyacetic acids as herbicide application are 2,4-D for small grains, corn, pastures, MCPA for small grains and establishment of grasses and 2,4-DB for alfalfa and soybeans. Lesions by phenoxyacetic acids can vary depending on the culture and the concentration of herbicide that remains in the equipment. For example, all phenoxyacetic acids can produce similar symptoms in sugar beet. The sugar beet leaves will be flattened on the ground a few hours after exposure to phenoxy acetic acid herbicides. Leaf petioles show symptoms of epinasia or leaf torsion, sugar beet exposed to phenoxyacetic acids in cotyledonous or in an early stage of developmental growth may develop fused petioles, which is called "stalking or" trumpeting. The growth of new leaves after exposure will generally have an incorrect shape, with wrinkled margins, parallel veins or leaf binding. Thus, overall yield and root growth can be severely affected.
[0280] Benzoic acids are another class of pesticide that can cause damage to crops. Specific examples of the use of benzoic acids (for example, dicamba) are used for corn, wheat, oats, sorghum, pastures and other areas that include non-agricultural areas. The application of dicamba that remains of residues that remain in the soil, for example, after the use of pre-planting burning procedures, can significantly reduce the
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116/166 emergence of culture. The dicamba residue in the soil in the initial growth stage can cause the symptom of “trumpeting (fused petioles). Similar symptoms of dicamba injury can occur if the dicamba residue is not properly cleaned from a tank used for subsequent spray applications on different crops or using different herbicide applications. The classic symptoms of injuries can include twisting and closing the leaves, and the development of the first true leaves can be inhibited. Burning in the leaves is also symptomatic of the dicamba lesion.
[0281] Pyridines form another class of pesticide capable of producing damage to the crop. Pyridines, such as clopyralid, for use as herbicide applications for small grains, sugar beet, corn and grass pastures, picloram for uncultivated land and pastures and triclopyr for uncultivated land and lawn pasture are widely used in agricultural practices. Symptoms of pyridine injury occur promptly accompanied by a hot and humid environment that favors phytotoxicity. The leaves may collapse or become flattened and the petioles may present epinastia. In addition, the leaves may be more belt-shaped. However, certain members of this class of herbicides can cause the leaves to roll upwards from the edges. Leaf curl is caused to a greater extent by clopyralid. Pyridines are also usually persistent for long periods of time in soils and can bind to other forms of organic matter, which can cause damage to plants and affect the compositional composition of the natural microbial flora and fauna in the soil environment.
[0282] Glyphosate is used as a post-emergent herbicide to control the growth of a wide variety of annual and perennial species of broadleaf weeds and weeds on cultivated land, including cotton production. Mixtures of herbicides with glyphosate may contain salts
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117/166 ammonium, which can be used as an additional fertilizer treatment. Ammonium salts (NH4 +) appear to be the active component of these fertilizer solutions and have improved the performance of a certain herbicide consistency in some weeds. Herbicides that seem to benefit from the addition of ammonium are relatively polar and weak acidic herbicides, such as sulfonylureas and imidazolinones. Glyphosate mixtures containing ammonium salts when added to a tank in a spray mixture can solubilize any crystallized dicamba residue that remains in the tank, pipes, nozzles or accessories. Therefore, glyphosate after an application of dicamba can cause unintended damage to non-target plants / crops. As a precautionary measure, any dicamba residue remaining in a tank must be detoxified and / or reduced before making any subsequent application using glyphosate.
[0283] A method of limiting or preventing any of the crop injuries described above includes using the methods described here (for example, Application Example 1, supra) to ensure that agricultural equipment (for example, a spray tank ) is sufficiently clean between pesticide applications. This reduces or eliminates cross-contamination and crop damage that can result from insufficiently clean equipment.
[0284] In addition, in one or more modalities, the method comprises using the system to monitor concentration levels of a cross-contaminated pesticide (for example, a pesticide other than the one being intentionally applied) during an application process. pesticide. If system 11 detects a sudden increase in the concentration of the cross contaminant, the system will properly generate a dispatch alert or alarm to alert that cross contaminant evidence has been detected, alerting the user to a possible pesticide residue crystal (eg herbicide ) that has dried on the inner surface of a
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118/166 line or a nozzle or accessory breaking free and then went into solution at a given time, resulting in an immediate increase in the level of concentration of the pesticide with cross contaminants. This can also help to reduce or eliminate crop damage.
[0285] Although the crop damage reduction methods in this section are described as being used with pesticides, it should be understood that the methods can also be used with other agrochemicals. APPLICATION EXAMPLE 4 - CLEANING EQUIPMENT THAT WAS NOT
COMPLETELY DRAINED
[0286] In one embodiment, the system 11 and the methods described in this document can be applied to the cleaning of agricultural equipment, such as a tank, which is configured so that it is impossible or undesirable to completely drain the fluid equipment after use. In other words, the system can be used in a method of cleaning agricultural equipment, in which agricultural equipment is never completely drained of fluid. Thus, in one or more modalities, a method within the scope of this disclosure comprises the step of cleaning agricultural equipment without completely draining agricultural fluid equipment. When the fluid in the agricultural equipment is not completely drained, the effectiveness of the cleaning agents can be greatly reduced and they may not even be effective in removing the pesticide residue that remains in the tank or other agricultural equipment. The method (s) described here provides a substantial benefit in this context. The spectral characteristics of the fluid can be monitored throughout the cleaning process to determine when the agrochemical product of interest has been sufficiently removed from the equipment. As needed, the cleaning process can be adjusted based on the information provided by system 11 to add one or more detoxifying formulations directly to the solution remaining in the tank or
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119/166 on other equipment. This can provide a more effective detoxification and / or removal process of the agrochemical product for the user (farmer, producer, custom operator, etc.).
APPLICATION EXAMPLE 5 - ESTIMATE AND PROVIDE FORECASTS FOR SAFE ZONE REQUIREMENTS
[0287] In one or more modalities, the agrochemical product detection system 11 and methods described herein can be applied in a method of predicting (1) absolute concentration of the pesticide at a predetermined time point or at several time points or ( 2) a safe zone concentration when the concentration of pesticides is low enough that during a spray or exchange with another pesticide, the level remaining in the equipment does not cause damage to a plant (target or non-target plant), a field of plants, a part of the plant, a waterway or a natural environment. If desired, forecasts can be formed only two or three measurements. Thus, systems and methods adequately predict when it will be safe to use agricultural equipment for subsequent applications or to dispose of the rinse safely after cleaning procedures have been performed. In addition, system 11 and the method described here can adequately confirm that the requirements of the safe zone have been met using measurement data at the end of a cleaning process. System 11 and the methods described in this document can also send dispatches to users in the form of safe zone recommendations, based on information provided by the user and / or stored in the system about the types of pesticides used and the types of crops to which they are applied. they are applied to reduce the variability of results related to the risk of injury caused by pesticide contaminants in plants, plant fields, parts of plants, waterways and other natural environments.
[0288] The safe zone levels, when reached, are
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120/166 properly sent to the user as dispatch alerts. For example, a first dispatch alert can be sent to the user when a first safe zone for a first type of crop with a greater tolerance for cross-contamination with the pesticide (s) involved is reached and a second dispatch can be sent to the user when a second safe zone for a second type of culture with a lower tolerance to cross contamination is achieved.
[0289] Concentrations of dicamba and 2,4-D that met the requirements for the safe zone developed for tank cleaning procedures after applications using dicamba and 2,4-D are recommended at or below 15 mg / ml. There was a moderate lesion in the soybean and cotton plants with a concentration of approximately 15 mg / l to 50 mg / l of dicamba or remaining 2,4-D. Concentrations in this range are considered in the warning zone. Concentrations of dicamba and 2,4-D above 50 mg / l are considered in the danger zone where the remaining herbicidal residue or rinse water containing the residue can be expected to cause damage to a plant, plant field, part plant, waterways or a natural environment. In one or more modalities, the respective dispatch alerts are generated when one or more of these concentration levels are detected by the system 11.
[0290] The systems and methods described in this document are also advantageous when used in the context of pre-planting cutting procedures, followed by subsequent applications of pesticides to plants or plant fields. Pre-planting burning is commonly used in many regions (mainly in the USA) to prepare fields for planting. The advantages of using pre-planting firing methods include: improved control of problematic weeds, cleaning the bed at the time of planting, better establishment of desired crops and freedom of rotation with short pre-planting intervals. The commonly used commercial herbicides,
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121/166 recommended for pre-planting soy burning procedures, include: acetochlor, 2,4-D, 2,4-D amine, chlorimurone + flumioxazin + pyroxasulfone, chlorimurone + tribenurone, metribuzin + chlorimurone, dimethenamide, imazetapyr + glyphosate , glyphosate, metribuzin, paraquat, metribuzin + chlorimurone, paraquat + metribuzin, tifensulfurone + tribenurone, imazetapyr, safluenacil, flumioxazin, chlorimurone and pyroxasulfone. Although common herbicides for pre-planting corn burning include: 2,4-D, dicamba, atrazine, iodosulfurone, s-metoachlor atrazine + glyphosate, paraquat, thifensulfurone + tribenurone, flumetsulam + clopiralid, metribuzin, saflufenacil, flumioxazin and acetum. Common herbicides used for pre-planting burning before planting direct wheat include: glyphosate, dicamba, paraquat, saflufenacil. metsulufurone, chlorosulfurone and carfentrazone.
[0291] After the application of the burning herbicides, the agricultural equipment must be carefully cleaned and the residual herbicides in the equipment sufficiently reduced to the expected safe zone levels for specific herbicide or herbicide mixtures. In any of the above scenarios, the systems and methods described in this document facilitate and expedite sufficient detoxification of agricultural equipment. For example, after executing a pre-planting cut application, the user can detoxify or reduce the pesticide in agricultural equipment in less time, providing the equipment's availability with a faster response for use in another application. Alternatively, the initial concentration of herbicide residues can be determined by the system prior to the application of the burning herbicide to confirm that the initial levels of herbicide concentration are consistent with the requirements for herbicide burning applications and then after use , to determine when safe zone levels during equipment cleaning procedures are followed.
[0292] Although the forecasting methods in this section are described as being used for pesticides (eg herbicides),
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122/166 if it is understood that the methods can also be used for other agrochemicals.
APPLICATION EXAMPLE 6 - CULTURE LOSS RISK MANAGEMENT
[0293] In one or more modalities, the systems 11 and methods described in this document can also be applied to crop loss risk management. The increased risk of injury from herbicide applications to non-target or sensitive plants can occur as more herbicides are used and new technologies are brought into the field. The development of new herbicide technologies, such as the production of herbicide-resistant crops, for example, soy, cotton, wheat and alfalfa, increases the likelihood that new and current herbicides will be used in crop management practices. In addition, new technologies for pesticides, fungicides and fertilizers continue to evolve and the risk factors associated with these technologies continue to change.
[0294] The Risk Management Agency, associated with the US Department of Agriculture, may approve one or more endorsements (for example, Good Management Practices - BMP Endorsement) for crop insurance products based on preferred detoxification procedures / cleaning agents recommended for spray application equipment used to apply agricultural pesticides.
[0295] An insurance product may include a culture risk insurance policy and an endorsement set associated with the culture insurance policy. The crop risk insurance policy component can guarantee risk of loss due to contamination by pesticide residues that remains in the equipment after an application and can be selective depending on the pesticide, as well as the target or non-target crops used with the application. The ancillary terms and conditions of the culture insurance policy may require that
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123/166 the insured (farmer, producer, custom operator) establishes or has BMP guidelines in place that have a compliance plan for cleaning and maintaining agricultural equipment used for crop pesticide spraying applications.
[0296] The systems and methods described in this document can be used to verify and ensure that a user has achieved compliance with the BMP guidelines or other ancillary insurance policy requirements related to reducing the risk of pesticide damage. The systems and methods described in this document can be used to accurately measure the concentration of the pesticide or a final pesticide product currently present on or on the equipment, in order to base BMP or other ancillary requirements based on the recommended concentrations required for obtaining effective detoxification and / or cleaning measures that guarantee reduced risks for plants, plant fields, parts of plants, nearby waterways or other natural environments can be developed. In addition, the systems and methods described here can also provide a timestamp to verify that proper cleaning of the equipment has been achieved to meet safe zone levels. In addition, or alternatively, reduced insurance premiums and / or other benefits under the policy may be conditioned on verification of the BMP or other ancillary requirements through the use of the systems and methods described in this document. Thus, the use of the recommendations provided by the system can result in a reduced cost for the deductible, as well as a reduction in premium rates for culture commodities insurance. Therefore, the method (s) of the present invention can be used to obtain lower average premiums for crop insurance associated with a higher likelihood of indemnity payments if losses occur. The increase in compensation payments for crop insurance is proportionally related to an increase in the
