Catalytic properties of cyclodextrins on the hydrolysis of parathion and paraoxon in aquatic medium containing humic acids

The inclusion catalysis effects of -,β- and γ-cyclodextrins(CyDs) on the hydrolysis rate of parathion, methyl parathion and paraoxon were investigated at 25°C in alkaline buffer solution(pH=8.5) containing humic acids. The hydrolysis rate of these pesticides was increased by the presence of humic acids. The inclusion catalysis of β-CyD inhibited parathion hydrolysis but promoted paraoxon hydrolysis. The CyD inclusion catalysis showed characteristic correlation with relative magnitudes of the inclusion-depth parameters of the pesticides which could be determined by the rotational-strength analysis of the induced circular dichroism. The essential properties of the CyD inclusion catalysis were explained in terms of the geometries of the CyD-pesticide inclusion complexes which determine degree of the proximity between the pesticide reaction site and the CyD catalytic site.     

Effects of cyclodextrins on photodegradation of organophosphorus pesticides in humic water

Cyclodextrin (CyD) effects on photodegradations of organophosphorus pesticides in humic water were monitored on the basis of the increase percentage of the photodegradation rate constant for CyD-containing humic water. Remarkable promotion effects of CyDs were observed in humic water for photo-induced radical generation. The promotion effects could be mainly assigned to the inclusion effects of CyDs to catalyze interactions of pesticides with reactive radicals generated by the humin photosensitizer and inclusion-trapped in CyDs.     

Evaluation of HCH isomers and metabolites in soils, leachates, river water and sediments of a highly contaminated area

In this work we evaluate the contamination caused by HCH residues in the soil, leachates, river water and sediments of an industrial estate of the NW of Spain. We study the distribution of the isomers in the different matrices, analysing 37 soil samples, collected in eight points at several depths, six natural leachates, four river water samples and three river sediments. Soil and leachate samples present very high levels of HCH isomers, higher than the established by legislation, and some pesticides were also detected in the analysed river water whereas no pesticides were detected in the river sediments. The distribution of isomers was different depending on the matrix analysed. Some natural degradation products and also other organochlorine pesticides were detected in the samples analysed.     

Organics in the water column of Llake Pontchartrain

A study was conducted to quantitatively screen the Inner Harbor Navigation Canal of Lake Pontchartrain for the presence of EPA priority pollutants and any other pollutants detected in significant concentration. Water column samples were collected at different depths and on the flood and ebb tides. Compounds identified include aliphatic and aromatic hydrocarbons, phthlates, phenols, alcohols, amines, pesticides, herbicides, aldehydes, quinolines, fatty acids, carboxylic acids. These compounds were detected at the parts-per-trillion level. The concentrations of the individual organics detected on the flood and ebb tides were not significantly different. The data derived from samples taken at two different depths suggest that the distribution of organics in the water column was homogeneous.     

Pesticide pollution remains severe after cleanup of a stockpile of obsolete pesticides at Vikuge, Tanzania

High levels of DDT residues and hexachlorocyclohexanes (HCHs) were found in soil, well water, and surface water around a collapsed pesticide storage shed at Vikuge Farm, Tanzania. Residues of DDT and HCHs were found at three soil depths down to 50 cm. Surface soil samples contained up to 28% total DDT and 6% total HCH residues. Water samples had concentrations of up to 30 microg L(-1) of organochlorine pesticides. Other compounds detected were aldrin, azinphos-methyl, carbosulfan, gamma-chlordane, chlorprofam, heptachlor, hexazinone, metamitron, metazachlor, pendimethalin, and thiabendazole. Although the visible remains of pesticides have been removed, the remaining soil is itself hazardous waste and poses a risk to the environment and the inhabitants of the surrounding villages. These findings show the necessity to follow up the environmental situation at former storage sites of obsolete stocks of pesticides, and that the environmental problems are not necessarily solved by removing the visible remains.     

