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    • 专利摘要:
    The present invention relates the use of an active ingredient in enhancing the dissipation of contaminants. The active ingredient can be purified cellulose; hemicellulose; lignin; humin; humic acids; fulvic acids; or purified sugar polymers or their derivatives from microorganisms/algae, such as agarose; each separately; in a mixture; or mixed or bound with other unspecified material(s); as well as combinations thereof. The active irvedient can have passed through a physical, chemical or microbial process. The active ingredient was shown to significantly enhance the dissipation of atrazine, terbutryn, hexazinone, and 2,6-dichlorobenzamide; and the atrazine degradation products desethylatrazine, deisoprobylatrazine, and desethyldeisopropylatrazine, the possibility to enhance the dissipation of other contaminants is included.
    公开号:FI20180056A1
    申请号:FI20180056
    申请日:2018-04-23
    公开日:2018-12-01
    发明作者:Merja Kontro；Vilhelmiina Harju
    申请人:Merja Kontro；Vilhelmiina Harju；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    The present invention relates to methods and devices to enhance the dissipation of contaminants by adding the active ingredients.
    BACKGROUND OF THE INVENTION
    Many organic compounds and inorganic elements can persist as contaminants for decades, and pose risks to the environment, and animal and human health. Similarly, many derivatives of organic compounds and inorganic elements, which may contain an attached group, can be resistant to dissipation. The examples of such groups are halogens and methylthio groups, though the attachment of other groups to contaminants cannot be excluded. Such molecules called environmental contaminants, persistent organic compounds, or xenobiotics (other possible names being included) are common in urban and natural environment, including industrial facilities, soil, sediment, water, groundwater and air, other possible environments are included. The examples of contaminants include fossil fuels and petroleum based compounds, halogenated organic compounds, combustion products, flame retardants, pesticides, heavy metals, and other molecules that are considered harmful, and whatever derivatives or combinations of them. The contaminants often do not have an appropriate remediation method, and their biotic and/or abiotic dissipation to a harmless form cannot be enhanced. Organic matter in different forms has been used to enhance contaminant dissipation (W02004079030 A2; US5902744 A; Dungan et al., 2001; Marin-Benito et al., 2014, Kerminen et al., 2018). However, in such systems part of contaminants can be adsorbed into the heterogenous material in an unreactive form, and large quantities of organic matter must be used as an additive. The purified active ingredients would be needed. The methods and devices to dissipate contaminants in biotic and/or abiotic processes into forms that are harmless to the environment, animals and humans would be utmost important.
    What would thus be desirable is to provide effective improvements in contaminant dissipation in situ, ex situ, on site, off site or in some other system, process, or device. It would further be desirable that the environments for the enhanced dissipation include water, soil, sediments, bioreactors and other possible methods or systems, in which the dissipation of contaminants can be enhanced by the active incredient. It would be desirable to provide a fast, cost efficient, and safe method for the improved dissipation of a wide range of different contaminants.
    20180056 prh 23 -04- 2018
    SUMMARY OF THE INVENTION
    The problem underlying the present invention was to find additional economical methods to fasten the dissipation of organic and inorganic contaminants to another form, as many of the contaminants may be difficult to dissipate with the existing methods. The present invention relates the use of the novel active ingredient in enhancing the dissipation of contaminants. The active ingredient can be cellulose; hemicellulose; lignin; humin; humic acids; fulvic acids; or sugar polymers or their derivatives from microorganisms/algae, such as agarose; each separately; in a mixture; or mixed or bound with other unspecified materials); as well as combinations thereof. A single active ingredient is purified to a concentration that is higher than in its natural context source. The method involves the addition of the active ingredient to the contaminated environmental sample, though the addition of the active ingredient in contexts of other materials is included. The active ingredient can also be bound to the support material(s) or molecule(s), and enhance the contaminant dissipation therefrom. The active ingredient can be passed through abiotic or biotic process(es) prior to use, such as autoclaving. The active ingredient was shown to enhance significantly the dissipation of atrazine, hexazinone, terbutryn, and 2,6-dichlorobenzamide (BAM, dichlobenil degradation product); and the atrazine degradation products desethylatrazine (DEA), deisoprobylatrazine (DIA), desethyl-deisopropylatrazine (DEDIA), the possibility to enhance the dissipation of other contaminants is included.
