Obsolete pesticides and application of colonizing plant species for remediation of contaminated soil in Kazakhstan

In Kazakhstan, there is a problem of finding ways to clean local sites contaminated with pesticides. In particular, such sites are the deserted and destroyed storehouses where these pesticides were stored; existing storehouses do not fulfill sanitary standards. Phytoremediation is one potential method for reducing risk from these pesticides. Genetic heterogeneity of populations of wild and weedy species growing on pesticide-contaminated soil provides a source of plant species tolerant to these conditions. These plant species may be useful for phytoremediation applications. In 2008–2009 and 2011, we surveyed substances stored in 80 former pesticide storehouses in Kazakhstan (Almaty oblast) to demonstrate an inventory process needed to understand the obsolete pesticide problem throughout the country, and observed a total of 354.7 t of obsolete pesticides. At the sites, we have found organochlorine pesticides residues in soil including metabolites of dichlorodiphenyltrichloroethane and isomers of hexachlorocyclohexane. Twenty-four of the storehouse sites showed pesticides concentrations in soil higher than maximum allowable concentration which is equal to 100 μg kg^?1 in Kazakhstan. Seventeen pesticide-tolerant wild plant species were selected from colonizing plants that grew into/near the former storehouse’s pesticides. The results have shown that colonizing plant annual and biannual species growing on soils polluted by pesticides possess ability to accumulate organochlorine pesticide residues and reduce pesticide concentrations in soil. Organochlorine pesticides taken up by the plants are distributed unevenly in different plant tissues. The main organ of organochlorine pesticide accumulation is the root system. The accumulation rate of organochlorine pesticides was found to be a specific characteristic of plant species and dependent on the degree of soil contamination. This information can be used for technology development of phytoremediation of pesticide-contaminated soils.     

Accelerated remediation of pesticide-contaminated soil with zerovalent iron

High pesticide concentrations in soil from spills or discharges can result in point-source contamination of ground and surface waters. Cost-effective technologies are needed for on-site treatment that meet clean-up goals and restore soil function. Remediation is particularly challenging when a mixture of pesticides is present. Zerovalent iron (Fe0) has been shown to promote reductive dechlorination and nitro group reduction of a wide range of contaminants in soil and water. We employed Fe0 for on-site treatment of soil containing > 1000 mg metolachlor, > 55 mg alachlor, > 64 mg atrazine, > 35 mg pendimethalin, and > 10 mg chlorpyrifos kg(-1). While concentrations were highly variable within the windrowed soil, treatment with 5% (w/w) Fe0 resulted in > 60% destruction of the five pesticides within 90 d and increased to > 90% when 2% (w/w) Al2(SO4)3 was added to the Fe0. GC/MS analysis confirmed dechlorination of metolachlor and alachlor during treatment. Our observations support the use of Fe0 for ex situ treatment of pesticide-contaminated soil.     

Comparative studies of the fate of atrazine‐14C and pentachlorophenol‐14C in various laboratory and outdoor soil‐plant systems

Abstract

Mass balance and fate of atrazine‐ ¹⁴C and pentachlorophenol‐ ¹⁴C (PCP‐ ¹⁴C) were studied in short‐term tests in a closed aerated laboratory soil‐plant system, using two concentrations in soil and two plant species, as well as under outdoor conditions for one vegetation period. In the laboratory, for both pesticides bioaccu‐mulation factors of radiocarbon taken up by the roots into plants were low. They were higher for lower (1 ppm) than for higher soil concentrations (6 ppm for atra‐zine, 4 ppm for pentachlorophenol) and varied with the plant species. Mineralization to ¹⁴CO₂ in soil was negatively related to soil concentration only for PCP‐ ¹⁴C. Conversion rates in soil including the formation of soil‐bound residues were higher for the lower concentrations of both pesticides than for the higher ones; conversion rates in plants were species‐dependent. In 14 terms of CO₂ formation and of conversion rates, PCP was less persistent in soil than was atrazine. For both pesticides, laboratory data on conversion and mineralization gave a rough prediction of their persistence in soil under long‐term outdoor conditions, whereas bio‐accumulation factors in plants under long‐term outdoor conditions could not be predicted by short‐term laboratory experiments.     