Leaching and degradation of 21 pesticides in a full-scale model biobed

Filling and cleaning of pesticide sprayers presents a potential risk of pollution of soil and water. Three different solutions for handling sprayers have been suggested: Filling and cleaning in the field, filling and cleaning on hard surfaces with collection of the waste water, and filling and cleaning on a biobed, which is an excavation lined with clay and filled with a mixture of chopped straw, sphagnum and soil with turf on top, and with increased sorption capacity and microbial activity for degradation of the pesticides. In the present study the degradation and leaching of 21 pesticides (5 g of each) was followed in an established full-scale model biobed. Percolate was collected and analysed for pesticide residues, and the biobed material was sampled at three different depths and analysed by liquid chromatography double mass spectrometry (LC-MSMS). During the total study period of 563 days, no traces of 10 out of 21 applied pesticides were detected in the percolate (detection limits between 0.02 and 0.9 μg l⁻¹) and three pesticides were only detected once and at concentrations below 2 μg l⁻¹. During the first 198 days before second application, 14% of the applied herbicide bentazone was detected in the leachate with maximum and mean concentrations of 445 and 172 μg l⁻¹, respectively. About 2% of the initial mecoprop and fluazifop dose was detected in the percolate, with mean concentrations of 23 μg l⁻¹, while MCPA and dimethoate had mean concentrations of 3.5 and 4.7 μg l⁻¹, respectively. Leachate concentrations for the remaining pesticides were generally below the detection limit (0.02–0.9 μg l⁻¹, below 1% of applied). Sorption studies of five pesticides showed that compounds with a low K_d value appeared in the leachate. After 169 days, all pesticides in the biobed profile were degraded to a level below 50% of the calculated initial dose. Pesticides with K_oc values above 100 were primarily found in the uppermost 10 cm and degraded slowest due to the low bioavailability. The 11 most degradable pesticides were all degraded such that less than 3% remained in the biobed after 169 days.

Following second pesticide application of the biobed, leachate was sampled 215 and 365 days after the treatment. This showed the same pesticides to be leached out and at concentrations comparable to those of the first treatment. The same pesticides as after the first treatment were retained in the biobed.     

Soil temperature effect in calculating attenuation and retardation factors

The effect of annual variation of daily average soil temperature, at different depths, in calculating pesticides ranking indexes retardation factor and attenuation factor is presented. The retardation factor and attenuation factor are two site-specific pesticide numbers, frequently used as screening indicator indexes for pesticide groundwater contamination potential. Generally, in the calculation of these two factors are not included the soil temperature effect on the parameters involved in its calculation. It is well known that the soil temperature affects the pesticide degradation rate, water-air partition coefficient and water-soil partition coefficient. These three parameters are components of the retardation factor and attenuation factor and contribute to determine the pesticide behavior in the environment. The Arrhenius equation, van't Hoff equation and Clausius-Clapeyron equation are used in this work for estimating the soil temperature effect on the pesticide degradation rate, water-air partition coefficient and soil-water partition coefficient, respectively. These dependence relationships, between results of calculating attenuation and retardation factors and the soil temperature at different depths, can aid to understand the potential pesticide groundwater contamination on different weather conditions. Numerical results will be presented with pesticides atrazine and lindane in a soil profile with 20 degrees C constant temperature, minimum and maximum surface temperatures varying and spreading in the soil profile between -5 and 30 degrees C and between 15 and 45 degrees C.     

Leaching of 2,4-D from a soil in the presence of beta-cyclodextrin: laboratory columns experiments

This study reports on the effect of the presence of beta-cyclodextrin (beta-CD) on the adsorption and mobility of the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) through soil columns. The previous application of beta-CD to the soil produced a retarded leaching of 2,4-D through the soil column, due probably to herbicide adsorption on the soil through beta-CD adsorbed. However, the application of beta-CD solution to the soil column where 2,4-D had been previously adsorbed, led to the complete desorption of the herbicide, due to the formation of water-soluble 1:1 inclusion complexes between 2,4-D and beta-CD. Beta-CD can be viewed as a microscopic organic-phase extractant. It can be an advantage to remove from soil pesticides which are able to form inclusion complexes with cyclodextrins, making them possible candidates for use in in situ remediation efforts.     