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124/166 percentage of total liabilities (maximum indemnity), which also implies a higher premium subsidy rate.
[0297] The systems and methods described in this document can minimize (1) the amount of liability insurance required by the user to accompany a culture insurance policy and (2) the amount of payment for a liability insurance policy provided by the company insurance to reduce the risk of injury to a crop, resulting in less crop loss (for example, loss of revenue related to crop loss or reduction in crop yield). The systems and methods described here can also provide savings on crop commodity insurance and reduce the risk of crop loss, as designated in various risk categories, such crops include, but are not limited to: corn, soy, wheat, small grains (oats, rye, barley), fodder (alfalfa, corn silage, silage), fruits, vegetables and flowers for use in commodities.
[0298] The systems and methods described in this document can also minimize the amount of liability insurance required to cover the security risks associated with tank cleaning operations. The systems and methods described in this document also facilitate safer and greener solutions for detoxifying or removing a pesticide or pesticide residue from equipment compared to commercially available cleaning products.
[0299] The systems and methods described in this document can also reduce or eliminate the risk of damage caused by the rinse disposal in a plant, a plant field, a part of the plant, a waterway or a natural environment.
APPLICATION EXAMPLE 7 - MANUFACTURING AND PRODUCTION EQUIPMENT
[0300] In one or more modalities, the systems and methods
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125/166 described in this document can be applied to the manufacture or development of a pesticide or pesticide-based product. The main steps in the manufacture of a pesticide are (a) preparation of process intermediates; (b) introduction of functional groups; (c) coupling and esterification; (d) separation processes, such as washing and pickling; and (e) purification of the final product. In the manufacture of pesticides, an active ingredient in pesticides is first synthesized in a factory or chemical laboratory. Then, a formulator, for example, mixes the active ingredient with a carrier (for liquid pesticides) or with inert powders or dry fertilizers (for powder pesticides). Active ingredients and vehicles are added to the formulation, as in the manufacture of a pesticide supplied in a liquid formulation or in active ingredients and inert powders, as in the manufacture of a pesticide supplied in a powder formulation. Each of these steps can include a monitoring step performed by system 11, in which the concentration of the precursor (s), pesticide (s) or intermediate (s) related to the pesticide (s) or product (s) ) final (s) must be measured in a single moment or using continuous monitoring. This multi-stage process can involve several pieces of equipment, such as those used in the synthesis of pesticides, increase production and batch formulation up to the final liquid, dust, paste, granules, etc. containing the pesticide. In this multi-stage process, many different manufacturing equipment can be included in production and can include, among others, tanks, mixers, grid devices, spray devices, adapters, hoses, etc. to synthesize, manufacture, formulate, dilute, distribute and pack the pesticide for delivery as a product provided, but not limited to, a farmer or producer for use in agriculture.
[0301] The systems and methods described in this document can be used during any stage of the pesticide manufacturing process to determine the concentration of the precursor, intermediate or
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126/166 final pesticide product to ensure that the desired or precise concentration is delivered during manufacture. The systems and methods described here can also be used at any stage of the process to determine whether any of the equipment involved has been properly cleaned and / or maintained after manufacturing is complete. The systems and methods described in this document can also be used to monitor the concentration of a pesticide in any of the equipment used in the processes from manufacturing to packaging.
[0302] Although the manufacturing and development methods in this section are described as being used for pesticides (eg herbicides), it should be understood that the methods can also be used for other agrochemicals.
APPLICATION EXAMPLE 8 - RETURNABLE / REUSABLE CONTAINER CHECK
[0303] Agrochemicals, such as pesticides and pesticide-related products (eg, pesticide precursors or other chemicals involved in the manufacture of pesticides) are often transported and stored in drums or other containers. In addition, it is common for drums or other containers to be returned to the seller for reuse or to be reused after their contents are exhausted. Drums generally include one or more valves or couplers (for example, from Micro Matic) that can be used to pump material from the container. Drums and any accessories, couplers and / or valves must be cleaned before being returned and / or reused. Failure to clean the containers can lead to the formation of crystals or dry solids which can affect the functionality of the couplers, valves or other accessories and which can lead to the deterioration of the seals associated with them.
[0304] Thus, in one or more modalities, system 11 can be
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127/166 used to check the cleanliness of returnable or reusable drums and their accessories at any time before, during or after cleaning. For example, a drum can be checked prior to cleaning to identify any agrochemicals in or on the drum. This information can be used to determine how the drum will be cleaned (for example, what type of cleaner or other chemicals to use). The drum can be checked during cleaning to monitor progress. The drum can be checked after cleaning to confirm that the drum has been cleaned properly. Likewise, a supplier who accepts the return of containers that should have been cleaned can use system 11 to check the containers after receipt, to confirm that the customer has done an appropriate cleaning job.
EXAMPLE OF CONCEPT TEST 1 - PROOF OF CONCEPT OF AGRICULTURAL PRODUCTS DETECTION SYSTEM
[0305] In this section, procedures used to validate the concept of systems 11 and the methods disclosed above are described.
[0306] In a test procedure, a spectrophotometer 13 with UV VIS features was operationally connected to a stainless steel flow cell 17 with a gap of 1 cm using solarization-resistant optical fibers 19. One of the two different light sources 39 was connected by a second solarization resistant fiber optic cable 19 to the opposite side of flow cell 17. Light sources 39 delivered light through optical fibers 19 and flow cell 17, and spectrophotometer 13 detected the light after it interacted with the substance received in the flow cell. It has been found that the ideal light source can vary depending on conditions and objectives. For example, light in the UV range between 220 nm and 290 nm allows good visibility of the absorbance of phenoxy herbicides (auxin type). The light sources 39 used for testing included a DH-2000 light source, comprising a halogen light source and a deuterium light source, and a PV200 UV VIS light source,
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128/166 comprising a xenon pulse lamp. Both light sources tested 39 transmitted UV and VIS to flow cell 17. The flow cell was equipped with two transparent windows 37 which allow UV and VIS free transmission through the windows.
[0307] To facilitate the concept test, a recirculation test system with certain characteristics corresponding to conventional agricultural spraying equipment was set up. The recirculation test system included a pump 111 configured to recirculate fluid from a spray tank with 100 I recirculation 103. Pump 111 was configured to circulate liquid from tank 103 through a series of three boom lines 107 made of different material (stainless steel, carbon fiber and rubber). At least one spray nozzle 119 was connected to each boom 107. The recirculation test system included a return line configured to transport sprayed fluid from each nozzle 119 back to tank 103. This completed a loop of recirculation through the lines spray heads, spray boom line 107 and spray nozzles 119, back to main tank 103.
[0308] Several different arrangements of the detection system 11 have been tested in the recirculation test system described above. In a first arrangement, system 11 was fluidly coupled to the recirculation test system on the return line downstream of a nozzle 119. More specifically, the return line from nozzle 119 to tank 103 has been modified to pass through the flow cell 17 of system 11. In a second arrangement, a sampling line provided fluid communication between one end of the bar line and flow cell 17. In a third arrangement, a sampling line provided fluid communication between the tank and flow cell 17. In a fourth arrangement, the cuvette samples were removed from the tank by means of a tap and placed in a cuvette holder.
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129/166 configured to store 2 ml of sample. The cuvette holder was operationally arranged between light 39 and spectrophotometer 13, so that the spectrophotometer could receive light from the light source after interaction with the sample in the cuvette holder. Several other arrangements of the system have also been tested. The tests demonstrated that spectral data useful for a fluid can be obtained in any of the arrangements described here.
[0309] The same test procedure was used for each of the four system 11 provisions specifically listed above: spectrophotometer 13 was initially switched on and a dark measurement was made without light from light source 39. Twenty liters of tap water were delivered to the recirculation test system. The light source 39 was then turned on and a blank measurement was made. Dicamba was then added to the recirculation test system to obtain a calibrated dicamba concentration of 6 g / l in the recirculation test system. After recirculating the dicamba for ten minutes, the spectrophotometer 13 was used to obtain spectral traces, including spectral data in the range of 220 to 240 nm and in the range of 250 to 280 nm. In each of the four test arrangements listed above, at least three spectral data samples from the dicamba solution were obtained using the spectrophotometer 13. The data for each sample was wirelessly transferred to a laptop and processed, based on data from measurement readings in the dark and in white, to isolate the spectral data relevant to dicamba in the solution. The data processed for each sample were shown on the laptop screen. Some of the processed data was analyzed using two methods of analysis described below.
[0310] In a first analysis method, the peak absorbance ratios of the spectra at certain wavelengths were calculated and compared to the corresponding reference ratios for auxin-type herbicides. It was found that at least certain herbicides could
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130/166 be positively identified based on the absorbance ratios at least at the following wavelengths: 276 nm: 230 nm; 285 nm: 230 nm; 259 nm: 230 nm; 237 nm: 230 nm; 252 nm: 230 nm; 252 nm: 285 nm. These reasons have been found to be useful for identifying and distinguishing various auxin-like herbicides. For example, when an absorbance rate of a substance at 276 nm: 230 nm is greater than the absorbance rate at 285 nm: 230 nm, spectral characteristics suggest that the substance probably contains a dicamba herbicide than an amine herbicide 2, 4-D. It is believed that agrochemicals can be identified using spectral characteristics at other wavelengths in other modalities.
[0311] In a second analysis method, the absorbance peak values of the acquired spectra were compared with predetermined standards to quantify a concentration of herbicide in the sample. The second method of analysis can be performed after the identification of a specific herbicide using the first method of analysis discussed above or as an independent method of analysis. In an example of the second method of analysis, absorbance at a spectral peak (for example, a known spectral peak for a herbicide or class of herbicides) can be used to determine a concentration of herbicide in a substance. For example, peak absorbance at a wavelength in the range of 220 nm to 240 nm or in a range from 250 nm to 280 nm, or alternatively, a peak absorbance ratio at two wavelengths can be identified and compared to an empirically derived standard (for example, a standard curve) that compares the absorbance at the respective wavelength or the respective absorbance ratio with the concentration of an herbicide of interest. This comparison was found to provide useful estimates of the concentration of herbicide in a sample during the test. Match the detected peak absorbance or absorbance rate to the standards
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131/166 predetermined (for example, standard curves) allows the quantification of auxin-type herbicides or other agrochemicals. It was also found that the concentration can be estimated based on a comparison (for example, a ratio) of an absorbance at a spectral peak with an absorbance level without a peak (for example, in the background) at a defined wavelength , such as absorption at a wavelength of 200 nm.
[0312] Additionally, based on the tests performed, it is believed that obtaining spectral measurements at different times in time can allow extrapolation and prediction of herbicide changes (for example, changes in concentration) during a cleaning process. Using absorbance readings at two or more points in time, a projection line or curve can be generated that models the herbicide concentration (or other characteristic of the herbicide) versus time. The slope of the projection line can be an estimate of the rate at which the herbicide concentration is changing. Using this determined rate, it is possible to predict an extrapolation for the time when the herbicide concentration will reach zero or a predetermined desired level.
[0313] Using the systems arrangements and the second method of analysis described above, the concentration of dicamba in a recirculation test system was tested during a triple rinse treatment procedure. A triple rinse treatment procedure is an industry standard procedure for removing herbicides from spray equipment. This triple rinse treatment carried out involved washing the lines and the tank of the recirculation test system three times. After each wash, 10 I of fresh water was added to the recirculation test system and circulated for a period of ten minutes. After each recirculation step, system 11 was used to determine the concentration of herbicide in a
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132/166 sample of the recirculation test system. The results are shown in
Table 5.
TABLE 5 - REMAINING DICAMBA IN A TANK AFTER RINSE
CLEANING
Stage Absorbancepeak at 280 nm Concentration of Dicamba Additioninitial of Dicamba 4.2 6.0 g / l Rinse ^the end of 1 3.0 1.5 g / l Rinse ^the end of 2 0.4 220 mg / l End of 3 Rinse 0.2 35 mg / l
[0314] The results of this experiment show that the system 11 described above can effectively detect and measure the quantity (for example, concentration) of agrochemical product in agricultural equipment.
[0315] Although the tests described in this section were carried out with herbicides, it is believed that system 11 and the methods would work the same for other types of agrochemicals
EXAMPLE OF CONCEPT TEST 2 - SPECTRICAL SIGNATURES OF AGRICULTURAL PRODUCT
