Mitigation of dimethazone residues in soil and runoff water from agricultural field

Dimethazone, also known as clomazone [2-[(2-chlorophenyl) methyl]- 4,4-dimethyl-3-isoxaolidinone] is a pre-emergent nonionic herbicide commonly used in agriculture. A field study was conducted on a silty-loam soil of 10 % slope to monitor off-site movement and persistence of dimethazone in soil under three management practices. Eighteen plots of 22 x 3.7 m each were separated using stainless steel metal borders and the soil in six plots was mixed with municipal sewage sludge (MSS) and yard waste (YW) compost (MSS+YW) at 15 t acre?1 on dry weight basis, six plots were mixed with MSS at 15 t acre?1, and six unamended plots (NM) were used for comparison purposes. The objectives of this investigation were to: (i) monitor the dissipation and half-life (T?/?) of dimethazone in soil under three management practices; (ii) determine the concentration of dimethazone residues in runoff and infiltration water following natural rainfall events; and (iii) assess the impact of soil amendments on the transport of NO?, NH?, and P into surface and subsurface water. Gas chromatography/mass spectrometery (GC/MS) analyses of soil extracts indicated the presence of ion fragments at m/z 125 and 204 that can be used for identification of dimethazone residues. Intitial deposits of dimethazone varied from 1.3 μg g?1 dry native soil to 3.2 and 11.8 μg g?1 dry soil in MSS and MSS+YW amended soil, respectively. Decline of dimethazone residues in the top 15 cm native soil and soil incorporated with amendments revealed half-life (T?/?) values of 18.8, 25.1, and 43.0 days in MSS+YW, MSS, and NM treatments, respectively. Addition of MSS+YW mix and MSS alone to native soil increased water infiltration, lowering surface runoff water volume and dimethazone residues in runoff following natural rainfall events.     

固相萃取-毛细管气相色谱法测定蔬菜、土壤和水中的毒死蜱残留量

采用固相萃取技术提取蔬菜、土壤和水体中毒死蜱,建立了蔬菜、土壤和水体中毒死蜱的固相萃取-气相色谱测定方法,并与传统方法进行了比较。添加浓度为0.1、1、10 mg·L-1,两种方法的水样平均回收率分别在93.7%~102.7%和96.2%~100.2%,变异系数分别在2.2%~7.7%和3.3%~5.1%;土壤平均回收率分别在91.3%~100.7%和92.0%~104.8%,变异系数分别在1.4%~7.0%和0.3%~5.2%;蔬菜平均回收率分别在89.4%~101.4%和92.5%~101.8%,变异系数分别在5.2%~7.1%和3.1%~6.0%。试验结果表明,固相萃取法与传统方法的回收率和变异系数相当,但前者更加省时、省力和省溶剂。     

Molecularly imprinted polymers for the detection of benomyl residues in water and soil samples

Benomyl is a benzimidazol fungicide used against various crop pathogens. Although banned in many countries, it is still widely used worldwide and is listed in different monitoring programs among the substances to be monitored to assess human exposure to pesticide residues. The assessment of benomyl is mainly based on the analysis of the residues of its most important metabolite, carbendazim. Existing methods often lack of selectivity and display a limited performance because of the presence of co-extracted compounds. Molecularly imprinted polymers (MIPs) offer an alternative methodology, adsorbing preferentially those target molecules for which the polymers are specifically prepared. In this study, we optimized the synthesis of a polymer imprinted with benomyl. Tests of specificity recognition showed a good performance for carbendazim compared with other similar pesticides. The mean recovery of benomyl (measured as carbendazim) from water samples was estimated to be 90% for MIPs while with real soil samples collected in Morocco the recovery efficiency was 62%. Preliminary tests also suggest that this MIP can implement traditional SPE techniques for assessing benomyl residual concentrations in environmental samples.     

Organochlorine residues in water from the Mahala water reservoir, Jaipur, India

Residues of p,p'-DDE, p,p'-DDT alpha-, beta-, gamma-isomers of HCH, aldrin and heptachlor in water, from four different sites of the Mahala water reservoir were monitored periodically from September 1985 to October 1987. All the samples contained the above residues in varying concentrations. Isomers of HCH predominated and were followed in relative dominance by aldrin, total DDT and heptachlor residues, p,p'-DDE and p,p'-DDD constituted the major fraction of total p,p'-DDT. Monthly total organochlorine residue levels in water ranged between 1.07 and 81.23 microg litre-1. The variation is attributed to the run-off or subsoil water movement from the catchment area.     