Determination of disulfoton and permethrin residues in an organic soil and their translocation into lettuce,onion and carrot 1

Abstract

The residues of disulfoton and permethrin in an organic soil and in vegetables grown in soil treated with a granular formulation of the pesticides were determined by gas chromatography. The residues were removed from soil or plant samples by successive extractions with acetone and hexane. Permethrin persisted in the soil for the initial 28 days and declined slowly during the rest of the season but disulfoton after persisting for one week at the applied concentration was degraded in the next two weeks. The insecticides did not translocate into the edible parts of the vegetables but were present in the root system of onion and lettuce. Carrot and lettuce yields were not significantly different from those of the controls but onion yields were substantially decreased by the use of per‐methrin.     

Residues of five pesticides in field‐treated alfalfa seeds and alfalfa sprouts

Abstract

Residues of five different pesticides applied to alfalfa seed crops were determined in the harvested seeds and in sprouts grown from these seeds. Although seeds are usually used for future production of alfalfa plants, some of these seeds may be sprouted for human food consumption. The pesticides studied — aldicarb (Temik®), chlorothalonil (Bravo®), chlorpyrifos (Lorsban®), methamidophos (Monitor®) and propargite (Comite®) — were applied at a normal usage rate and at two to three times that rate. Residues on the seeds and sprouts, if any, were insignificant at rates of application.     

Use of coal to retard pesticide movement in soil

Abstract

Three different coals and an activated carbon were mixed with prescribed amounts of a sandy loam soil and added to soil columns to test their ability to retard pesticide movement. The pesticides chosen were prometon, prometryn, 2,4‐D, carbofuran, dinoseb, fenamiphos, and two oxidation products of fenamiphos, fenamiphos sulfoxide, and fenamiphos sulfone. These compounds were chosen to represent different chemical classes of pesticides and because they were considered to have a high potential for transport in soils. All the coals were more effective in retaining the pesticides than the soil, however, some were more effective than others. One of the coals was the most effective in retaining the majority of the pesticides with an overall retention of 94.7% in a 4:1 soil/coal ratio compared to the soil only with a retention of 48.5%. The moisture content of the coal appears to have a positive correlation with the ability of the coal to retain the pesticides under the conditions used for this experiment.     

Effects of different treatments on soil-borne DDT and HCH dynamics and plant uptake

Pot experiments were conducted to examine the effects of various fertilizers, as well as soil dilution treatments on the dynamics of soil-borne DDTs [sum of dichlorodiphenyltrichloroethane (DDT), chlorodiphenyldichloroethylene (DDE) and di- chlorodiphenyldichloroethane (DDD)] and hexachlorocyclohexanes (HCHs, sum of α-HCH, β-HCH, γ-HCH and δ-HCH) and their subsequent impacts on the uptake of DDTs and HCHs by a test plant. The results show that the soil residual DDTs and HCHs concentrations in the iron-rich fertilizer-treated soil were significantly lower than those in other fertilizer-treated soils. There was a close relationship between the soil residual DDTs and the plant tissue DDTs. This suggests that the uptake rate of DDTs by the plant was dependent on the concentration of soil-borne DDTs. A less close relationship between soil residual HCHs and plant tissue HCHs was also observed. Dilution of pesticide-contaminated soil with the non-contaminated soil not only physically reduced the concentration of pesticides in the soil but also enhanced the loss of soil-borne pesticides, possibly through the improvement of soil conditions for microbial degradation. Soil dilution had a better effect on promoting the loss of soil-borne HCHs, relative to soil-borne-DDTs. The research findings obtained from this study have implications for management of heavily contaminated soils with DDTs and HCHs. Remediation of DDTs and HCHs-contaminated soils in a cost-effective way can be achieved by incorporating treatment techniques into conventional agricultural practices. Applications of iron-rich fertilizer and soil dilution treatments could cost-effectively reduce soil-borne DDTs and HCHs, and subsequently the uptake of these organochlorine pesticides by vegetables.     

Effects of different treatments on soil-borne DDT and HCH dynamics and plant uptake