[0316] As explained above, system 11 can be used to detect, measure, analyze and monitor one or more agrochemicals, such as pesticides, final pesticide products, fertilizers or mixtures of fertilizers and pesticides. More specifically, system 11 can be used to detect
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133/166 a signature or distinct spectral marker associated with one or more agrochemicals or concentrations of agrochemicals. The spectral signature can then be used to identify the agrochemical product or the concentration of agrochemical products in various methods, as described above. This section describes tests performed to show that agrochemicals of various types have discernible spectral signatures that are useful for this type of analysis.
[0317] As described in more detail below, a test procedure was used to obtain spectral data for various agrochemical product solutions. Table 6 shows a peak absorbance ratio at wavelengths of 230 nm and 280 nm for certain tested pesticides. In addition, the spectral traces for various agrochemicals are shown in Figures 25A to 31F. As shown in Table 6, the absorbance rate at wavelengths of 230 nm and 280 nm differs between pesticides. Thus, in one or more modalities, this reason can be used as a signature to identify a pesticide when using the systems and methods described above. As indicated in Figures 25A to 31F, the spectral line for each of the different agrochemical products is unique and, therefore, provides a signature that distinguishes the agrochemical product from all others. It will be appreciated, therefore, that the systems and methods described in this document can be used to detect and identify agrochemicals, at least in part, based on their spectral signature (for example, spectral trace, absorbance ratio at certain wavelengths) .
[0318] To generate the spectral data mentioned in Table 6 and in Figures 25A to 31F, the following test procedure or a functionally equivalent procedure was used. The samples of the respective agrochemical products were measured using a high-level plate reader
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134/166 BioTek SYNERGY HTX UV-VIS yield (BioTek Instrument Inc.). A solution of each of the agrochemicals was made at a concentration of 1X and then recirculated through a spray tank of 100 I for a period of 10 min before being sampled. For certain agrochemicals, 1X pesticide solutions were further diluted, as shown in Figures 26 to 29 (in the Figures, the number before 'X' indicates the dilution multiple of the original 1X solution). The solutions were pipetted using a multichannel pipettor (200 pl each) on a UV-Star® microplate (GREINER BIO-ONE). Serial dilutions of some of the samples were prepared by adding MilliQ water to each sample to raise the final volume to 200 μΙ. The absorbance of the samples was measured at a wavelength of at least 200 nm to a maximum of 800 nm. For many of the samples, the absorbance at 230 nm and 280 nm wavelengths was recorded (as explained below, some classes of pesticides showed absorbance peaks adjacent to these wavelengths). The absorbance at a wavelength of about 250 nm was also recorded for several of the samples and used as a spectral control to distinguish between the wavelength regions of 230 nm and 280 nm.
[0319] Figures 25A to 25F show the absorbance spectra detected in a wavelength range from 200 nm to 400 nm of various concentrations of formulated MCPA (LVE ARGITONE®) (Figure 25A), MCPB (Figure 25B), mecoprop (methylchlorophenoxypropionic acid, MCCP) (Figure 25C), dichloroprop-P (Figure 25D), mcoprop-P (Figure 25E) and dichloroprop (Figure 25F). The sample X concentrations listed on the right margin of each of Figures 26A to 26F are multiples of the 1X concentrations listed in Table 6. As can be seen, the spectra of each sample are unique. The graphs in Figures 25A to 25F include vertical bars superimposed on wavelengths of 230 ± 5 nm, 250 ± 5 nm and 280 ± 5 nm. As can be seen, each
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135/166 pesticide has a local absorbance peak adjacent to each bar of 230 ± 5 nm and 280 ± 5 nm. An absorbance ratio of about 230 nm and 280 nm differs for each agrochemical tested, as shown in Table 6. In addition, the peak absorbance at 230 nm and 280 nm decreased with the concentration of each of the pesticides in Figures 25A at 25F.
[0320] Figures 26A to 26D show the absorbance spectra detected at a wavelength from 200 nm to 400 nm of various concentrations of clopyralide (Figure 26A), formulated fluroxypyr (ALIIGARE fluxopy) (Figure 26B), pichoram (Figure 26C) and triclopyr (Figure 26D). The X concentrations of sample X listed on the right margin of each of Figures 26A to 26D are multiples of the 1X concentrations listed in Table 6. As can be seen, the spectra of each sample are unique. The graphs in Figures 26A to 26D include vertical bars superimposed on wavelengths of 230 ± 5 nm, 250 ± 5 nm and 280 ± 5 nm. An absorbance ratio at wavelengths of about 230 nm and 280 nm differs for each agrochemical tested, as shown in Table 6. In addition, for each agrochemical, the absorbance at 230 nm, 250 nm and 280 nm decreased with the concentration of each of the pesticides in Figures 26A to 26D.
[0321] Figures 27A to 27F show the absorbance spectra detected in a wavelength range from 200 nm to 400 nm of various agrochemicals, including formulated dicamba (CLASH ™) and 2,4-D (WEEDAR®) ( Figure 27A); formulated dicamba (CLASH ™) and glyphosate (ROUNDUP POWERMAX®) (Figure 27B); formulated dicamba (XTENDIMAX® VAPORGRIP®), methyl metsulfurone (MANOR®) and a combination of them (Figure 27C); a combination of formulated dicamba (XTENDIMAX® VAPORGRIP®) and MCPB (Figure 27D); a combination of formulated dicamba (XTENDIMAX® VAPORGRIP®) and mecoprop (Figure 27E) and formulated 2,4-D (WEEDAR® 64) (Figure 27F). The sample X concentrations listed in
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136/166 right margin of each of Figures 27A to 27F are multiples of the 1X concentrations listed in Table 6 for the respective chemical. As can be seen, the spectra of each sample are unique. The graphs in Figures 27A to 27F include vertical bars superimposed at wavelengths of 230 ± 5 nm, 250 ± 5 nm and 280 ± 5 nm. An absorbance ratio at wavelengths of about 230 nm and 280 nm differs for each agrochemical or combination of tested agrochemicals, as shown in Table 6. In addition, the peak absorbance at 230 nm and 280 nm decreased with the concentration of each of the pesticides or combinations of pesticides in Figures 27A to 27F.
[0322] While the examples above belong to herbicides, it has also been shown that other pesticides tested have identifiable spectral signatures. Figures 28C to 28D show the absorbance spectra detected in a wavelength range from 200 nm to 400 nm of various concentrations of the fungicide Captan (Figure 28C) and the alpha-cypermethrin insecticide (ASTOUND DUO) (Figure 28D). The sample X concentrations listed on the right margin of each of Figures 8C to 28D are multiples of the 1X concentrations listed in Table 6. As can be seen, the spectra of each sample are unique. The graphs in Figures 25A to 25F include vertical bars superimposed on wavelengths of 230 ± 5 nm, 250 ± 5 nm and 280 ± 5 nm. As can be seen, an absorbance ratio at about 230 nm and 280 nm differs for each agrochemical tested, as shown in Table 6. In addition, the peak absorbance at 230 nm and 280 nm decreased with the concentration of each of the pesticides in Figures 25A to 25F. TABLE 6: PESTICIDES FOR DETECTION, MEASUREMENT AND QUANTIFICATION
Composition Chemical Description Active ingredient (1X solution) Amax. λ 230/280 nm AbsSpectral Ratio (R): 230/280 Panel Number and Letter Number MCPA formulated Herbicide 13.11 g / l 3,639 / 1.293 R: 25A
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Composition Chemical Description Active ingredient (1X solution) Amax. λ 230/280 nm AbsSpectral Ratio (R): 230/280 Panel Number and Letter Number (L.V.E. Argritone®) 2.81MCPB Herbicide 18.2 g / l 3,598 / 1,588 R:2.27 25B Mecoprop Herbicide 14.16 g / l 3.562 / 3.503 R:1.01 25C Dichlorprop-P Herbicide 0.01 g / l 0.245 / 0.073 R: 3.35 25D Mecoprop-P Herbicide 0.01 g / l 0.611 / 0.134 R: 4.56 25E Dicloprop Herbicide 0.01 g / l 0.888 / 0.189 R:4.70 25F Clopyralide Herbicide 0.050 g / l 3,613 / 3,111 R:1.16 26A Formulated Fluroxypyr Herbicide 0.67 g / l 3.291 / 2.809 R:1.17 26B Picloram Herbicide 0.01 g / l 3.598 / 0.879 26C Triclopir Herbicide 0.02 g / l 3,613 / 3,111 R:1.16 26D Formulated Dicamba (CLASH ™) Herbicide 6.0 g / l 3,684 / 3,010 R:1.22 27A, 27B 2,4-D (WEEDAR® 64) Herbicide 4.5 g / l 3.148 / 0.744 R:4.23 27A, 27F Glyphosate (Roundup PowerMax®) Herbicide 18.52 g / l 0.814 / 0.342 R: 2.380 27B Formulated Dicamba (Xtendimax®) Herbicide 12.03 g / l 3.385 / 0.519 R:6.52 27C, 27D, 27E MetusulfuroneMethyl (Manor®) Herbicide 0.37 g / l 1.234 / 0.114 R:10.82 27C Captan Fungicide 6.2 ml / l 3,561 / 1,592 R:2.24 28C Alpha-cypermethrin (Astound® Duo) Insecticide 2.5 g / l 3.474 / 1.707 R:2.04 28D
[0323] Although the above examples belong to pesticides, it has also been shown that other tested agrochemicals have identifiable spectral signatures. Figure 28A shows the absorbance spectra detected in a wavelength range from 200 nm to 400 nm of various concentrations of the fertilizer, RHIZO-LINK®, in the 9-15-3 ratio (nitrogen / phosphorus / potassium), which has a 1X concentration of 100 ml / l. Like
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[0324] Table 7 provides a non-exhaustive list of other fertilizers that (based on the successful identification of spectral signatures of other agrochemicals described here) are believed to have an identifiable spectral signature.
TABLE 7: OTHER COMMON WATER SOLUBLE FERTILIZERS
USED AVAILABLE FOR PLANTS FOR DETECTION AND MEASUREMENT
Fertilizer description General percentage of active ingredient Urea 46% nitrogen Ammonium nitrate 33% nitrogen Ammonium sulfate 21% nitrogen Calcium nitrate Variable Diamonium phosphate 18% nitrogen Monoammonic Phosphate 11% or less of nitrogen; 48% phosphate Super triple phosphate variable Potassium nitrate 44% potassium Potassium chloride 60 to 62% potassium
[0325] Figure 28B shows the absorbance spectra
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139/166 detected in a wavelength range of 200 nm to 400 nm of various concentrations of the nonionic surfactant, ALLIGARE SURFACE ™, which has a concentration of 1X of 0.625 ml / l. As can be seen, the spectra for the ALLIGARE SURFACE ™ samples are unique when compared to the spectra for the other agrochemicals shown in Figures 25A to 31F. Figure 28B includes vertical bars superimposed on the wavelengths of 230 ± 5 nm, 250 ± 5 nm and 280 ± 5 nm. As can be seen, an absorbance ratio of about 230 nm and 280 nm differs from the other tested agrochemicals. In addition, the absorbance peak at 230 nm and 280 nm decreased with the concentration of the surfactant in the sample.
[0326] Figure 29 shows the absorbance spectra at a wavelength from 150 nm to 750 nm of various concentrations of an inoculant, bacillus thuingiensis, with an optical density of 5.84, which has a concentration of 1X of 1, 55x10 ⁸ spores / ml. As can be seen, the spectra for the inoculant samples are unique when compared to the spectra for the other agrochemicals shown in Figures 25A to 31F. The inoculant exhibited an absorbance peak at a wavelength of about 255 nm. Combined products that contain an inoculant with a pesticide can also be distinguished due to the segregation of their absorbance peaks. For example, a combination product may exhibit an absorbance peak at a wavelength of 230 nm +/- 5 nm due to the pesticidal component as described above and another absorbance peak at a wavelength of 255 nm +/- 5 nm, as shown in Figure 29.
[0327] Figures 30A to 30D show the absorbance spectra detected from different final pesticide products. For example, Figure 30A shows the absorbance spectra detected in a wavelength range from 200 nm to 500 nm for dichlorosalicylic acid (DCSA), a final product of dicamba, in various concentrations indicated at
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140/166 right. Figures 30B to 30D show, respectively, the absorbance spectra detected in a wavelength range from 200 nm to 400 nm for 2-chloroanisole, 3-chloroanisole and 2,5-chloroanisole, each being a final dicamba product. , in various concentrations listed on the right. DSCA is shown in Figure 30A having an absorbance peak around 310 nm, and the absorbance at the 310 nm peak is shown decreasing with concentration. The spectra for each of the final chloroanisole products exhibited distinct spectral peaks at about 230 nm, 250 nm and 260 nm (Figures 30B to 30D), and the absorbance at the peaks tends to decrease with concentration. Thus, Figures 30A to 30D show that certain final pesticide products have identifiable spectral fingerprints that can be detected and analyzed using the systems and methods described above.
[0328] As explained above, the apparatus is particularly useful for detecting a contaminating pesticide or a contaminating trace of a pesticide that can remain as residue on agricultural equipment subsequently used for or with another agrochemical product. Figures 31A to 31F show detected spectral data that illustrate the viability of this technique. Figure 31A shows spectral data for a dicamba solution, which has a pronounced absorbance peak at 280 nm. Figure 31C shows spectral data for a substantially pure glufosinate solution and Figure 31B shows spectral data for a glufosinate solution that is contaminated with residual dicamba. As can be seen, the contaminated sample shows a lower absorbance peak at about 280 nm, caused by the residual dicamba. The systems and methods described above can be configured to dispatch an alert indicating the detection of the residual dicamba when a lower absorbance peak for the residual dicamba is displayed.
[0329] Likewise, Figure 31C shows spectral data
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141/166 for an imidacloprid solution, which has a pronounced absorbance peak at 275 nm. Figure 31C shows spectral data for a substantially pure glufosinate solution and Figure 31D shows spectral data for a glufosinate solution that is contaminated with residual imidacloprid. As can be seen, the contaminated sample shows a lower absorbance peak at about 275 nm, caused by the residual imidacloprid. Likewise, Figure 31F shows spectral data for an azoxystrobin solution that is contaminated with residual imidacloprid. The contaminated azoxystrobin sample also exhibits an absorbance peak less than 275 nm. The systems and methods described above can therefore be configured to send an alert indicating the detection of the residual imidacloprid when a lower absorbance peak for the residual imidaclopride is displayed. It is also considered possible to detect other agrochemicals based on unexpected minor peaks in the spectral data based on the test data.
COMPOSITIONS CONTAINING AGRICULTURAL PRODUCT AND MARKING DYES OR MARKING PIGMENTS AND METHODS FOR USING THESE COMPOSITIONS
[0330] Any of the devices described here can be used to detect and / or quantify a pesticide or other agrochemical that has been combined with a marker dye or a marker pigment. Marker dyes and marker pigments can be combined with pesticides or other agrochemicals in a composition and used as an alternative means to detect and measure the amount of a pesticide in a liquid.
[0331] Tables 8 and 9 provide lists of illustrative dye and marker pigments suitable for this purpose. The dye and marker pigments listed in Tables 8 and 9 absorb in spectral bands
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TABLE 8: SAMPLES OF DYES AND MARKING PIGMENTS
WITH AMAX IN THE UV BAND, FOR USE WITH PRODUCTS
AGROCHEMICALS
Color ofPigment orDyeHighlighter Code / Description Amax(nm) UV / VIS Blue ADA3209 * (UV visible fluorescent blue organic pigment) 408 UV / VIS Blue ADA3216 (Fluorescent Blue Visible in UV) 377 UV Blue ADA3217 (Organic Pigment Green-Fluorescent Blue Visible in UV) 404 UV / VIS Blue ADA3218 365 UV Blue ADA3230 393 UV Blue ADA5205 398 UV Green ADA6798 (Organic PigmentFluorescent Green Visible in UV) 397 UV Green ADA9102 (Organic PigmentYellow / Fluorescent Green visible in UV) 250 a320 UV Orange ADA3204 378 UV