    DEFINITIONS
    The term ‘contaminant(s)’ used herein is an organic or inorganic molecule, or a mixture of different contaminant molecules, which do not belong to environment as natural components in existing concentrations, or which can be regarded as undesirable compounds. Contaminants are not easily dissipated in the environment, and they can be called environmental contaminants or persistent compounds or xenobiotics, other possible names for such compounds are included. Contaminants can also be pure compounds or a mixture of compounds. When contaminants dissipate due to the presence of the active ingredient, their chemical structure and/or oxidation state is/are changed. The dissipation product of the original contaminant can also be a contaminant. The examples of contaminants are fossil fuel and petroleum based compounds; halogenated organic compounds; combustion products; flame retardants; pesticides, herbicides, insecticides; heavy metals; other molecules regarded as harmful; and whatever derivatives or combinations of them.
    20180056 prh 23 -04- 2018
    The term ‘environment’ is describing here the place of the addition of the active ingredient to enhance the dissipation rate of contaminant(s). The environments range from deep subsurface groundwater and sediment layers to surface soil and bioreactors, seas and surface waters, air being included as a possible remediating environment. The other possible environments are included, including man-made environments, laboratories, pilot-units, full-scale facilities and filtration units (including water filtration units, reactive walls), as well as pure contaminant compound(s). The materials in the environment include earth, soil, ground, sand, clay, mud, sediment, sludge, slurry, water, peat, dredging mass, compost, litter, ash, waste streams, and mixtures thereof, possible other materials being included.
    The term ‘dissipation’ of contaminant(s) used here refer to at least partial change in the chemical structure (transformation) or oxidation state of contaminant(s) to another form from the original one, in accordance with the principles of the present invention. The derivatives of the contaminant(s) can also be contaminant(s), and dissipated by adding the active ingredient for indefinite numbers of time. The term include the aging of compounds, in which contaminant(s) become unextractable due to reactions with the active ingredient although carbon is not mineralized to CO2. The dissipation can be biotic or abiotic process, and includes the adsorption of contaminant(s) (immobilization).
    The term ‘active ingredient’ is used here to refer cellulose; hemicellulose; lignin; humin; humic acids; fulvic acids; or sugar polymers or their derivatives from microorganisms/algae, such as agarose; each separately; in a mixture; or mixed or bound with other unspecified material(s), as well as combinations thereof. The active ingredient is purified to a concentration that is higher than in its natural context source, and its concentration during the dissipation of contaminants can be whatever above 0 %. The active ingredient can be passed through abiotic or biotic process(es), such as autoclave sterilization, prior to the use.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1 is a representation of the performance of the enhanced dissipation of (a,b) atrazine, (c,d) terbutryn, (e) hexazinone, and (f) 2,6-dichlorobenzamide (BAM) after the addition of an active ingredient in groundwater sediment slurries or sterilized groundwater sediment slurries, in relation to the sediment slurries (□) or sterilized sediment slurries () without the active ingredient, in accordance with the principles of the present invention. The active ingredients were cellulose (·), sterilized cellulose in sterilized sediment slurries (o), hemicellulose (0), lignin (♦), humin (A),
    20180056 prh 23-04- 2018 humic acids (Δ), fulvic acids (x), or sterilized fulvic acids in sterilized sediment slurries (x). The average of the standard deviations of pesticide concentrations was 1.4 mg/L.