Influence of the DMPP (3,4-dimethyl pyrazole phosphate) on nitrogen transformation and leaching in multi-layer soil columns

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, using a multi-layer soil column device, the influence of new nitrification inhibitor DMPP (3,4-dimethyl pyrazole phosphate) was studied for understanding the nitrogen vertical transformation and lowering the nitrate leaching at different soil profile depths. The results indicated that, within 60 d of experiment, the regular urea added 1.0% DMPP can effectively inhibit the ammonium oxidation in the soil, and improve the ammonium concentration in soil solution over the 20cm depths of soil profile, while decline the concentrations of nitrate and nitrite. No obvious difference was found on ammonium concentrations in soil solution collected from deep profile under 20cm depths between regular urea and the urea added 1.0% DMPP. There was also no significant difference for the nitrate, ammonium and nitrite concentrations in the soil solution under 40cm depths of soil profile with the increasing nitrogen application level, among the treatments of urea added 1.0% DMPP within 60 d. It is proposed that DMPP could be used as an effective nitrification inhibitor in some region to control ammonium oxidation and decline the ion-nitrogen leaching, minimizing the shallow groundwater pollution risk and being beneficial for the ecological environment.     

Modeling depth-variant and domain-specific sorption and biodegradation in dual-permeability media

A dual-permeability model (S_1D_DUAL) was developed to simulate the transport of land-applied pesticides in macroporous media. In this model, one flow domain was represented by the bulk matrix and the other by the preferential flow domain (PFD) where water and chemicals move at faster rates. The model assumed the validity of Darcian flow and the advective-dispersive solute transport in each of the two domains with inter-domain transfer of water and solutes due to pressure and concentration gradients. It was conceptualized that sorption and biodegradation rates vary with soil depth as well as in each of the two flow domains. In addition to equilibrium sorption, kinetic sorption was simulated in the PFD. Simulations were conducted to evaluate the combined effects of preferential flow, depth- and domain-variant sorption, and degradation on leaching of two pesticides: one with strong sorption potential (trifluralin) and the other with weak sorption potential (atrazine). Simulation results for a test case showed that water flux in the PFD was three times more than in the matrix for selected storm events. When equilibrium sorption was considered, the simulated profile of trifluralin in each domain was similar; however, the atrazine profile was deeper in the PFD than in the bulk matrix under episodic storm events. With an assumption of negligible sorption in the PFD, both the atrazine and the trifluralin profiles moved twice deeper into the PFD. The simulated concentrations of the chemicals were several orders higher in the PFD than in the matrix, even at deeper depths. The volume fraction of the macropores and the sorption and biodegradation properties of the chemicals could also affect the amount of pesticides leaving the root zone. For an intense storm event, slow sorption reaction rates in the PFD produced higher breakthrough concentrations of atrazine at the bottom of the simulated soil profile, thus posing the risk for breakthrough of chemicals from the root zone.     

Effects of thiobencarb in combinations with molinate and chlorpyrifos on selected soil microbial processes

The impact of pesticides, namely thiobencarb (TBC), molinate (MOL) and chlorpyrifos (CPF), on soil microbial processes was studied in two Australian soils. Substrate induced respiration (SIR), substrate induced nitrification (SIN) and phosphatases and chitinase enzymatic activities were assessed during a 30-day microcosm study. The pesticides were applied to soils at recommended rates either alone, or as binary mixtures with TBC. Soil samples were sampled at 5, 15 and 30 days after pesticide treatments. Substrate induced respiration was only transiently affected by pesticides in both soils. In contrast, the process of indigenous nitrification was affected by the presence of pesticides in both soils, especially when the pesticides were applied as binary mixtures. Substrate induced nitrification increased with pesticides in the Griffith soil (except with MOL+TBC after 5 days) whereas SIN values were non-significantly different to the control on the Coleambally soil. The binary mixtures of pesticides with TBC resulted in a decrease in SIN in both soils, but the effects disappeared within 30 days. The enzymatic activities were not consistently affected by pesticides, and varied with the soil and pesticides studied. This study showed that, when applied at recommended application rates, TBC, MOL, and CPF (individually or as binary mixtures), had little or only transitory effects on the functional endpoints studied. However, further investigations are needed to assess the effect on microbial densities and community structure despite the low disturbance to the functions noted in this work.     

Sample preparation for GC analysis of selected pesticides in surface water.