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Color ofPigment orDyeHighlighter Code / Description Amax(nm) UV / VIS Orange red ADA3210 390 UV Red ADA2041 (Organic PigmentFluorescent Red Visible in UV) 342,408,470 UV / VIS Red ADA3202 (Organic pigmentthermofluorescent red visible in UV) 390 UV Red ADA3215 (Red PigmentUV Visible Fluorescent) 390 UV Red ADA3232 (Organic PigmentUV Visible Fluorescent) 365 UV Red ADA3233 (Red PigmentUV Visible Fluorescent) 382 UV Red ADA3245 360 UV Red ADA4160 390 UV Red and blue ADA5762 (Organic Pigment UV-ARed / UV-C Blue BifluorescentVisible in UV) 381,272 UV Red ADA6826 (UV visible thermofluorescent organic red dye) 390 UV
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Color ofPigment orDyeHighlighter Code / Description Amax(nm) UV / VIS Red,Yellow green ADA7226 381,250 UV Red UV381A * ** 381 UV Red UV381B 381 UV Red UV382A 382 UV Brown C101 *** (Ruthenium-based dye with the structure:Ví VV H í NCSHO. > · <> A í ΊΟ X(f'OH) 546,403,338,307 UV / VIS
* Dyes and pigments with codes starting with “ADA” are available from HW Sands Corp. (Jupiter, FL).
** Dyes and pigments with codes starting with “UV” are available from OCR Solutions Corp. (Port St. Lucie, FL).
*** Dye C101 is available from Sigma-Aldrich (St. Louis, MO).
TABLE 9: SAMPLES OF DYES AND MARKING PIGMENTS
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WITH AMAX IN THE VISIBLE RANGE, FOR USE WITH PRODUCTS
AGROCHEMICALS
Color ofPigment or Marker Dye Code Name Amax (nm) UV / VIS Yelloworange E100 * Curcumin 425 to 430 VIS Yelloworange E101 * Riboflavin 430 to 435 VIS Yelloworange E101a * Riboflavin-5’-Phosphate 430 to 435 VIS Yellow E102 * Tartrazine (azo triazine dye) 425 VIS BrownRed E103 Alcanina 490 to 510 VIS Green yellow E104 * Yellow quinolineWS 406 VIS Yellow E105 Yellow Fast AB 425 VIS Yellow E106 Riboflavin-5’-SodiumPhosphate 425 VIS Yellow E107 Yellow 2G 425 VIS Yelloworange E110 *; ** Sunset Yellow FCF 490 VIS
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Color ofPigment or Marker Dye Code Name Amax (nm) UV / VIS Orange E111 Orange GGN 452 to 460 VIS Crimson E120 * Cochineal, AcidCarmin, Carmine 530 to 550 VIS Dark red E121 * Citrus Red 2 580 VIS Dark red E123 * Amaranth 555 VIS Red E124 * Ponceau 4R 530 VIS Red E127 * Erythrosine 530 VIS Red E128 Red 2G 530 VIS Red E129 * Red Allura AC 530 VIS Blue E130 Blue Indanthrene RS 630 VIS Dark blue E131 * Blue Patent V 660 VIS indigo E132 * indigo carmine 675 VIS Bluereddish E133 * Brilliant Blue FCF 590 to 610 VIS Green E140 * Chlorophyllins 440, 680 VIS Green E142 * Green S 400, 650 VIS Sea green E143 * Green Fast FCF 630 VIS
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Color ofPigment or Marker Dye Code Name Amax (nm) UV / VIS Brown E150a * Plain Caramel 500 VIS Brown E150b * Caustic SulphiteCaramel 500 VIS Brown E150c * Ammonia Caramel 500 VIS Brown E150d ** Ammonium sulphiteCaramel 500 VIS Brown E155 * HT brown 500 VIS Orange Yellow to Brown E160a * Alpha-carotene, beta-carotene, Gamma-carotene 450 VIS Orange E160b *; ** Annatto, Bixin,Norbixin 460 VIS Red E160c *; ** Oleoresin paprika, Capsanthin, Capsorubin 530 VIS RedBright aDark E160d *; ** Lycopene 550 VIS OrangeRed toYellow E160e *; ** Beta-apo-8’carotenal 445 VIS
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Color ofPigment or Marker Dye Code Name Amax (nm) UV / VIS Orange Yellow to Brown E160f * Acid ethyl esterbeta-apo- 8-carotene 450, 510 a520 VIS Yellowgolden abrownish E161a Flavoxanthin 450 VIS Orange red aYellow E161b * Lutein 430, 480 VIS Orange Red E161c Cryoptoxanthin 490 to 500 VIS Orange Red E161d Rubixanthin 490 to 500 VIS Orange E161e Violaxanthin 430, 475 VIS Purple E161f Rhodoxanthin 580 to 585 VIS Violet E161g *; ** Canthaxanthin 580 VIS Orange Red E161h Zeaxanthin 430, 480 VIS Deep Violet E161 i Citranaxantina 520 to 530 VIS Red E161j Astaxanthin 520 to 530 VIS
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Color ofPigment or Marker Dye Code Name Amax (nm) UV / VIS Red E162 *; ** Bethanine 520 to 530 VIS Orange Red E164 ** Saffron 442 VIS Red E180 * Rubine, LitholRubine BK 520 to 530 VIS Purple E182 Orcein 580 VIS Orange Red - - 625 VIS Blue VIS404A *** - 404 VIS
E-numbers with (*) are codes for substances that can be used as food additives for use in the European Union and EFTA. Ο Έ ”means“ Europe ”and has complied with the European Food Safety Authority's safety assessment and approval. E-numbers with (**) are codes for substances that can be used as food additives for use in the USA. *** Available from OCR Solutions Corp. (Port St. Lucie, FL).
[0332] A composition is provided. The composition comprises an agrochemical product and a marker dye or marker pigment.
[0333] The composition may optionally comprise more than one agrochemical product, more than one marker dye and / or more than one marker pigment. The composition can optionally comprise one or more marker dyes and one or more marker pigments.
[0334] A method is provided to detect the presence of a
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150/166 agrochemical product in a liquid. The method comprises obtaining an absorbance spectrum for the liquid. The liquid came into contact with the equipment previously exposed to a composition comprising the agrochemical product and a marker dye or marker pigment. The method also comprises comparing the absorbance spectrum with a reference absorbance spectrum for the marker dye or marker pigment. The reference spectrum for the marker dye or marker pigment having a maximum absorbance (Amax) at one or more wavelengths. The presence of an Amax in the absorbance spectrum for the liquid at the same wavelength or wavelengths indicates that the agrochemical is present in the liquid.
[0335] The equipment may comprise agricultural equipment, seed treatment equipment, manufacturing equipment (for example, pesticide manufacturing equipment, packaging lines, fill lines, chemigation equipment, fertigation equipment or a combination of any of the same).
[0336] The method may also comprise determining the concentration of the agrochemical product in the liquid. The concentration of agrochemical product in the liquid can be determined by comparing the absorbance in Amax in the absorbance spectrum for the liquid with a standard curve correlating the absorbance of the marker dye or marker pigment to the concentration of the agrochemical product.
[0337] At least one of the steps for obtaining the absorbance spectrum and comparing the absorbance spectrum with a reference spectrum can be performed using any of the devices described here, any of the systems described here, any of the accessories described here, any of the nozzles described here, or any of the tanks described here.
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[0338] Marker dyes can also be incorporated into commercial agricultural products and used to distinguish a product from another similar product or an authentic product from an imitation or counterfeit product.
[0339] A method is provided to detect a counterfeit agricultural composition. The method comprises obtaining an absorbance spectrum from an agricultural composition suspected of falsification and comparing the absorbance spectrum obtained for the agricultural composition suspected of falsification with a reference absorbance spectrum for a genuine agricultural composition. The genuine agricultural composition comprises an agrochemical product and a marker dye or marker pigment. The reference spectrum has a maximum absorbance (Amax) for the dye or pigment at one or more wavelengths. The absence of an Amax in the absorbance spectrum for the agricultural composition suspected of falsification at the same wavelength or wavelengths indicates that the agricultural composition suspected of falsification is a falsified composition.
[0340] In any of the compositions containing a marker dye or marker pigment, or in any of the methods that involve the use of a marker dye or marker pigment, the marker dye or marker pigment preferably has one or more maximum absorbance (Amax) within the ultraviolet (UV) or visible range of the electromagnetic spectrum.
[0341] Thus, the marker dye or marker pigment can have a maximum absorbance (Amax) at a wavelength between about 100 nm and about 700 nm.
[0342] For example, the marker dye or marker pigment may have one or more absorbance maximums in the UV range.
[0343] The marker dye or marker pigment can have a
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Amax at a wavelength between about 100 nm and about 410 nm.
[0344] For example, the marker dye or marker pigment can have an Amax in the wavelength between about 100 nm and about 400 nm.
[0345] The marker dye or marker pigment can have an Amax in the wavelength between about 100 nm and about 399 nm.
[0346] The marker dye or marker pigment can have an Amax in the wavelength between about 100 nm and about 398 nm.
[0347] The marker dye or marker pigment can have an Amax in the wavelength between about 100 nm and about 395 nm.
[0348] The marker dye or marker pigment can have an Amax in the wavelength between about 250 nm and about 410 nm.
[0349] The marker dye or marker pigment can have an Amax in the wavelength between about 250 nm and about 400 nm.
[0350] The marker dye or marker pigment can have an Amax in the wavelength between about 250 nm and about 399 nm.
[0351] The marker dye or marker pigment can have an Amax in the wavelength between about 250 nm and about 398 nm.
[0352] The marker dye or marker pigment can have an Amax in the wavelength between about 250 nm and about 395 nm.
[0353] The marker dye or marker pigment can have an Amax in the wavelength between about 300 nm and about 410 nm.
[0354] The marker dye or marker pigment can have an Amax in the wavelength between about 300 nm and about 400 nm.
[0355] The marker dye or marker pigment can have an Amax in the wavelength between about 300 nm and about 399 nm.
[0356] The marker dye or marker pigment can have an Amax in the wavelength between about 300 nm and about 398 nm.
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[0357] The marker dye or marker pigment can have an Amax in the wavelength between about 300 nm and about 395 nm.
[0358] The marker dye or marker pigment can have an Amax in the wavelength between about 350 nm and about 410 nm.
[0359] The marker dye or marker pigment can have an Amax in the wavelength between about 350 nm and about 400 nm.
[0360] The marker dye or marker pigment can have an Amax in the wavelength between about 350 nm and about 399 nm.
[0361] The marker dye or marker pigment can have an Amax at a wavelength between about 350 nm and about 398 nm.
[0362] The marker dye or marker pigment can have an Amax in the wavelength between about 350 nm and about 395 nm.
[0363] The marker dye or marker pigment can have an Amax at a wavelength between about 250 and about 320 nm.
[0364] The marker dye or marker pigment can have an Amax at one or more wavelengths selected from the group consisting of: about 250 nm, about 272 nm, about 307 nm, about 338 nm, about 342 nm, about 360 nm, about 365 nm, about 377 nm, about 378 nm, about 381 nm, about 382 nm, about 390 nm, about 393 nm, about 397 nm, about 398 nm, about 403 nm, about 404 nm, about 408 nm and combinations of any of them.
[0365] The marker dye or marker pigment may comprise a fluorescent blue organic pigment visible in UV, with an Amax at a wavelength of about 408 nm.
[0366] The marker dye or marker pigment can comprise a fluorescent blue organic pigment visible in UV, with an Amax at a wavelength of about 377 nm.
[0367] The marker dye or marker pigment can
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[0368] The marker dye or marker pigment can comprise a fluorescent green organic pigment visible in UV with an Amax at a wavelength of about 397 nm.
[0369] The marker dye or marker pigment may comprise a fluorescent yellow / green organic pigment visible in UV, with an Amax at a wavelength of about 250 nm to about 320 nm.
[0370] The marker dye or marker pigment may comprise a fluorescent red organic pigment visible in UV, with Amax at wavelengths of about 342 nm, about 408 nm and about 470 nm.
[0371] The marker dye or marker pigment may comprise a thermofluorescent red organic pigment visible in UV, with an Amax at a wavelength of about 390 nm.
[0372] The marker dye or marker pigment may comprise a fluorescent red pigment visible in UV with an Amax at a wavelength of about 390 nm.
[0373] The marker dye or marker pigment can comprise a fluorescent organic pigment visible in UV with an Amax at a wavelength of about 365 nm.
[0374] The marker dye or marker pigment can comprise a fluorescent red pigment visible in UV with an Amax at a wavelength of about 382 nm.
[0375] The marker dye or marker pigment can comprise a bifluorescent organic pigment visible in UV with Amax at wavelengths of about 272 nm and about 381 nm.
[0376] The marker dye or marker pigment can
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155/166 comprise a thermofluorescent red organic dye visible in UV with an Amax at a wavelength of about 390 nm.
[0377] The marker dye or marker pigment may comprise a ruthenium-based dye with Amax at wavelengths of about 307 nm, about 338 nm, about 403 nm and about 546 nm.
[0378] The marker dye or marker pigment may comprise a combination of two or more of any of the marker dyes or marker pigments described here.
[0379] The marker dye or marker pigment can have one or more absorbance maximums in the visible range of the electromagnetic spectrum.
[0380] The marker dye or marker pigment can have an Amax at a wavelength between about 400 nm and about 700 nm
[0381] For example, the marker dye or marker pigment can have an Amax at a wavelength between about 410 nm and about 700 nm.
[0382] The marker dye or marker pigment can have an Amax at a wavelength between about 425 nm and about 625 nm.
[0383] The marker dye or marker pigment can have an Amax at a wavelength within a range of about 425 to about 430 nm.
[0384] The marker dye or marker pigment can have an Amax at a wavelength within a range of about 430 nm to about 435 nm.
[0385] The marker dye or marker pigment can have an Amax at a wavelength within a range of about 490 nm to about 510 nm.
[0386] The marker dye or marker pigment can have a
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Amax at a wavelength within a range of about 452 nm to about 460 nm.
[0387] The marker dye or marker pigment can have a
Amax at a wavelength within a range of about 530 nm to about 550 nm.
[0388] The marker dye or marker pigment can have a
Amax at a wavelength within a range of about 590 nm to about 610 nm.
[0389] The marker dye or marker pigment can have a
Amax at a wavelength within a range of about 510 nm to about 520 nm.
[0390] The marker dye or marker pigment can have a
Amax at a wavelength within a range of about 450 nm to about 500 nm.
[0391] The marker dye or marker pigment can have a
Amax at a wavelength within a range of about 580 nm to about 585 nm.
[0392] The marker dye or marker pigment can have a
Amax at a wavelength within a range of about 520 to about 530 nm.
[0393] The marker dye or marker pigment can have an Amax at one or more wavelengths selected from the group consisting of: about 400 nm, about 406 nm, about 425 nm, about 430 nm, about 440 nm, about 442 nm, about 445 nm, about 450 nm, about 460 nm, about 470 nm, about 475 nm, about 480 nm, about 490 nm, about 500 nm, about 530 nm, about 546 nm, about 550 nm, about 555 nm, about 580 nm, about 625 nm, about 630 nm, about 650 nm, about 660 nm, about 675 nm, about 680 nm and combinations of
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157/166 any of these.
[0394] The marker dye or marker pigment can have an Amax at about 425 nm, about 530 nm or about 625 nm.
[0395] The marker dye or marker pigment can comprise curcumin, riboflavin, riboflavin-5'-phosphate, riboflavin-5'-sodium phosphate, tartrazine, alkaline, Quinoline WS Yellow, Fast AB Yellow, 2G Yellow, Sunset FCF Yellow , GGN orange, cochineal, carminic acid, carmine, Citrus red 2, Amaranth, Ponceau 4R, Erythrosine, Red 2G, Allura AC red, Indanthrene RS blue, Patent V blue, Patent V blue, Indigo carmine, Brilliant FCF blue, chlorophylline, Verde S, Verde Fast FCF, a common caramel, caustic sulfite caramel, ammonia caramel, ammonia sulfite caramel, HT brown, alpha-carotene, beta-carotene, gamma-carotene, annatto, bixin, norbixin, paprika oleoresin, capsanthin , capsorubine, lycopene, beta-apo8'-carotenal, beta-apo-8-carotenic acid ethyl ester, flavoxanthin, lutein, cryoptoxanthin, rubixanthin, violaxanthin, rhodoxanthin, canthaxanthin, zeaxanthin, citranaxanthin, astaxanthin, betanthin, rubanthine, betanthrane orcein or a combination of any of them.