    DETAILED DESCRIPTION OF THE INVENTION
    In accordance with the principles of the present invention, the active ingredient was used to enhance the dissipation of environmental contaminants. The active ingredient cellulose; hemicellulose; lignin; humin; humic acids; fulvic acids; or the sugar polymer or its derivative from microorganisms/algae, agarose was used to enhance the dissipation of contaminants. In the present invention, the active ingredient was added in environmental samples with or without autoclave sterilization, or in a pure contaminant system to enhance the dissipation of contaminants, such as for example atrazine, terbutryn, hexazinone, and BAM. In this embodiment the environmental samples were groundwater sediment slurries. The active ingredient addition enhanced the dissipation of the studied contaminants, and the dissipation of atrazine degradation products, DEA, DIA, and DEDIA, showing that the contaminants resulting from the dissipation of the parent compound can also be dissipated. The use of autoclave-sterilized systems with the active ingredient (cellulose and agarose results shown) showed that the active ingredient can be active after passing through a physical process, and that the dissipation may be chemical. The dissipation of contaminants has not been earlier shown to be related to the active ingredient described here.
    The present invention produces a new approach for environmental remediation or whatever other purposes to enhance the dissipation of contaminants using the active ingredient cellulose; hemicellulose; lignin; humin; humic acids; fulvic acids; or sugar polymers or their derivatives from microorganisms/algae such as agarose; each separately; in a mixture; or mixed with other unspecified material(s), as well as combinations thereof. The active ingredient can be used in excess, in quantities partly causing the dissipation of the contaminants, or in proportions and amounts established in small incubated batches to be sufficient beneficial for the dissipation of the contaminants.
    In an embodiment, the active ingredient can be mixed with the contaminants, with the contaminated material, or into the contaminated environment using means known by those skilled in the art, including manual mixing, the equipment used in soil mixing for agricultural purposes and in construction industry, and their modifications. The mixing equipment for composting, drilling machinery, excavator with a screening bucket, and front loaders are possible to use for mixing the active ingredient with the contaminated material, and other possible mixing methods are included. Alternatively, the active ingredient can be applied on the surface of the contaminated area, where
    20180056 prh 23 -04- 2018 the penetration into the contaminated material can be enhanced by water irrigation (sprinkling), or by other methods known by those skilled in the art of science.
    In an embodiment, other unspecified materials, which are added with the active ingredient, can be air, ozone, (Ca)-peroxide, and wood chips to add oxygen and reactive species. Other possible materials can be included by those skilled in the art of science, such as nutrients for microorganisms degrading contaminants or degradation products. In another embodiment, the active ingredient can be applied as slurry, which is pumped into the polluted material or injected into a borehole. Other possible formulations of the active ingredient include powder, pellet, granule, and the mixture with the binders. The formulations can be mixed with the contaminated material as presented above, or applied on the surface of the contaminated area, where the penetration in the contaminated material can be enhanced by water irrigation, or by other methods known by persons skilled in the art of science.
    In an embodiment, the active ingredient can embedded in a filter unit as a pure formulated material, or as bound to a carrier matrix, such as small household filtration units, or full-scale industrial filters. The active ingredient can be embedded in the sediment column, or reactive wall, in which contaminants dissipate, when water passes through the system. Other possible application fields may be found by persons skilled in the art of science.
    The present invention can be applied to increase the dissipation of contaminants in a wide variety of applications in different environments. The in situ techniques involve the contaminant dissipation in the natural environment after adding the active ingredient. They are appropriate e.g. in sites where the mixing of the active ingredient with the contaminated material is possible, and the excavation of contamination is expensive. Reactive walls in a water flow zone are examples of in situ techniques, and other in situ approaches may be found by those skilled in the art of science. The ex situ techniques may be appropriate, when in situ techniques cannot be performed, such as in dense soil (clay), or in the presence of risk for contaminant elution to groundwater. The ex situ techniques require the removal of contaminated material from the natural environment prior to the treatment, which then can be performed on site, or after transportation to another site (off site).
    This invention has been described with specific embodiments. However, other alternatives, modifications and variations will be possible to those skilled in the art of science. The invention will be intended to include all alternatives, modifications and variations within the fields and scopes of the claims presented below.
    The following are non-limiting examples in accordance with the principles of the present invention.
    20180056 prh 23 -04- 2018
    EXAMPLE 1.