A new isolation procedure for the determination of nitrogen/phosphorous containing pesticides and organochlorine pesticides in water was tested, and statistical evaluation of the recoveries was performed. The procedure, designed specifically for the analysis of semi-volatile compounds in water containing Suspended Particulate Matter (SPM), utilizes a specially designed filtration vessel coupled directly to an SPE cartridge. The studies were based on surface water samples (from the Vistula River) spiked with pesticides. SPM separation and analyte isolation/concentration were carried out in a special filtration vessel. Pesticides were sorbed both on the SPE cartridge and on the suspended matter. The cartridge and the filter with the suspended matter were extracted separately with a solvent, which enabled the determination of analyte distribution between the two. For organochlorine pesticides, between 3 and 60% of the initial amount was found on the filter, while the recoveries in the filtrate ranged from 30 to 98%. Total recoveries of organochlorine pesticides from surface water samples spiked with pesticides using the method described were high, ranging from 90 to 101%. The amounts of nitrogen/phosphorus containing pesticides recovered from the filter were lower than 2%, while those from the filtrate ranged from 69 to 92%. Total recoveries of nitrogen/phosphorus containing pesticides from surface water samples were high, ranging from 71 to 92%.     

Effects of synthetic pyrethroids and methidation on activities of some digestive enzymes in carp (Cyprinus carpio L.).

The effects of pyrethroid pesticides (deltamethrin, permethrin and cypermethrin) and an organophosphate ester (methidation) on the activities of carp trypsin, alpha-chymotrypsin, carboxypeptidase A and lipase were studied. The enzymes were isolated from the gastrointestinal tract and the effects of the pesticides were investigated during incubation for 5 min. The activity of trypsin was influenced only slightly by the presence of deltamethrin and methidation, whereas permethrin and cypermethrin caused significant inhibition. The pyrethroid pesticides at lower concentrations resulted in a slight activation of alpha-chymotrypsin. Methidation inhibited the alpha-chymotrypsin activity by about 20%. These pesticides modified the lipase activity to a lesser extent; the highest inhibition was measured with cypermethrin. The carboxypeptidase A activity was inhibited by both pyrethroid pesticides and methidation. The results suggest that these pesticides might interact with the active conformation of the studied hydrolytic enzymes, resulting in changes in their activities.     

Effects of synthetic pyrethroids and methidation on activities of some digestive enzymes in carp (Cyprinus carpio L.)

Abstract

The effects of pyrethroid pesticides (deltamethrin, permethrin and cypermethrin) and an organophosphate ester (methidation) on the activities of carp trypsin, α‐chymotrypsin, carboxypeptidase A and lipase were studied. The enzymes were isolated from the gastrointestinal tract and the effects of the pesticides were investigated during incubation for 5 min. The activity of trypsin was influenced only slightly by the presence of deltamethrin and methidation, whereas permethrin and cypermethrin caused significant inhibition. The pyrethroid pesticides at lower concentrations resulted in a slight activation of α‐chymotrypsin. Methidation inhibited the α‐chymotrypsin activity by about 20%. These pesticides modified the lipase activity to a lesser extent; the highest inhibition was measured with cypermethrin. The carboxypeptidase A activity was inhibited by both pyrethroid pesticides and methidation. The results suggest that these pesticides might interact with the active conformation of the studied hydrolytic enzymes, resulting in changes in their activities.     

LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.     

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.     

Accumulation and persistence of chlorobiphenyls, organochlorine pesticides and faecal sterols at the Garroch Head sewage sludge disposal site, Firth of Clyde