[0396] When the marker dye or marker pigment comprises a dye or pigment with an Amax in the visible range of the electromagnetic spectrum, the dye or pigment is preferably a dye or pigment that has been approved as a food additive in Europe and / or the United States . These dyes and pigments include, but are not limited to, curcumin, riboflavin, riboflavin-5'-phosphate, tartrazine, Quinoline WS Yellow, Sunset FCF Yellow, cochineal, carminic acid, carmine, Citrus Red 2, amaranth, Ponceau 4R, erythrosine, Allura Red AC, Blue Patent V, indigo carmine, Blue Bright FCF, a florophylline, Green S, Green Fast FCF, common caramel, caustic sulfite caramel, Ammonia Caramel, Sulfite Ammonia Caramel, HT Brown, alpha-carotene, beta-carotene, range -carotene, annatto, bixin,
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158/166 norbixin, oleoresin from paprika, capsanthin, capsorubin, lycopene, beta-apo8'-carotenal, beta-apo-8-carotenic acid ethyl ester, lutein, canthaxanthin, bethanine, saffron and ruby dyes. The marker dye or marker pigment can comprise any combination of two or more of these dyes or pigments.
[0397] For example, the marker dye or marker pigment may comprise one or more chlorophyllins with Amax at about 440 nm, at about 680 nm or both at about 440 nm and about 680 nm.
[0398] As another example, the marker dye may comprise a simple caramel with an Amax at about 500 nm.
[0399] When the marker dye comprises a rubine dye, the rubine dye may comprise Lithol Rubine BK.
[0400] The marker dye or marker pigment may comprise tartrazine, erythrosine or a combination thereof.
[0401] In any of the compositions or methods, the agrochemical product may comprise any of the agrochemical products described herein. For example, the agrochemical product can comprise a pesticide, a fertilizer, a plant growth regulator, a biostimulant or a combination of any of them.
[0402] When the agrochemical product comprises a pesticide, the pesticide may comprise a herbicide, an insecticide, a fungicide, a nematicide, a virucide, an acaricide, a molluscicide, an algaecide, a bactericide or a combination of any of them.
[0403] For example, the pesticide can comprise a herbicide.
[0404] When the pesticide comprises a herbicide, the herbicide may comprise an auxin herbicide (for example, a phenoxy herbicide, a benzoic acid herbicide or a combination thereof).
[0405] When the herbicide comprises a phenoxy herbicide, the
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159/166 phenoxy herbicide may comprise 2,4-dichlorophenoxyacetic acid (2,4-D), 2-methyl-4-chlorophenoxyacetic acid (MCPA), 4- (4-chloro-otolyloxy) butyric acid (MCPB), mecoprop, 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), dichlorprop, dichlorprop-p, mecoprop-p, a salt of any of them, an ester or any of them or a combination of any of the same.
[0406] For example, the phenoxy herbicide can comprise 2,4-D.
[0407] When the herbicide comprises a benzoic acid herbicide, the benzoic acid herbicide may comprise dicamba, chlorambene, 2,3,6-trichlorobenzoic acid (2,3,6-TBA), a salt of any of them, an ester of any of them, or a combination of any of them.
[0408] For example, the benzoic acid herbicide may comprise dicamba.
[0409] For example, in any of the methods or compositions, the agrochemical product may comprise dicamba and the marker dye may comprise tartrazine.
[0410] As another example, in any of the methods or compositions, the agrochemical product may comprise 2,4-D and the marker dye may comprise erythrosine.
[0411] As another example, in any of the methods or compositions, the agrochemical product may comprise dicamba and the marker dye or marker pigment may comprise a dye or pigment having an Amax at about 625 nm.
[0412] In any of the methods or compositions, the ratio of the agrochemical to the dye or pigment can be from about 10: 1 to about 1: 100.
EXAMPLE - SPECTROPHOTOMETRIC MEASUREMENT AND IDENTIFICATION OF PESTICIDES USING MARKER DYES
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[0413] UV-VIS spectra were obtained for formulated dicamba herbicides (CLASH ™; 56.8% 3,6-dichloro-o-anisic acid diglycolamine salt) and 2,4-D (WEEDAR® 64; 48 , 6% 2,4dichlorophenoxyacetic acid, dimethylamine salt) supplied separately or in combination with marker dyes used as distinctive markers for each of the herbicides (Figures 32A to 32H). The formulated dicamba and 2,4-D herbicides were supplied as 1X solutions following the recommended usage rates, so that the dicamba was at a concentration of 6.0 g / l and 2,4-D at a concentration of 4,533 g / l. The solutions containing herbicide were then diluted to a concentration of 0.5X (a recommended usage rate of 0.5X) from the original formulated product, so that the concentration of dicamba was 3.0 g / l and the concentration of 2, 4-D was 2.267 g / l. Additional dilutions were prepared for both herbicides, as listed in Figures 32A and 32B.
[0414] Two distinct marker dyes, as described in Table 9, were selected for use with the two herbicides. A yellow tartrazine dye was selected for use in combination with dicamba and a red erythrosine dye was selected for use in combination with 2,4-D. The yellow tartrazine marker dye was supplied in a solution with a molecular weight of 534.36 grams / mol and diluted by adding 1 drop of dye (from a 100 pl pipette tip) to 1 ml of sterile deionized water to form a concentration 1X for the yellow dye. Likewise, the erythrosine red marker dye was supplied in solution with a molecular weight of 879.86 grams / mol and then also diluted by adding 1 drop of dye (from a 100 pl pipette tip) to 8 ml of sterile deionized water to form a 1X concentration for the red dye. Further dilutions of each of the marker dyes were prepared as listed in Figure 32C (for the yellow dye) and Figure 32D (for the red dye).
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[0415] The marker dyes were combined with the herbicides dicamba and 2,443. In particular, starting with the initial 1X solutions of the herbicides and dyes, the formulated dicamba was mixed with the yellow dye in a 10: 1 ratio (dicamba: yellow dye) and the formulated 2,4-D was mixed with the red dye in the 3: 1 ratio (2,4-D: red dye). The resulting mixtures of herbicide and dye were designated as 1X solutions and were then subjected to a series of dilutions adding the appropriate amount of sterile deionized water. These dilutions are listed in Figures 32E and 32F, together with the herbicide ratios: dye in parentheses (dicamba: yellow dye in Figure 32E and 2,4-D: red dye in Figure 32F). The concentrations of herbicide and dye in the ratios in parentheses in Figures 32E and 32F are given in relation to the 1X concentrations of formulated solutions of herbicide and dye.
[0416] In addition, mixtures 1: 1 and 2: 1 of the dicamba / yellow dye and 2,4-D / red dye compositions were prepared, starting with 1X solutions (dicamba 10: 1: yellow dye and 3: 1 2, 4: D: red dye) described above. Dilutions of these 1: 1 and 2: 1 mixtures were then prepared by adding an appropriate volume of sterile deionized water. The dilutions are shown in Figures 32G and 32H. The reasons in Figures 32G and 32H are dicamba / yellow dye reasons: 2-4D / red dye.
[0417] The solutions were pipetted (200 pl each) on a UV-STAR® microplate (GREINER BIO-ONE). Spectral traces using a wavelength of 200 to 700 nm (+/- 5 nm) were collected using a BioTek SYNERGY HTX plate reader (BioTek Instruments Inc.). Spectral signatures and maximum absorbance spectra were collected individually for each herbicide (dicamba and 2,4-D), each of the marker dyes (tartrazine (yellow) and erythrosine (red)) and for each of the combinations herbicides / dye. Spectra are
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162/166 shown in Figures 32A to 32H.
[0418] The IIV-VIS spectra for the formulated herbicides are shown in Figure 32A for dicamba (CLASH ™) and Figure 32B for 2,4-D (WEEDAR®64). The UV-VIS spectra for the marker dyes are shown for the marker dyes in Figure 32C (yellow tartrazine dye; Amax = 425 nm) and Figure 32D (erythrosine red dye, Amax = 530 nm). The spectra for the marker dyes combined with the herbicides are shown in Figure 32E (yellow dye and formulated dicamba) and Figure 32F (red dye and formulated 2,4-D). Figures 32G and 32H provide spectra for mixtures 1: 1 (Figure 32G) and 2: 1 (Figure 32H) containing dicamba and yellow dye and 2,4-D and red dye.
[0419] The yellow and red marker dyes have distinct absorbance maximums that can be used to identify the dyes separately from each other and separately from the dicamba or 2,4D herbicides. The marker dyes can be used to detect and quantify the individual herbicides in a mixture. The yellow and red marker dyes, supplied in combination with formulated dicamba or 2,4-D individually or as a mixture with the two herbicides, were used to detect and distinguish between the different herbicides in the mixture.
[0420] Marker dyes can also be used to detect dicamba in a product formulated to reduce volatility. Dicamba herbicide (XTENDIMAX® containing 42.8% digicolamine salt of dicamba (3,6-dichloro-anisic acid) with VAPORGRIP® technology) was detected and quantified using a marker dye (an orange red dye; Amax = 625 nm ) and a device described here. A formulated dicamba solution (XTENDIMAX® VAPORGRIP®) was added using the recommended usage rate after dilution in water to a 100 I spray tank (Optima Croplands). This spray tank that was designed to
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163/166 operate with precision and function as a miniaturized version of a spray tank was connected to system 11 through tubes placed to recirculate the flow of the herbicide solution from the tank to the device. The spectral traces using the device were collected using a spectrophotometer with UV VIS features that was aligned with a 1 cm gap stainless steel flow cell that allows free movement of liquid through the flow cell using a resistant fiber optic cable solarization.
[0421] The formulated dicamba herbicide (XTENDIMAX® VAPORGRIP®) was detected using a marker dye that absorbs at an Amax of around 625 nm. After dilution in water in the 100 I spray tank, the formulated dicamba was present at the estimated recommended use rate of 12.03 g / l of dicamba (1X concentration). A series of dilutions was then prepared by adding an appropriate volume of sterile deionized water to create compositions in which dicamba was present at 6.02 g / l (0.5X), 3.01 g / l (0.25X) or 0.301 g / l (0.025 X). The tested dilutions are listed in Figure 33A.
[0422] Spectral traces using a wavelength range of 200 to 800 nm (+/- 5 nm) were generated using the device. The UV spectral range of the dicamba was compared with that of the marker. The marker dye absorbs in a UV / VIS spectral range at an Amax wavelength different from the dicamba herbicide and vapor reduction compounds in the XTENDIMAX® VAPORGRIP® formulation and therefore can be effectively used as an alternative measure to quantify the concentration of dicamba.
[0423] The UV / VIS spectra for the formulated dicamba (XTENDIMAX® VAPORGRIP®) mixed with the marker dye were collected using the apparatus and are shown in Figure 33A. The spectra for the 1X solution and the dilution series are shown and compared with a
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164/166 OX baseline control (without dicamba). The formulated dicamba resulted in two prominent spectral peaks (Amax of 230 and 280 nm). The marker dye has a maximum absorbance (Amax of 625 nm) in a different portion of the UV / VIS spectral range, and thus can be used to detect and quantify the dicamba.
[0424] To generate a standard curve for dicamba (XTENDIMAX® VAPORGRIP®), UV / VIS spectra from 200 to 800 nm were collected using a range of dicamba concentrations in mixtures that included the marker dye, as shown in Figure 33A. The Amax spectral peak (at about 625 nm) for the marker dye was correlated with the amount of dicamba using the dilutions as described in Figure 33A to show that the marker dye can be used as an alternative means to quantify the dicamba concentration. The standard curve was derived from the correlation of the maximum absorbance wavelength (Amax of about 625) for the marker dye to dicamba concentration (Figure 33B), which was linear and highly correlated (R ² value = 0.9989 ). This standard curve was used to accurately determine the concentration of formulated dicamba (XTENDIMAX® VAPORGRIP®) in a sample solution.
[0425] When introducing elements of aspects of the invention or its modalities, the articles “one”, “one”, “the one and the said” are meant to mean that there is one or more of the elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be elements other than those listed.
[0426] In view of the above, it will be seen that several advantages of aspects of the invention are achieved and other advantageous results are achieved.
[0427] Not all components illustrated or described may be necessary. In addition, some implementations and modalities can
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165/166 include additional components. Variations in the arrangement and type of components can be made without departing from the spirit or scope of the claims, as set forth in this document. Additional, different or lesser components can be supplied and components can be combined. Alternatively, or in addition, a component can be implemented by several components.
[0428] The above description illustrates aspects of the invention by way of example and not by way of limitation. This description allows one skilled in the art to make and use aspects of the invention, and describes various modalities, adaptations, variations, alternatives and uses of aspects of the invention, including what is currently believed to be the best way to carry out aspects of the invention. Furthermore, it should be understood that aspects of the invention are not limited in application to the details of construction and arrangement of the components set out in the description below or illustrated in the drawings. Aspects of the invention are capable of other modalities and of being practiced or carried out in various ways. In addition, it will be understood that the phraseology and terminology used here are for description purposes and should not be considered limiting.
[0429] Having described aspects of the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of aspects of the invention, as defined in the appended claims. It is contemplated that several changes can be made to the constructions, products and processes above, without departing from the scope of aspects of the invention. In the previous specification, several preferred embodiments have been described with reference to the accompanying drawings. However, it will be evident that various modifications and changes can be made, and additional modalities can be implemented, without departing from the broader scope of aspects of the invention, as set out in the following claims. The specification and
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166/166 drawings should be considered as illustrative and not restrictive.
[0430] When introducing elements of the present invention or its preferred modalities, the articles “one”, “one”, “the one and the said” are meant to mean that there is one or more of the elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be elements other than those listed.
[0431] In view of the above, it will be seen that the various objects of the invention are achieved and other advantageous results are achieved.
[0432] As several changes can be made to the products and methods above without departing from the scope of the invention, it is intended that all the matter contained in the description above be interpreted as illustrative and not in a limiting sense.