Pot experiments were conducted to examine the effects of various fertilizers, as well as soil dilution treatments on the dynamics of soil-borne DDTs [sum of dichlorodiphenyltrichloroethane (DDT), chlorodiphenyldichloroethylene (DDE) and di- chlorodiphenyldichloroethane (DDD)] and hexachlorocyclohexanes (HCHs, sum of α-HCH, β-HCH, γ-HCH and δ-HCH) and their subsequent impacts on the uptake of DDTs and HCHs by a test plant. The results show that the soil residual DDTs and HCHs concentrations in the iron-rich fertilizer-treated soil were significantly lower than those in other fertilizer-treated soils. There was a close relationship between the soil residual DDTs and the plant tissue DDTs. This suggests that the uptake rate of DDTs by the plant was dependent on the concentration of soil-borne DDTs. A less close relationship between soil residual HCHs and plant tissue HCHs was also observed. Dilution of pesticide-contaminated soil with the non-contaminated soil not only physically reduced the concentration of pesticides in the soil but also enhanced the loss of soil-borne pesticides, possibly through the improvement of soil conditions for microbial degradation. Soil dilution had a better effect on promoting the loss of soil-borne HCHs, relative to soil-borne-DDTs. The research findings obtained from this study have implications for management of heavily contaminated soils with DDTs and HCHs. Remediation of DDTs and HCHs-contaminated soils in a cost-effective way can be achieved by incorporating treatment techniques into conventional agricultural practices. Applications of iron-rich fertilizer and soil dilution treatments could cost-effectively reduce soil-borne DDTs and HCHs, and subsequently the uptake of these organochlorine pesticides by vegetables.     

Degradation of atrazine, metolachlor, and pendimethalin in pesticide-contaminated soils: effects of aged residues on soil respiration and plant survival

This study was conducted to determine the effects of pesticide mixtures on degradation patterns of parent compounds as well as effects on soil microbial respiration. Bioavailability of residues to sensitive plant species was also determined. Soil for this study was obtained from a pesticide-contaminated area within an agrochemical dealer site. Degradation patterns were not affected by the presence or absence of other herbicides in this study. Atrazine concentrations were significantly lower at 21 through 160 days aging time compared to day 0 concentrations. Metolachlor and pendimethalin concentrations were not significantly different over time and remained high throughout the study. Microbial respiration was suppressed in treated soils from day 21 to day 160. Soybean and canola were the most successful plant species in the germination and survival tests. Generally, with increased aging of pesticides in soil, germination time decreased. Survival time of plants increased over time for some treatments indicating possible decreased bioavailability of pesticide residues. In some cases, survival time decreased at the longer 160-day aging period, possibly indicating a change in bioavailability, perhaps as the result of formation of more bioavailable and phytotoxic metabolites. No interactive effects were noted for mixtures of pesticides compared to individually applied pesticides in terms of degradation of the parent compound or on seed germination, plant survival, or microbial respiration.     

Pesticides in the surface waters of the Camanducaia River watershed,Brazil

Abstract

Camanducaia River is part of the Piracicaba watershed responsible for pumping water into the Cantareira System, which is one of the main water sources for the metropolis of São Paulo and Campinas, Brazil. Intensive use of pesticides and hilly topography represents a situation of high risk for river water contamination. Therefore, water samples from 12 locations were collected along the Camanducaia River and its tributaries, over a period of 4?mo during the rainy season, and analyzed by GC-MS/MS or UPLC- MS/MS for the presence of 46 pesticides. Seven pesticides (fipronil, methyl parathion, metolachlor, atrazine, carbofuran, diuron, and simazine) were positively detected. Only atrazine (the most frequently detected) and diuron were present at concentrations above the limit of quantification of the analytical method (0.32 and 0.57?μg L^?1 for atrazine and diuron, respectively). Pesticides detection frequency was higher than expected for a river system where only 11.8% of the land area is under agriculture. The vulnerability of the Camanducaia basin to pesticide contamination is attributed to the high annual precipitation (> 1.5?m y^?1 in the headwaters), associated with topographical features (steep terrain) and soil types that favor surface runoff, which has been exacerbated by poor soil management practices.     

Determining the role of humic substances in the fate of pesticides in the environment

Abstract

The data presented in this paper emphasize that the behavior and fate of pesticides in the environment is influenced by humic substances. Various methods most frequently used for the characterization of humic substances are discussed. Both humic acid and fulvic acid can solubilize in water certain organic compounds and are important carriers of some pesticides in soil. Humic substances have the potential for promoting the nonbiological degradation of many pesticides. Several methods of bleaching humus color from drinking water, including chlorination, ozonation, and UV‐radiation, are described. Finally, the photochemical stability to UV‐radiation of certain pesticides in aqueous fulvic acid solution is discussed.     