The sediment concentrations of organic carbon, faecal sterols, individual chlorobiphenyl congeners and organochlorine pesticides have been measured in seabed cores from the sewage sludge disposal area at Garroch Head in the Firth of Clyde. The measurements confirm the accumulative nature of the site with high levels of sedimentary faecal sterols (152 mg kg(-1) coprostanol). Levels of chlorobiphenyls, DDT compounds and dieldrin in surface sediment were elevated by factors of 12, 40 and 120, respectively, over those observed at a site remote from the effects of dumping. Total chlorobiphenyl levels of 515 microg kg(-1) Arochlor 1254 in surface sediment were comparable to levels found in other areas heavily contaminated with sewage sludge. The 20-cm depth of heavily sludge-contaminated sediment overlays a mixed sludge/basal sediment layer some 10 cm in depth. Levels of organochlorine contaminants were elevated to depths of 90 cm in the sediment, suggesting that the surface layer is a source of contaminants to the deeper sediment. Within the upper 15-20 cm sediment in the disposal area, chlorobiphenyls are conservative, the variation in their concentration with respect to depth being related to historical input. Lindane and possibly dieldrin, and hexachlorobenzene are not conservative. Faecal sterols are removed in sub-surface sediment, in contrast to conservative behaviour previously found at other sewage polluted sites.     

Modelling the dissipation kinetics of six commonly used pesticides in two contrasting soils of New Zealand

We used three non-linear bi-phasic models, bi-exponential (BEXP), first-order double exponential decay (FODED), and first-order two-compartment (FOTC), to fit the measured degradation data for six commonly used pesticides (atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone) in two New Zealand soils. Corresponding DT₅₀ and DT₉₀ values for each compound were numerically obtained and compared against those estimated by simple first-order kinetic (SFOK) model. All 3 non-linear models gave good fit of the measured data under both soil depths and were well supported by the values obtained for the respective statistical indices (RMSE, CRM and r ²). The FOTC model gave by far the best fit for most compounds, followed by the FODED and BEXP models. Overall, DT₅₀ values derived by non-linear models for the six compounds in soils from both sites were lower than the values obtained by the SFOK model. Differences in the SFOK and the three non-linear models derived DT₉₀were, however, an order of magnitude higher for some compounds, while for others differences were very small. Although all three non-linear models described most data by giving excellent fits, in a few instances > 5–10% asymptotes hindered the estimation of DT₉₀ values. This work shows that when degradation deviates from first-order kinetic, application of non-linear decay models to describe the kinetics of degradation becomes important in order to derive the true end-points for pesticides in soil.     

Contamination of vegetables of different seasons with organophosphorous pesticides and related health risk assessment in northern India

India is an agrarian country. The use of pesticides, herbicides and fungicides were introduced in India during the mid-sixties, which are now being used on a large scale and is a common feature of Indian agriculture. The main intention of the introduction of pesticides was to prevent and control insects, pests and diseases in the field crops. Initially the use of pesticides reduced pest attack and paved way for increasing the crop yield as expected. Simultaneously, increased use of chemical pesticides has resulted in contamination of environment and also caused many long-term affect on the society. In the present study an effort has been made to evaluate the residual concentration of selected organophosphorous pesticides (methyl parathion, chlorpyriphos and malathion) in vegetables grown in different seasons (summer, rainy and winter). Data obtained was then used for estimating the potential health risk associated with the exposure to these pesticides. The pesticides residue concentrations in vegetables of different season shows that the winter vegetables are the most contaminated followed by summer and rainy vegetables. The concentration of the various pesticides were well below the established tolerances but continuous consumption of such vegetables even with moderate contamination level can accumulate in the receptor's body and may prove fatal for human population in the long term. The analysis of health risk estimates indicated that chlorpyriphos and malathion did not poses a direct hazard, however, exposure to methyl parathion has been found to pose some risk to human health.     

Relationships between pesticides and organic carbon fractions in sediments of the Danshui River estuary and adjacent coastal areas of Taiwan

In order to understand the fate of pesticides in marine environments, concentrations of pesticides and different carbonaceous fractions were determined for surface sediments in the Danshui River and nearby coastal areas of Taiwan. The major compounds detected were tetrachlorobenzene, HCHs, chlordane, aldrin, DDDs, DDEs and DDTs. Total concentrations of pesticides in the sediments ranged from not detectable to 23 ng g(-1), with the maximum value detected near the discharge point of the marine outfall from the Pali sewage treatment plant. These results confirm that pesticides persist in estuarine and nearby coastal environments of the Danshui River well after their ban. Concentrations of total pesticides significantly correlate with concentrations of total organic carbon and black carbon in these sediments, suggesting that total organic carbon and black carbon regulate the distribution of trace organic pollutants in fluvial and coastal marine sediments.