权利要求:
Claims (124)
[1]
1. APPLIANCE TO DETECT, MEASURE AND QUANTIFY the quantity of at least one agrochemical product in an environment, the apparatus being characterized by the fact that it comprises:
a light source a spectrophotometric device comprising a detector positioned to receive light from the light source after light has been transmitted through or reflected by said environment, wherein the spectrophotometric device is configured to measure the intensity of the light received as a function of wavelength to determine spectral characteristics of the received light; and a processor configured to measure a concentration of said agrochemical product using the spectral characteristics of the received light.
[2]
2. APPLIANCE, according to claim 1, characterized by the fact that it also comprises:
a structure that defines a space to contain a flowing fluid;
a pair of substantially transparent windows;
where the light source is positioned adjacent to one of the windows and the spectrophotometric device is positioned adjacent to the other window and the windows are arranged so that the spectrophotometric device can detect light from the light source after the light passes through the windows and interacts with the material in said space to contain the flowing fluid.
[3]
3. APPLIANCE, according to claim 1, characterized by the fact that it also comprises:
a structure that defines a space to contain a flowing fluid;
a pair of substantially transparent windows;
an optical fiber positioned so that one end of the
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2/32 optical fiber is adjacent to one of the windows; wherein one of the light source and the spectrophotometric device is positioned adjacent to the opposite end of the optical fiber, so that the optical fiber is positioned to transmit light between said light source and spectrophotometric device and the window adjacent to the opposite end of the optical fiber, with the windows, optical fiber, spectrophotometric device and light source arranged so that the spectrophotometric device can detect the light from the light source after the light passes through the optical fiber and windows and interact with any material in that space to contain the fluid that flows.
[4]
4. APPLIANCE, according to claim 3, characterized by the fact that the optical fiber is an optical fiber resistant to solarization.
[5]
Apparatus according to any one of claims 3 to 4, characterized by the fact that the optical fiber is a first optical fiber, the apparatus further comprising a second optical fiber, the second optical fiber being positioned to extend between the other between the spectrophotometric device and the light source and the window that is not adjacent to the end of the first optical fiber, the window, the first and the second optical fibers being arranged, spectrophotometric device and light source so that the spectrophotometric device can detect the light from the light source after the light passes through the first and second optical fibers and windows and the interaction with any material in said space to contain the flowing fluid.
[6]
6. APPLIANCE, according to claim 5, characterized by the fact that the second optical fiber is an optical fiber resistant to solarization.
[7]
7. Apparatus according to any one of claims 2 to 6, characterized in that said structure is selected from the group consisting of a conduit, a tube, a pipe, a fluid line, a flow cell, a bucket, spray bar, spray nozzle
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3/32 spray, a nozzle body, a filter body, a spray ball and an emitter.
[8]
Apparatus according to any one of claims 2 to 7, characterized in that the structure comprises a conduit, the conduit having a connector at one end configured to connect the conduit to an in-line filter or in-line screen.
[9]
Apparatus according to any one of claims 2 to 7, characterized in that the structure comprises a duct, the apparatus further comprising a connector at one end of the duct configured to connect the duct to a spray bar.
[10]
10. APPLIANCE, according to claim 9, characterized by the fact that the connector is a first connector, the apparatus further comprising a second connector at the opposite end of the duct configured to connect the duct to at least one of a spray nozzle, a nozzle body, a filter body, a spray ball and an emitter.
[11]
11. Apparatus according to any one of claims 2 to 7, characterized in that the structure comprises a spray nozzle with a nozzle body and the windows are installed in the nozzle body generally on opposite sides of the nozzle body.
[12]
12. Apparatus according to any one of claims 2 to 7, characterized by the fact that it further comprises a protective coating that involves at least one light source and the spectrophotometric device.
[13]
13. APPLIANCE, according to claim 12, characterized by the fact that the protective coating is at least resistant to water, shock, heat, chemicals, vibrations, solvents and dust.
[14]
14. APPLIANCE according to any one of claims 2 to 6, characterized in that said structure comprises a tank.
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[15]
15. APPARATUS, according to claim 14, characterized by the fact that the light source and the spectrophotometric device are built into a wall of the tank.
[16]
16. APPLIANCE, according to claim 14, characterized by the fact that it also comprises a protective coating that involves the light source and the spectrophotometric device.
[17]
17. APPLIANCE according to any one of claims 1 to 16, characterized by the fact that it also comprises a mounting system comprising a support for mounting the light source and spectrophotometric device on a piece of equipment, the support being built to have at least one of the following characteristics: ability to isolate the assembled component (s) from vibrations; the ability to form a mechanical interface with a corresponding piece of equipment on which the system or a component of the system is to be mounted; water resistance; heat resistance; chemical resistance to one or more agrochemicals; and combinations thereof.
[18]
18. APPLIANCE, according to claim 17, characterized by the fact that the support comprises a damper configured to isolate from vibrations at least one of the light source and the spectrophotometric device.
[19]
19. APPLIANCE, according to any one of claims 1 to 18, characterized by the fact that it also comprises a data exchange interface for transmitting information about the concentration of said agrochemical product to another device.
[20]
20. Apparatus according to any one of claims 1 to 19, characterized in that the spectrophotometric device comprises a plurality of detectors spaced apart from each other to receive said light in different locations.
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[21]
21. Apparatus according to any one of claims 1 to 20, characterized in that the spectrophotometric device comprises a filter adapted to filter a spectral bandwidth of said received light.
[22]
22. APPARATUS, according to any one of claims 1 to 21, characterized by the fact that the apparatus comprises a cuvette positioned in a light path from the light source.
[23]
23. APPARATUS, according to any one of claims 1 to 22, characterized in that the apparatus comprises an in-line flow cell adapted to receive a flow of a solution containing said agrochemical product and to direct said flow through light of the light source.
[24]
24. APPARATUS, according to any one of claims 1 to 23, characterized by the fact that the processor is configured to determine from a single absorbance reading at least one of the following:
(i) whether or not there are detectable levels of agrochemicals present; and (ii) whether or not a safe zone has been reached, using at least one of the following:
(a) a comparison of the global absorbance at a defined wavelength for a threshold level; and (b) a prediction based on the calibration of the single absorbance reading against a non-absorbent background wavelength.
[25]
25. APPLIANCE according to any one of claims 1 to 24, characterized by the fact that it further comprises a processor configured to perform at least one of the following:
estimate a concentration of agrochemical product in a
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6/32 moment Í2 based on at least one measurement of the concentration of said agrochemical product taken at time h, where h is not equal to Í2j to estimate a concentration of agrochemical product at time t3 based on at least two measurements of the concentration of the said agrochemical product carried out in time h and time Ϊ2, where Ϊ2> ti and the change in concentration from time h to time Ϊ2 represents a reduction of the agrochemical product in the environment;
estimate a concentration of the final agrochemical product at a time t3 based on at least two measurements of the concentration of that final agrochemical product performed at time h and time Ϊ2, where Ϊ2> ti and the change in concentration from time h to time Ϊ2 represents an accumulation of agrochemicals in the environment;
estimate a concentration of agrochemical product based on at least two measurements of the concentration of agrochemical product performed at time h and time Í2, where Ϊ2> h and the change in concentration from time h to time Ϊ2 represents an accumulation of agrochemicals in the environment;
estimate a concentration of agrochemical final product based on at least two measurements of the concentration of agrochemical final product taken at time h and time Ϊ2, where Ϊ2> h and the change in concentration from time h to time Ϊ2 represents a reduction of the agrochemical product in environment; and combinations thereof.
[26]
26. APPARATUS according to any one of claims 1 to 25, characterized in that it further comprises a processor configured to compare the measured concentration of the agrochemical product with a desired concentration of an agrochemical product and provide an indication of a comparison result .
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[27]
27. APPARATUS, according to any one of claims 1 to 26, characterized by the fact that it further comprises a processor configured to measure an application rate of application of the agrochemical product using the spectral characteristics of the received light.
[28]
28. APPLIANCE, according to claim 27, characterized by the fact that it further comprises a processor configured to compare the measured application usage rate of the agrochemical product with a desired application usage rate for the agrochemical product and provide an indication of the Comparation.
[29]
29. APPARATUS according to any one of claims 27 and 28, characterized by the fact that the agrochemical product for which the application rate is measured comprises a fertilizer.
[30]
30. APPARATUS, according to any one of claims 1 to 29, characterized by the fact that it also comprises a sensor configured to measure a parameter of the environment selected from the group consisting of: temperature, pH, GPS location and osmolarity.
[31]
31. APPARATUS, according to claim 30, characterized by the fact that the sensor is configured to measure an osmolarity.
[32]
32. APPARATUS, according to any one of claims 1 to 31, characterized by the fact that it also comprises a detector configured to measure a concentration in the environment of a substance selected from the group consisting of: an adjuvant, a fertilizer, a solvent, a surfactant, a dye, a colorant, a phytosanitary agent, a plant growth regulator, a micronutrient, a biological control agent, an inoculant, an osmoprotector, a protector, a marker molecule and a solute in hard water.
[33]
33. APPARATUS, according to any one of claims 1 to 32, characterized by the fact that the spectrophotometric device is
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8/32 positioned to receive light after the light interacts with a material in a structure selected from the group consisting of: a tank, a seed treatment device, a sprayer, a spray bar, a container, a nozzle, a screen nozzle, a nozzle filter, a nozzle fitting, a screen, a sieve, a valve, a duct and a spray emitted by a sprayer.
[34]
34. APPARATUS, according to claim 33, characterized by the fact that the spectrophotometric device is positioned to receive light after the light has interacted with a spray emitted by a sprayer.
[35]
35. APPARATUS, according to any one of claims 1 to 34, characterized by the fact that the spectrophotometric device is configured to measure the concentration of an agrochemical product selected from the group consisting of: an herbicide, an insecticide, a growth regulator of insects, a biological control agent, a fungicide, a bactericide, a nematicide, an acaricide, a virucide, a fertilizer and their combinations.
[36]
36. APPLIANCE according to any one of claims 1 to 35, characterized by the fact that the processor has a data exchange interface, in which the processor data exchange interface is configured to receive information about a product concentration agrochemical in the environment, said information including a series of measurements of the concentration of the agrochemical product;
the processor being configured to use information about the concentration of the agrochemical product to:
predict at time t; a first predicted rate of change of said concentration using a first set of filter parameters;
calculate an expected concentration of said agrochemical product at time Í2 based on said information and said rate
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9/32 expected change, in which time Í2 is later than time t ;
comparing said predicted concentration of said agrochemical product at time Í2 with a measurement of said concentration of said agrochemical product corresponding to time Í2 to determine the difference between the predicted concentration at time t2 and the concentration measured at time Í2j to determine a second set of parameters different from the first set of filter parameters based on the said difference between the predicted concentration at time t2 and the measured concentration at time Í2j and calculate a predicted concentration of said agrochemical product at a time Í3 using said second set of parameters filter, where time Í3 is different from time h and different from time Í2.
[37]
37. APPARATUS, according to any one of claims 1 to 36, characterized by the fact that the processor is configured to identify a substance in the environment based on the spectral characteristics of the received light.
[38]
38. APPLIANCE, according to claim 37, characterized by the fact that the substance is a substance selected from the group consisting of: a pesticide, a herbicide, an insecticide, an insect growth regulator, a biological control agent, a fungicide, a bactericide, a nematicide, an acahcida, a fertilizer, a virucide, a plant growth regulator and their combinations.
[39]
39. APPLIANCE according to any one of claims 1 to 38, characterized by the fact that it also comprises a portable electronic device with a display configured to display information from the processor.
[40]
40. APPLIANCE according to any one of claims 1 to 39, characterized by the fact that it also comprises a controlled valve
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10/32 by the processor.
[41]
41. APPARATUS, according to claim 40, characterized by the fact that the valve is connected to several different sources containing several different fluids and the processor is configured to selectively drive the valve to switch which of the various different fluids flows through the valve.
[42]
42. APPARATUS, according to any one of claims 1 to 40, characterized by the fact that it also comprises a power supply connected to at least one of the light source, spectrophotometric device and processor.
[43]
43. APPARATUS, according to any one of claims 1 to 42, characterized by the fact that the light source and the spectrophotometric device are mounted on a level gauge to be immersed in a fluid.
[44]
44. APPARATUS, according to any one of claims 1 to 42, characterized by the fact that at least one of the spectrophotometric device and the light source are mounted in a container selected from the group consisting of a tank, a drum, a tote, a jar, a barrel, a manufacturing receptacle and a storage receptacle.
[45]
45. APPARATUS, according to any one of claims 1 to 44, characterized by the fact that the spectrophotometric device comprises at least one of: a spectrophotometer, a photodiode, a matrix of photodiodes, a photosensor, a photodetector and a laser device , a microelectromechanical system, a nanosensor and a nanoelectromechanical system (NEMS).
[46]
46. APPARATUS, according to any one of claims 1 to 45, characterized by the fact that the agrochemical product comprises at least one of a fertilizer, a pesticide and a final pesticide product.
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[47]
47. APPARATUS, according to any one of claims 1 to 46, characterized in that the device further comprises an optical probe.
[48]
48. SYSTEM for analyzing the quantity of an agrochemical product in an environment, the system being characterized by the fact that it comprises:
a processor having a data exchange interface, where the processor data exchange interface is configured to receive information about a concentration of the agrochemical product in the environment of another data exchange interface, the said information including a series of measurements of the concentration of the agrochemical product;