Destruction of halogen-containing pesticides by means of detonation combustion

Pesticides that contain a halogen functional group have been destructed by means of detonative combustion. The following compounds were examined: (1) atrazine—2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine—herbicide; (2) bromophos—O,4-bromo-2,5-dichlorophenyl O,O-dimethyl phosphorothioate—insecticide; (3) chloridazon—5-amino-4-chloro-2-phenylopyridazin-3(2H)-one—herbicide; (4) linuron—3-(3,4-dichlorophenyl)-1-metoxy-1-methylurea—herbicide; (5) metoxychlor—1,1,1-trichloro-2,2-bis(4-metoxyphenyl)ethane—insecticide and acaricide; and (6) trichlorfon—dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate—insecticide. Explosive material has been produced on the basis of ammonium nitrate, which served as an oxidizer while the pesticides were used as fuels. Composition of the explosive was adjusted in such a way as to respect thermodynamic parameters. Detonative decomposition of the mixtures has been carried out in shot-holes pre-drilled in soil. Efficiency of the pesticide decomposition has been examined with gas chromatography in order to determine pesticides residues in the environment. It was found that for some, the amount of pesticides in some compounds in the analyzed samples after decomposition was below the determination threshold of the applied method.     

Monitoring transport of selected pesticides and phenols in soil columns by high performance liquid chromatography

Abstract

Soil columns were used to study pesticides and phenols transport under rapid infiltration land treatment conditions. An analytical procedure is described for the quantitative determination of atrazine, diuron, carbofuran, phenol, 2,4‐dinitrophenol, 2,4‐dimethylphenol, and 2,4‐dichlorophenol in soil and wastewater. Recoveries of all analytes were greater than 90%. The method detection limits for all analytes were ≤0.03 μg/ml (s/n=4) in wastewater and ≤ 0.1 μg/ml (s/n=5) in soil.     

The effect of vegetation on pesticide dissipation from ponded treatment wetlands: quantification using a simple model

Field data shows that plants accelerate pesticide dissipation from aquatic systems by increasing sedimentation, biofilm contact and photolysis. In this study, a graphical model was constructed and calibrated with site-specific and supplementary data to describe the loss of two pesticides, endosulfan and fluometuron, from a vegetated and a non-vegetated pond. In the model, the major processes responsible for endosulfan dissipation were alkaline hydrolysis and sedimentation, with the former process being reduced by vegetation and the latter enhanced. Fluometuron dissipation resulted primarily from biofilm reaction and photolysis, both of which were increased by vegetation. Here, greater photolysis under vegetation arose from faster sedimentation and increased light penetration, despite shading. Management options for employing constructed wetlands to polish pesticide-contaminated agricultural runoff are discussed. The lack of easily fulfilled sub-models and data describing the effect of aquatic vegetation on water chemistry and sedimentation is also highlighted.     

Degradation of atrazine,metolachlor, and pendimethalin in pesticide‐contaminated soils: Effects of aged residues on soil respiration and plant survival

Abstract

This study was conducted to determine the effects of pesticide mixtures on degradation patterns of parent compounds as well as effects on soil microbial respiration. Bioavailability of residues to sensitive plant species was also determined. Soil for this study was obtained from a pesticide‐contaminated area within an agrochemical dealer site. Degradation patterns were not affected by the presence or absence of other herbicides in this study. Atrazine concentrations were significantly lower at 21 through 160 days aging time compared to day 0 concentrations. Metolachlor and pendimethalin concentrations were not significantly different over time and remained high throughout the study. Microbial respiration was suppressed in treated soils from day 21 to day 160. Soybean and canola were the most successful plant species in the germination and survival tests. Generally, with increased aging of pesticides in soil, germination time decreased. Survival time of plants increased over time for some treatments indicating possible decreased bioavailability of pesticide residues. In some cases, survival time decreased at the longer 160‐day aging period, possibly indicating a change in bioavailability, perhaps as the result of formation of more bioavailable and phytotoxic metabolites. No interactive effects were noted for mixtures of pesticides compared to individually applied pesticides in terms of degradation of the parent compound or on seed germination, plant survival, or microbial respiration.     

Release behavior of triazine residues in stabilised contaminated soils

This paper reports the release behavior of two triazines (atrazine and simazine) in stabilised soils from a pesticide-contaminated site in South Australia. The soils were contaminated with a range of pesticides, especially with triazine herbicides. With multiple extractions of each soil sample with deionised water (eight in total), 15% of atrazine and 4% of simazine residues were recovered, resulting in very high concentrations of the two herbicides in leachate. The presence of small fractions of surfactants was found to further enhance the release of the residues. Methanol content up to 10% did not substantially influence the concentration of simazine and atrazine released. The study demonstrated that while the stabilisation of contaminated soil with particulate activated carbon (5%) and cement mix (15%) was effective in locking the residues of some pesticides, it failed to immobilise triazine herbicides residues completely. Given the higher water solubility of these herbicides than other compounds more effective strategies to immobilise their residues is needed.     