    Subsurface sediments were collected to plastic bags in drillings in an aquifer having pesticides in groundwater (Kerminen et al., 2018). Sediments (15.0 g, dry weight, dry wt) and 50 ml of sterilized water in 100 mL sterilized flasks with aluminum foil-covered caps (hole diameter 5 mm) were amended with 30 mg/L of atrazine, hexazinone, terbutryn and BAM (stock 10 g/L in methanol), and shaken at 120 rpm (Laboshake, Gerhardt, Koningswinter, Germany). The pesticide dissipation was followed in the sediment slurries, and in the sediment slurries amended with 2 wt-% of the active ingredient. The experiments in triplicate included the sterilized sediment slurries, and the sterilized sediment slurries amended with 2 wt-% of the active ingredient, which were autoclaved for 1 h (121 °C, 101 kPa) on three successive days, as presented in Kerminen et al. (2018). Samples were collected after 35, 79, 156, and 236 days from the slurries with and without the active ingredient. The flasks were weight prior to and after samplings, and the evaporated water was replaced with the sterilized distilled water, to avoid concentration changes due to evaporation. The pesticides were analyzed gas chromatography - mass spectrometry (GC-MS) as presented in Kerminen et al (2018). Six standards contained atrazine, hexazinone, terbutryn, BAM, DEA, DIA and DEDIA in concentrations 0.5-12.6 mg/L, and 8.6 mg/L of propazine was added to standards and samples as an internal standard. All values are presented on the dry weight basis, which was determined as presented in Kerminen et al. (2018).
    As can be seen from Fig. 1, one or several of the active ingredients, including cellulose, hemicellulose, lignin, humin, humic acids, or fulvic acids, enhanced the dissipation of atrazine, hexazinone, terbutryn, or BAM. Atrazine concentrations dissipated in 236 days from 30 mg/L to 21.5, 17.6, and 0.6 mg/L in the sediment slurries amended with the active ingredient humic acids, humin, or lignin, respectively, compared with 26.6 mg/L of the sediment slurries without the active ingredients (Fig. la). Atrazine concentrations dissipated in 236 days from 30 mg/L to 22.8 mg/L in the sediment slurries amended with the fulvic acids, and to 9.1 mg/L in the sterilized sediment slurries amended with the sterilized fulvic acids, compared with 26.6-27.0 mg/l of the sediment and sterilized sediment slurries without the active ingredients (Fig. lb). The degradation products DEA, DIA and DEDIA we not detected in the sediment slurries. Therefore, the active ingredient humic acids, humin, lignin, or fulvic acids enhanced atrazine dissipation. The sterilization enhanced atrazine dissipation in the fulvic acids amended sediment slurries. The active ingredient also enhanced the dissipation of the atrazine degradation products.
    Terbutryn concentration dissipated in 79 days from 30 mg/L to 11.9, 8.7, 8.7, and 0.9 mg/L mg/L in the sediment slurries amended with the active ingredient hemicellulose, fulvic acids,
    20180056 prh 23 -04- 2018 humin, or lignin, respectively, while the concentration after 79 days was 17.2 mg/L in the slurries without the additives (Fig. lc). Terbutryn dissipation weakened slightly in the sediment slurries amended with the active ingredient cellulose, being 17.1 mg/L with cellulose, and 15.2 mg/L without cellulose after 79 days, which could be due to adsorption of terbutryn in cellulose (Fig. Id). In contrast, in the sterilized slurries with the sterilized cellulose, terbutryn dissipation improved slightly, the concentration being 11.5 mg/L with the sterilized cellulose and 13.3 mg/L without the sterilized cellulose after 79 days. Thus, lignin, humin, fulvic acids, hemicellulose or sterilized cellulose enhanced terbutryn dissipation.
    Hexazinone concentration dissipated from 30 mg/L to 14.2 mg/L in 156 days in the sediment slurries amended with the active ingredient lignin, while the concentration was 23.4 mg/L in the slurries without the active ingredient. Similarly, BAM concentration dissipated in 79 days to 18.6 mg/L in the sediment slurries amended with the active ingredient lignin, while the concentration in the slurries without the active ingredient was 23.7 mg/L.