the processor being configured to use information about the concentration of the agrochemical product to:
predicting over time a predicted first rate of change of said concentration using a first set of filter parameters;
calculate a predicted concentration of said agrochemical product at time t2 based on said information and on said predicted rate of change, where time Í2 is after time t ;
comparing said predicted concentration of said agrochemical product at time Í2 with a measurement of said concentration of said agrochemical product corresponding to time Í2 to determine the difference between the predicted concentration at time t2 and the concentration measured at time Í2j to determine a second set of parameters different from the first set of filter parameters based on the said difference between the predicted concentration at time t2 and the measured concentration at time Í2j and calculate a predicted concentration of said agrochemical at a time Í3 using said second set of parameters filter, where time Í3 is different from time h and different from
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12/32 time Í2.
[49]
49. METHOD FOR DETECTING, MEASURING AND QUANTIFYING the quantity of at least one agrochemical product in an environment, the method being characterized by the fact that it comprises:
receiving light from a light source after the light has been transmitted through or reflected by said environment;
measure the intensity of the light received as a function of the wavelength to obtain spectral characteristics of the light received; and determining a concentration of said agrochemical product using the spectral characteristics of the received light.
[50]
50. Method, according to claim 49, characterized by the fact that it further comprises directing the light that was transmitted through or reflected by said environment through an optical fiber resistant to solarization.
[51]
51. METHOD, according to any one of claims 49 to 50, characterized by the fact that it further comprises using a data exchange interface to generate information on the concentration of said agrochemical product for another device.
[52]
52. METHOD, according to any of claims 49 to 51, characterized by the fact that the receipt of light comprises the use of a plurality of detectors spaced apart from one another to receive said light in different locations after the light has been transmitted through or reflected by said environment.
[53]
53. METHOD, according to any of claims 49 to 52, characterized by the fact that it further comprises the filtering of a spectral bandwidth from said received light.
[54]
54. METHOD according to any of claims 49 to 53, characterized by the fact that receiving light comprises receiving light
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13/32 after the light is transmitted through or reflected by a material in that environment which is in a bucket.
[55]
55. METHOD according to any one of claims 49 to 54, characterized by the fact that it further comprises a material flowing in said environment through a flow cell and in which the receiving of light comprises receiving the light after it has been transmitted through or reflected by the material in the flow cell.
[56]
56. METHOD according to any one of claims 49 to 55, characterized by the fact that it further comprises estimating a concentration of agrochemical product at time t2 based on at least one measurement of the concentration of said agrochemical product taken at time h, in which h is not equal to Í2.
[57]
57. METHOD, according to claim 56, characterized by the fact that it also comprises estimating a concentration of agrochemical product in a tac moment based on at least two measurements of the concentration of said agrochemical product carried out at the time h and a time t2 Í2> h and the change in concentration from time h to time t2 represents a reduction in the agrochemical product in the environment.
[58]
58. METHOD, according to claim 56, characterized by the fact that it also comprises the estimation of a concentration of agrochemical product based on at least two concentration measurements made at time h and time Í2, where Í2> h and the change in concentration from time h to time Í2 represents an accumulation of agrochemicals in the environment.
[59]
59. METHOD, according to any one of claims 49 to 58, characterized by the fact that it also comprises the measurement of a parameter of the environment selected from the group consisting of: a temperature, a pH and an osmolarity.
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[60]
60. METHOD, according to any of claims 49 to 59, characterized by the fact that it further comprises using a detector to measure a concentration in the environment of a substance selected from the group consisting of: an adjuvant, a fertilizer, a growth regulator , a micronutrient, a biological control agent, a phytosanitary agent, an inoculant, a surfactant, an osmoprotector, a protector, a marker molecule and a solute in hard water.
[61]
61. METHOD, according to any of claims 49 to 60, characterized by the fact that light is received after being transmitted through, reflected or emitted by a material from said environment that is in a structure associated with agricultural equipment.
[62]
62. METHOD, according to any of claims 49 to 60, characterized by the fact that light is received after being transmitted through, reflected or emitted by a material from said environment that is in a structure associated with the treatment equipment of seeds.
[63]
63. METHOD, according to any of claims 49 to 60, characterized by the fact that light is received after being transmitted through, reflected or emitted by a material from said environment that is in a structure associated with equipment for the manufacture of agrochemical products.
[64]
64. METHOD according to any one of claims 49 to 63, characterized by the fact that the agrochemical product is selected from the group consisting of: a herbicide, an insecticide, an insect growth regulator, a biological control agent, a fungicide, a bactericide, a nematicide, an acaricide, a virucide and combinations thereof.
[65]
65. METHOD according to any one of claims 49 to 64, characterized by the fact that the method further comprises performing at least one of the following steps based on the determined concentration of the
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15/32 agrochemical product:
cleaning agricultural equipment that defines the environment with a cleaning agent;
stop cleaning agricultural equipment that defines the environment;
use agricultural equipment that defines the environment with another agrochemical product;
refrain from using agricultural equipment that defines the environment with another agrochemical product;
discard the rinse water in agricultural equipment that defines the environment;
add cleaning agent to rinse in agricultural equipment that define the environment; spray another equipment agrochemical product from agricultural spray that defines the environment;
avoid or interrupt the spraying of an agrochemical product solution with another agrochemical agent in agricultural spray equipment that defines the environment;
refrain from treating seeds with a seed treatment comprising another agrochemical using environment-defining seed treatment equipment;
treating seeds with a seed treatment comprising another agrochemical using environment-defining seed treatment equipment;
generate a dispatch alert indicating that a residue of the agrochemical product is present in the environment when the environment is expected to be substantially free of the agrochemical product;
add a detoxifying formulation to a solution in agricultural equipment that defines the environment;
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16/32 generate a dispatch alert indicating that the concentration of the agrochemical product in agricultural equipment that defines the environment is in a concentration of safe zone;
determine compliance with crop loss insurance requirements;
adjust a crop loss insurance premium rate and a crop loss insurance deductible;
advancing a production process for an agrochemical product to a subsequent processing step;
postpone advancing an agrochemical product production process to a later processing step;
determine whether you want to clean a drum that defines the environment; clean a returned drum that defines the environment; and refrain from cleaning a re-taken drum that defines the environment.
[66]
66. ACCESSORY for agricultural spraying equipment, the accessory being characterized by the fact that it comprises:
a conduit for containing a fluid containing agrochemical product;
a pair of windows, at least one window formed in the conduit, to at least one window configured to transmit electromagnetic radiation through the window;
a connector configured to connect the duct to at least one of an in-line filter and a spray bar; and a detector to detect electromagnetic radiation transmitted through the window associated with the fluid containing the agrochemical product, the detector being configured to detect the agrochemical product based on the electromagnetic radiation that is transmitted through the window.
[67]
67. ACCESSORY, according to claim 66, characterized by the fact that it is in combination with a spray bar, the connector
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17/32 being connected to the spray boom so that the fluid from the spray boom flows through the duct.
[68]
68. ACCESSORY, according to claim 66, characterized by the fact that it is in combination with an in-line filter, the connector being connected to the in-line filter so that the fluid of the in-line filter flows through the conduit.
[69]
69. NOZZLE for applying an agrochemical product, the nozzle being characterized by the fact that it comprises:
a nozzle body that defines an outlet opening through which a fluid containing agrochemical product can be dispensed;
a pair of windows installed on generally opposite sides of the nozzle body, at least one window formed on the nozzle body, at least one window being configured to transmit electromagnetic radiation through the window; and a detector to detect electromagnetic radiation transmitted through the window associated with the fluid containing the agrochemical product, the detector being configured to detect the agrochemical product based on the electromagnetic radiation that is transmitted through the window.
[70]
70. NOZZLE according to claim 69, characterized in that it further comprises agricultural spraying equipment, in which the nozzle is mounted on agricultural spraying equipment to spray an agrochemical product.
[71]
71. TANK to contain a solution containing agrochemicals, the tank being characterized by the fact that it comprises: a wall that at least partially encloses a space to retain the solution; and a system for determining an amount of an agrochemical product in the solution, the system comprising:
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18/32 a light source a spectrophotometric device comprising a detector positioned to receive light from the light source after the light has been transmitted or reflected by said solution, wherein the spectrophotometric device is configured to measure the intensity of the light received as a function of wavelength to determine spectral characteristics of the received light; and a processor configured to measure a concentration of said agrochemical product using the spectral characteristics of the received light, in which at least the light source and the photometric device are built into the wall.
[72]
72. KIT to install a system to determine an amount of an agrochemical product in a solution contained in a piece of agricultural spraying equipment in agricultural spraying equipment, the kit being characterized by the fact that it comprises:
a light source a spectrophotometric device comprising a detector, wherein the spectrophotometric device is configured to measure the intensity of the light received by the detector as a function of the wavelength to determine the spectral characteristics of the received light;
a processor configured to measure a concentration of said agrochemical product using the spectral characteristics of the received light, a conduit for flowing fluid in a space between the light source and the spectrophotometric device;
a connector to connect the flue to the agricultural spraying equipment, so that the fluid from the spraying equipment part
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19/32 can flow through the conduit; and instructions for connecting the connector to the part's agricultural spray equipment.
[73]
73. KIT according to claim 72, characterized by the fact that the piece of agricultural spraying equipment is selected from the group consisting of a tank, a duct, a spray boom, a spray nozzle, a spray ball and an emitter.
[74]
74. METHOD FOR MEASURING A CONCENTRATION OF A SUBSTANCE in an environment, the method being characterized by the fact that it comprises:
receiving light from a light source after the light has been transmitted through or reflected by said environment;
measure the intensity of the light received as a function of the wavelength to obtain spectral characteristics of the light received; and determine a concentration of the substance using the spectral characteristics of the light received, where the substance is selected from the group consisting of an adjuvant, a fertilizer, a growth regulator, a micronutrient, a biological control agent, a phytosanitary agent, a inoculant, a surfactant, an osmoprotector, a protector, a marker molecule and a hard water solute.
[75]
75. APPARATUS for measuring a concentration of a substance in an environment, the device being characterized by the fact that it comprises:
a light source a spectrophotometric device comprising a detector positioned to receive light from the light source after the light has been transmitted through or reflected by said environment, in which the device
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20/32 spectrophotometric is configured to measure the intensity of the light received as a function of the wavelength to determine the spectral characteristics of the light received; and a processor configured to measure a concentration of the substance using the spectral characteristics of the light received, where the substance is selected from the group consisting of an adjuvant, a fertilizer, a growth regulator, a micronutrient, a biological control agent, a phytosanitary agent, an inoculant, a surfactant, an osmoprotector, a protector, a marker molecule and a solute of hard water.
[76]
76. METHOD FOR ASSESSING THE CLEANING OF A RETURNABLE OR REUSABLE CONTAINER, the method being characterized by the fact that it comprises:
receiving light from a light source after the light has been transmitted through or reflected by a material on or flowing from the container;
measure the intensity of the light received as a function of the wavelength to obtain spectral characteristics of the light received; and determining a concentration of an agrochemical product using the spectral characteristics of the received light.
[77]
77. METHOD FOR EVALUATING THE USE OF AN AGROCHEMICAL PRODUCT, THE METHOD IS CHARACTERIZED BY THE FACT THAT UNDERSTANDS
providing a fluid that can include the agrochemical product;
receiving light from a light source after the light has been transmitted through or reflected by at least a portion of the fluid;
measure the intensity of the light received as a function of the wavelength to obtain spectral characteristics of the light received; and determining a concentration of the agrochemical product in the fluid using the spectral characteristics of the received light.
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[78]
78. METHOD, according to claim 77, characterized by the fact that it also comprises dispensing the fluid.
[79]
79. METHOD according to claim 78, characterized in that the step of receiving light from the light source comprises receiving light transmitted through or reflected by a portion of the fluid that is flowing as the fluid is being dispensed.
[80]
80. METHOD, according to any of claims 78 and 79, characterized by the fact that it further comprises determining an application rate of the agrochemical product as the fluid is being dispensed.
[81]
81. METHOD, according to claim 80, characterized by the fact that it also comprises comparing the determined application rate with a desired application rate for the agrochemical product.
[82]
82. METHOD, according to claim 81, characterized by the fact that it further comprises adjusting a flow rate at which the fluid is dispensed based on the comparison between the determined application rate and the desired application rate.
[83]
83. METHOD according to any of claims 78 to 82, characterized in that the step of dispensing the fluid comprises directing the fluid to flow through a fenestrated structure and the step of receiving light from the light source comprises receiving light that passes through the fenestrated structure.
[84]
84. METHOD according to any one of claims 77 to 83, characterized by the fact that it further comprises comparing the determined concentration of agrochemical product with a desired concentration of the agrochemical product.
[85]
85. METHOD, according to claim 84, characterized by the fact that it also comprises adjusting an amount of the agrochemical product in the fluid supplied based on the comparison between the concentration