Sorption of Pesticides on Kaolinite and Montmorillonite as a Function of Hydrophilicity

Pesticides and other organic species are adsorbed by soil via different mechanisms, with bond strengths that depend on the properties of both the soil and the pesticide. Since the clay fraction in soil is a preferential sorbent for organic matter, reference kaolinite and montmorillonite are useful models for studying the mechanism and the strength of sorption. This paper presents the results of batch experiments to investigate the interactions of kaolinite KGa-1 and montmorillonite SWy-1 with the following pesticides and organic species resulting from the natural degradation of pesticides in the environment: atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine), simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine), diuron [1,1-dimethyl-3-(3,4-dichlorophenyl)urea], aniline, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol. Each of these chemicals has different hydrophilicity. Systems containing 2.0 g of clay were put in contact with 100.0 mL of solutions of the pesticides at known concentration ranging from 1.0 to 5.0 mg/L, and the amount of solute adsorbed was evaluated through RP-HPLC analysis of the pesticide still present in the aqueous suspension. To test for electrostatic interactions between the clay surface and the pesticides, potentiometric titration was used to determine the permanent surface charge of clays. Experiments were performed at different pH values. The results indicate that, for the chemicals studied, neutral molecules are preferentially retained relative to ionized ones, and that montmorillonite is a more effective sorbent than kaolinite.     

Paper electrophoretic separations of some common pesticides : Determination of monocrotophos,rogor and malathion in soil samples

Abstract

Paper electrophoretic movements of a number of pesticides belonging to organophosphorus, organochlorine and pyethroid groups in various acid background electrolytes have been studied. The effect of pH and pKa of the acids on the movement of these pesticides have also been studied. It has been observed that the movement of most of the pesticides is enhanced with increase in the degree of ionisation of the acids (pKa) studied as background electrolytes. The movement also increases with increase in the pH of acids. On the basis of differential movement of pesticides towards cathode and anode, a number of separations have been achieved from binary mixtures. Monocrotophos, rogor and malathion have been determined quantitatively (28.6 ‐ 29.2 μg) in alcoholic extracts of soil samples.     

Some models for the adsorption kinetics of pesticides in soil

Abstract

Three models describing adsorption‐desorption kinetics of pesticides in soil, that could be incorporated into computer programs on pesticide movement in soil, were discussed, The first model involved single first‐order rate equations for adsorption and desorption. Results from an analytical and a numerical solution for local equilibration were compared. Concentration‐time relationships for the solution and adsorbed phases were calculated for different rate constants, initial conditions, and partition ratios at equilibrium. The second model described simultaneous adsorption‐desorption equilibration with two mechanisms, both with their own rate constants. After a comparatively fast equilibration with the first mechanism, there was a gradual increase in extent of overall‐adsorption, accompanied with a shift to greater amounts adsorbed by the second mechanism. With the third model, adsorption equilibration occurred by diffusion into a stagnant region. With diffusion distances ranging from 0.1 to 4.0 cm, the time needed for approach to adsorption equilibrium varied from about 0.25 days to about one year. Some of the possibilities of these models were discussed considering published experimental results.     

Impact of long‐term pesticide applications on some soil biological parameters

Abstract

The soil oxidative and anaerobic processes, as well as, the microbial biomass were followed during three years in a cotton farm (Tatuí) where the recommended pesticides have been used for several years, and in an experimental field (São Paulo) treated first time with the same pesticides. The oxidative process was monitored by the dehydrogenase (DHA)‐activity using triphenyltetrazolium chloride (TTC) as substrate. The anaerobic process was followed by the iron‐oxide reduction, and the microbial biomass was estimated by the substrate (glucose)‐indiced respiration. Increases in DHA‐activity and in the microbial biomass occurred only in the farm soil, with concomitant decreases in iron‐reduction. In the experimental field soil, the increases in DHA‐activity were followed only by decreases in iron‐reduction. Soil characteristics were the determining factor for different biological parameters after pesticide inputs. All the pesticides produced at least one clear but transient effect.