    In conclusion, the active ingredient cellulose, hemicellulose, lignin, humin, humic acids, or fulvic acids enhanced the dissipation of atrazine, terbutryn, hexazinone, or BAM, and further the dissipation of the atrazine degradation products DEA, DIA, or DEDIA, in accordance with the principles of the present invention. The processing of the active ingredients fulvic acids and cellulose by autoclaving improved atrazine and terbutryn dissipation, respectively, in accordance with the principles of the present invention.
    EXAMPLE 2.
    Agarose (1.5%) solubilized in distilled water was autoclave-sterilized for 20 min at 121 °C (101 kPa). When the temperature was cooled to 50 °C, 30 mg/L of atrazine was added, and 10 ml of the solution was divided into 20 ml test tubes. After 25 days incubation at the room temperature of 21 ±2 °C, atrazine was extracted from three parallel 10 ml portions and analyzed by GC-MS as presented in Mattsson et al. (2015) using the same standard concentrations presented in example 1. The results showed that atrazine concentration dissipated from 30 mg/L to 4.H0.2 mg/L in 25 days. The pure active ingredient, which was sugar polymer or their derivative from microorganisms/algae, agarose, enhanced significantly pure atrazine dissipation, in accordance with the principles of the present invention.
    REFERENCES
    Dungan, R. S., Gan, J., Scott, R. Y. (2001). Effect of temperature, organic amendment rate and moisture content on the degradation of 1,3-dichloropropene in soil. Pest Management Science 57, 1107-1113.
    Kerminen, K., Le Moel, R., Harju, V., Kontro, M.H. (2018). Influence of organic matter, nutrients, and cyclodextrin on microbial and chemical herbicide and degradate dissipation in subsurface sediment slurries. Science of the Total Environment 618, 1449-1458.
    Marin-Benito, J. M., Herrero-Hernandez, E., Andrades, M. S., Sanchez-Martin, M. J., RodriguezCruz, M. S. (2014). Effect of different organic amendments on the dissipation of linuron, diazinon and myclobutanil in an agricultural soil incubated for different time periods. Acience of the Total Environment 476-477, 611-621.
    US5902744A. Gray, N. C. C., Moser, G. P., Moser, L. E. Compost decontamination of soil contaminated with chlorinated toxicants. 11.05.1999.
    W02004079030 A3. Seech, A. G., Hill, D. D., Dmitrovic, E., Bolanos-Shaw, K. W. Composite material for a permeable reactive barrier. 16.09.2004.
    权利要求:
    Claims (10)
    [1] CLAIMS:
    What is claimed is:
    1. A method of enhancing the dissipation of contaminants by adding the active ingredient, which is purified from plant material, or from sugar polymers or their derivatives of micro-organisms or algae. The concentrations of the purified compounds are higher than those naturally in plants, micro-organisms, and algae.
    [2] 2. The method of claim 1, wherein the active ingredient is lignin in concentration above 0 %.
    [3] 3. The method of claim 1, wherein the active ingredient is humin, humic acids, or fulvic acids in concentration above 0 %.
    [4] 4. The method of claim 1, wherein the active ingredient is hemicellulose or cellulose in concentration above 0 %.
    [5] 5. The method of claim 1, wherein the active ingredient is agarose in concentration above 0 %.
    [6] 6. The method of claim 1, wherein the active ingredient is whatever mixture of purified compounds presented in claims 2-5 in concentration above 0 %.
    [7] 7. The method of s 1-6, wherein the active ingredient is mixed or bound with some other material.
    [8] 8. The method of claims 1-7, wherein the active ingredient has passed through a physical, chemical or microbial process.
    [9] 9. The method of claims 1 -7, wherein the contaminant is an organic compound, which is considered harmful.
    [10] 10. The method of claims 1-7, wherein the contaminant is element, which is considered harmful.
    Figure 1.
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    同族专利:
    公开号 | 公开日
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2018-07-06| PC| Transfer of assignment of patent|Owner name: OKEPEM OY |
    2020-09-07| FD| Application lapsed|
    优先权:
    申请号 | 申请日 | 专利标题
    FI20170081|2017-05-31|
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