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22/32 determined and the desired concentration.
[86]
86. METHOD according to any one of claims 77 to 85, characterized by the fact that the agrochemical product comprises one of a fertilizer and a pesticide.
[87]
87. METHOD according to any one of claims 77 to 86, the method being characterized by the fact that it further comprises performing at least one of the following steps based on the determined concentration of the agrochemical product in the fluid:
cleaning agricultural equipment in which the fluid is received with a cleaning agent;
stop cleaning the agricultural equipment in which the fluid is received;
use agricultural equipment in which the fluid is received with another agrochemical product; refrain from using agricultural equipment in which the fluid is received with another agrochemical product;
discard rinsing water in agricultural equipment in which the fluid is received;
add cleaning agent to the rinse water in agricultural equipment where the fluid is received; spraying another agrochemical product from agricultural spraying equipment where the fluid is received;
refrain from or stop spraying a solution of an agrochemical product with another agrochemical agent in agricultural spray equipment in which the fluid is received;
refrain from treating seeds with a seed treatment comprising another agrochemical agent using seed treatment equipment in which the fluid is received;
treating seeds with a seed treatment comprising another agrochemical agent using seed treatment equipment in the
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23/32 which fluid is received;
generate a dispatch alert indicating that a residue of the agrochemical product is present in the fluid when the fluid is expected to be substantially free of the agrochemical product;
add a detoxifying formulation to the fluid;
generate a dispatch alert indicating that the concentration of the agrochemical product in the fluid is in a safe zone concentration;
determine compliance with crop loss insurance requirements;
adjust a crop loss insurance premium rate and a crop loss insurance deductible; advancing a production process for an agrochemical product to a subsequent processing step;
postpone advancing an agrochemical product production process to a later processing step;
determine the possibility of cleaning a returned drum in which the fluid is received; clean a resumed drum in which the fluid is received; and refrain from cleaning a taken up drum in which the fluid is received.
[88]
88. COMPOSITION characterized by the fact that it comprises an agrochemical product and a marker dye or a marker pigment.
[89]
89. METHOD FOR DETECTING the presence of an agrochemical product in a liquid, the method being characterized by the fact that it comprises:
obtain an absorbance spectrum for the liquid, in which the liquid came into contact with the equipment previously exposed to a composition comprising the agrochemical product and a marker dye or a marker pigment; and compare the absorbance spectrum with a spectrum of
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24/32 reference absorbance for the marker dye or marker pigment, the reference spectrum for the marker dye or marker pigment having a maximum absorbance (Amax) at one or more wavelengths;
where the presence of an Amax in the absorbance spectrum for the liquid at the same wavelength or wavelengths indicates that the agrochemical product is present in the liquid.
[90]
90. METHOD according to claim 89, characterized in that the equipment comprises agricultural equipment, seed treatment equipment, manufacturing equipment, packaging lines, filling lines, chemigation equipment, fertigation equipment or a combination of any of them.
[91]
91. METHOD, according to claim 89 or 90, characterized by the fact that it also comprises determining the concentration of the agrochemical product in the liquid, comparing the absorbance in Amax in the absorbance spectrum of the liquid to a standard curve correlating the absorbance of the marker dye or from the marker pigment to the concentration of the agrochemical product.
[92]
92. METHOD, according to any one of claims 89 to 91, characterized by the fact that at least one of the steps to obtain the absorbance spectrum and to compare the absorbance spectrum with a reference spectrum is carried out using an apparatus, in accordance with with any one of claims 1 to 47 and 75, a system according to claim 48, an accessory according to any of claims 66 to 68, a nozzle according to claim 69 or 70, or a tank according to claim 71.
[93]
93. METHOD FOR DETECTING a counterfeit agricultural composition, the method being characterized by the fact that it comprises:
to obtain an absorbance spectrum of an agricultural composition
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25/32 suspected falsification compare the absorbance spectrum obtained for the agricultural composition suspected of falsification to a reference absorbance spectrum for a genuine agricultural composition, where the genuine agricultural composition comprises an agrochemical product and a marker dye or a marker pigment and where the reference spectrum has a maximum absorbance (Amax) for the dye or pigment at one or more wavelengths;
where the absence of an Amax in the absorbance spectrum for the agricultural composition suspected of falsification at the same wavelength or wavelengths indicates that the agricultural composition suspected of falsification is a falsified composition.
[94]
94. COMPOSITION, according to claim 88, or method, according to any one of claims 89 to 93, characterized by the fact that the marker dye or marker pigment has a maximum absorbance (Amax) at a wavelength between about 100 nm and about 700 nm.
[95]
95. COMPOSITION OR METHOD, according to claim 94, characterized by the fact that the marker dye or marker pigment has an Amax at a wavelength between about 100 nm and about 410 nm.
[96]
96. COMPOSITION OR METHOD, according to claim 95, characterized in that the marker dye or marker pigment has an Amax at a wavelength between about 250 nm and about 410 nm.
[97]
97. COMPOSITION OR METHOD, according to claim 95, characterized by the fact that the marker dye or marker pigment has an Amax at a wavelength between about 300 nm and about 410 nm.
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[98]
98. COMPOSITION OR METHOD, according to claim 95, characterized by the fact that the marker dye or marker pigment has an Amax at a wavelength between about 350 nm and about 398 nm.
[99]
99. COMPOSITION OR METHOD, according to claim 95, characterized by the fact that the marker dye or marker pigment has an Amax in the wavelength within a range of about 250 to about 320 nm.
[100]
100. COMPOSITION OR METHOD, according to claim 95, characterized by the fact that the marker dye or marker pigment has an Amax at one or more wavelengths selected from the group consisting of: about 250 nm, about 272 nm, about 307 nm, about 338 nm, about 342 nm, about 360 nm, about 365 nm, about 377 nm, about 378 nm, about 381 nm, about 382 nm, about 390 nm, about 393 nm, about 397 nm, about 398 nm, about 403 nm, about 404 nm, about 408 nm and combinations of any of the same.
[101]
101. COMPOSITION OR METHOD, according to any of claims 95 to 100, characterized by the fact that the marker dye or marker pigment comprises:
a fluorescent blue organic pigment visible in UV with an Amax at a wavelength of about 408 nm;
a fluorescent blue organic pigment visible in UV with an Amax at a wavelength of about 377 nm;
a fluorescent green-blue organic pigment visible in UV with an Amax at a wavelength of about 404 nm;
a fluorescent green organic pigment visible in UV with an Amax at a wavelength of about 397 nm;
a fluorescent yellow / green organic pigment visible in UV,
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27/32 having an Amax at a wavelength of about 250 nm to about 320 nm;
a fluorescent red organic pigment visible in UV with Amax at wavelengths of about 342 nm, about 408 nm and about 470 nm;
a thermofluorescent red pigment visible in UV, having an Amax at a wavelength of about 390 nm;
an organic red fluorescent pigment visible in UV with an Amax at a wavelength of about 390 nm;
a fluorescent organic pigment visible in UV with an Amax at a wavelength of about 365 nm;
a fluorescent red pigment visible in UV with an Amax at a wavelength of 382 nm;
a bifluorescent organic pigment visible in UV with Amax at wavelengths of about 272 nm and about 381 nm;
a thermofluorescent red organic dye visible in UV with an Amax at a wavelength of about 390 nm;
a ruthenium-based dye with Amax at wavelengths of about 307 nm, about 338 nm, about 403 nm and about 546 nm;
or a combination of any of them.
[102]
102. COMPOSITION OR METHOD, according to claim 94, characterized by the fact that the marker dye or marker pigment has an Amax at a wavelength between about 400 nm and about 700 nm.
[103]
103. COMPOSITION OR METHOD, according to claim 102, characterized by the fact that the marker dye or marker pigment has an Amax at a wavelength between about 410 nm and about 700 nm.
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[104]
104. COMPOSITION OR METHOD, according to claim 102, characterized by the fact that the marker dye or marker pigment has an Amax at a wavelength between about 425 nm and about 625 nm.
[105]
105. COMPOSITION OR METHOD, according to claim 102, characterized by the fact that the marker dye or marker pigment has an Amax in the wavelength within a range:
from about 425 to about 430 nm;
from about 430 nm to about 435 nm;
from about 490 nm to about 510nm;
from about 452 nm to about 460 nm;
from about 530 nm to about 550nm;
from about 590 nm to about 610 nm;
from about 510 nm to about 520 nm;
from about 450 nm to about 500 nm;
from about 580 nm to about 585 nm;
from about 520 to about 530 nm;
[106]
106. COMPOSITION OR METHOD, according to claim 102, characterized by the fact that the marker dye or marker pigment has an Amax at one or more wavelengths selected from the group consisting of: about 400 nm, about 406 nm, about 425 nm, about 430 nm, about 440 nm, about 442 nm, about 445 nm, about 450 nm, about 460 nm, about 470 nm, about 475 nm, about 480 nm, about 490 nm, about 500 nm, about 530 nm, about 546 nm, about 550 nm, about 555 nm, about 580 nm, about 625 nm, about 630 nm, about 650 nm, about 660 nm, about 675 nm, about 680 nm and combinations of any of these.
[107]
107. COMPOSITION OR METHOD, according to the claim
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102 or 106, characterized by the fact that the marker dye or marker pigment has an Amax at about 425 nm, about 530 nm or about 625 nm.
[108]
108. COMPOSITION OR METHOD, according to any one of claims 102 to 107, characterized in that the marker dye or marker pigment comprises curcumin, riboflavin, riboflavin-5'-phosphate, riboflavin-5'-phosphate, tartrazine , alkaline, Quinoline WS yellow, Fast AB yellow, 2G yellow, Sunset FCF yellow, GGN orange, carminic acid scale, carmine, Citrus 2 red, amaranth, Ponceau 4R, erythrosine, 2G red, Allura AC red, Indanthrene RS blue, blue Patent V, indigo caramel, Brilliant FCF blue, a chlorophylline, S green, Fast FCF green, a common caramel, caustic sulfite caramel, ammonia caramel, sulfite ammonia caramel, HT brown, alpha-carotene, beta-carotene, gamma carotene, annatto, bixin, norbixin, paprika oleoresin, capsanthin, capsorubin, lycopene, beta-apo-8'-carotenal, beta-apo-8-carotenic acid ethyl ester, flavoxanthin, lutein, cryoptoxanthin, rubixanthin, violaxanthin, zoxoxin, zoxoxin , citranaxanthin, astaxanthin, betanine, turmeric, ruby dye, orcein or a combination of any of these.
[109]
109. COMPOSITION OR METHOD, according to claim 108, characterized by the fact that the marker dye or marker pigment comprises curcumin, riboflavin, riboflavin-5'-phosphate, tartrazine, Quinoline WS Yellow, Sunset FCF Yellow, cochineal, acid carminic, carmine, Citrus Red 2, amaranth, Ponceau 4R, erythrosine, Red Allura AC, Blue Patent V, indigo carmine, Blue Bright FCF, a florophylline, Green S, Green Fast FCF, common caramel, caustic sulfite caramel, Caramel Ammonia, Ammonia Caramel Sulfite, Brown HT, alpha-carotene, beta-carotene, gamma-carotene, annatto, bixin, norbixin, paprika oleoresin, capsanthin, capsorubine, lycopene, beta-apo-8'-carotenal, beta-ethyl ester -apo-8-carotene,
Petition 870190119456, of 11/18/2019, p. 413/482
30/32 lutein, canthaxanthin, betanine, turmeric, a ruby dye or a combination of any of them.
[110]
110. COMPOSITION OR METHOD, according to claim 108 or 109, characterized by the fact that the marker dye or marker pigment comprises:
one or more chlorophyllins with Amax at about 440 nm, at about 680 nm or at about 440 nm and about 680 nm; or an ordinary caramel with an Amax at about 500 nm.
[111]
111. COMPOSITION OR METHOD, according to claim 108 or 109, characterized by the fact that the rubine dye comprises Lithol Rubine BK.
[112]
112. COMPOSITION according to any one of claims 88 and 94 to 111, or method according to any one of claims 89 to 108, characterized in that the marker dye or marker pigment comprises tartrazine, erythrosine or a combination of the same.
[113]
113. COMPOSITION according to any one of claims 88 and 94 to 112, or method according to any one of claims 89 to 112, characterized in that the agrochemical product comprises a pesticide, a fertilizer, a growth regulator plants, a biostimulant or a combination of any of them.
[114]
114. COMPOSITION OR METHOD, according to claim 113, characterized by the fact that the agrochemical product comprises a pesticide, and the pesticide comprises a herbicide, an insecticide, a fungicide, a nematicide, a virucide, an acaricide, a molluscicide, an algaecide, a bactericide or a combination of any of these.
[115]
115. COMPOSITION OR METHOD, according to claim 114, characterized by the fact that the pesticide comprises a herbicide.
Petition 870190119456, of 11/18/2019, p. 414/482
31/32
[116]
116. COMPOSITION OR METHOD, according to claim 115, characterized by the fact that the herbicide comprises an auxin herbicide.
[117]
117. COMPOSITION OR METHOD, according to claim 116, characterized in that the auxin herbicide comprises a phenoxy herbicide, a benzoic acid herbicide or a combination thereof.
[118]
118. COMPOSITION OR METHOD, according to claim 117, characterized by the fact that the phenoxy herbicide comprises 2,4dichlorophenoxyacetic acid (2,4-D), 2-methyl-4-chlorophenoxyacetic acid (MCPA), acid 4 (4 -chloro-otolyloxy) butyric (MCPB), mecoprop, 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), dichlorprop, dichlorprop-p, mecoprop-p, a salt of any of them, a ester or any of them, or a combination of any of them.
[119]
119. COMPOSITION OR METHOD, according to claim 118, characterized by the fact that the phenoxy herbicide comprises 2,4-D.
[120]
120. COMPOSITION OR METHOD, according to any of claims 117 to 119, characterized by the fact that the benzoic acid herbicide comprises dicamba, chlorambene, 2,3,6-trichlorobenzoic acid (2,3,6TBA), a salt of any of them, an ester of any of them or a combination of any of them.
[121]
121. COMPOSITION OR METHOD, according to claim 120, characterized by the fact that the benzoic acid herbicide comprises dicamba.
[122]
122. COMPOSITION according to any one of claims 88 and 94 to 121, or method according to any one of claims 89 to 121, characterized by the fact that:
the agrochemical product comprises dicamba and the marker dye comprises tartrazine; and / or the agrochemical product comprises 2,4-D and the marker dye
Petition 870190119456, of 11/18/2019, p. 415/482
32/32 comprises erythrosine.
[123]
123. COMPOSITION according to any one of claims 88 and 94 to 121, or method according to any one of claims 89 to 121, characterized in that the agrochemical product comprises dicamba and the marker dye or marker pigment comprises a dye or pigment having an Amax at about 625 nm.
[124]
124. COMPOSITION according to any one of claims 88 and 94 to 123, or method according to any one of claims 89 to 123, characterized in that the ratio of the agrochemical to the dye or pigment is about 10: 1 to about 1: 100.

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同族专利:

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公开号 | 公开日

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US20210080385A1|2021-03-18|

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AU2018269707A1|2019-12-19|

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EP3625547A4|2021-01-13|

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US10788419B2|2020-09-29|

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WO2018213596A4|2019-01-10|

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CA3063925A1|2018-11-22|

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EP3625547A1|2020-03-25|

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WO2018213596A1|2018-11-22|

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AR111876A1|2019-08-28|

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US20180364155A1|2018-12-20|

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法律状态:
2021-10-19| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US201762507602P| true| 2017-05-17|2017-05-17|

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US62/507,602|2017-05-17|

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PCT/US2018/033213|WO2018213596A1|2017-05-17|2018-05-17|Devices, systems, and methods for agrochemical detection and agrochemical compositions|

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