Degradation kinetics of forchlorfenuron in typical grapevine soils of India and its influence on specific soil enzyme activities

The rate of degradation of forchlorfenuron, a cytokinin-based plant growth regulator (PGR) was explored in typical grapevine soils of India with simultaneous evaluation of its effect on biochemical attributes of the test soils in terms of the activities of specific soil microbial enzymes. In all the test soils, namely clay, sandy-loam and silty-clay, the dissipation rate was faster at the beginning, which slowed down with time, indicating a non-linear pattern of degradation. Degradation in soils could best be explained by two-compartment 1st + 1st order kinetics with half-life ranging between 4–10 days. The results suggest that organic matter might be playing a major role in influencing the rate of degradation of forchlorfenuron in soil. The rate of degradation in sandy-loam soil was fastest followed by clay and silty-clay soils, respectively. Comparison of the rate of degradation in natural against sterilized soils suggests that microbial degradation might be the major pathway of residue dissipation. Changes in soil enzyme activities as a consequence of forchlorfenuron treatment were studied for extra-cellular enzymes namely acid phosphatase, alkaline phosphatase and β -glucosidase and intracellular enzyme-dehydrogenase. Although small changes in enzyme activities were observed, forchlorfenuron did not have any significant deleterious effect on the enzymatic activity of the test soils. Simple correlation studies between degradation percentage and individual enzyme activities did not establish any significant relationships. The pattern and change of enzyme activity was primarily the effect of the incubation period rather than the effect of forchlorfenuron itself.     

Behaviour and redox sensitivity of antimicrobial residues during bank filtration

The behaviour of residues of antibiotic drugs during bank filtration was studied at a field site in Berlin, Germany, where bank-filtered water is used for the production of drinking water. The neighbouring surface water used for bank filtration is under the influence of treated municipal wastewater. Seven out of 19 investigated antimicrobial residues were found in the surface water with median concentrations between 7 and 151ngL(-1). Out of the seven analytes detected in the surface water only three (anhydroerythromycin, clindamycin and sulfamethoxazole) were found with median concentrations above their limits of quantitation in bank filtrate with a travel time of one month or less. With the exception of sulfamethoxazole, none of the 19 analytes were present in bank filtrate with a residence time larger than one month or in the water-supply well itself. Sulfamethoxazole found with a median concentration of 151ngL(-1) in the surface water was the most persistent of all antimicrobial residues. Nevertheless, it was also removed by more than 98% and only found with a median concentration of 2ngL(-1) in the water-supply well. The degradation of clindamycin and sulfamethoxazole appear to be redox-dependent. Clindamycin was eliminated more efficiently under oxic infiltration conditions while sulfamethoxazole was eliminated more rapidly under anoxic infiltration conditions. A slight preference for an improved degradation under oxic (clarithromycin and roxithromycin) or anoxic (anhydroerythromycin) conditions was also observed for the macrolide antibiotics. Nevertheless, all macrolides were readily removable by bank filtration both under oxic and anoxic conditions.     

Degradation kinetics of forchlorfenuron in typical grapevine soils of India and its influence on specific soil enzyme activities

The rate of degradation of forchlorfenuron, a cytokinin-based plant growth regulator (PGR) was explored in typical grapevine soils of India with simultaneous evaluation of its effect on biochemical attributes of the test soils in terms of the activities of specific soil microbial enzymes. In all the test soils, namely clay, sandy-loam and silty-clay, the dissipation rate was faster at the beginning, which slowed down with time, indicating a non-linear pattern of degradation. Degradation in soils could best be explained by two-compartment 1st+1st order kinetics with half-life ranging between 4-10 days. The results suggest that organic matter might be playing a major role in influencing the rate of degradation of forchlorfenuron in soil. The rate of degradation in sandy-loam soil was fastest followed by clay and silty-clay soils, respectively. Comparison of the rate of degradation in natural against sterilized soils suggests that microbial degradation might be the major pathway of residue dissipation. Changes in soil enzyme activities as a consequence of forchlorfenuron treatment were studied for extra-cellular enzymes namely acid phosphatase, alkaline phosphatase and beta -glucosidase and intracellular enzyme-dehydrogenase. Although small changes in enzyme activities were observed, forchlorfenuron did not have any significant deleterious effect on the enzymatic activity of the test soils. Simple correlation studies between degradation percentage and individual enzyme activities did not establish any significant relationships. The pattern and change of enzyme activity was primarily the effect of the incubation period rather than the effect of forchlorfenuron itself.     

Bound residues of organic compounds in the soil: the significance of pesticide persistence in soil and water: a European regulatory view

The paper discusses key aspects of the European Union (EU) regulatory policy for persistence of agricultural pesticide active substances (a.s.) in soil, which is examined in the context of the EU Authorisations Directive (91/414/EEC). For agricultural pesticide regulation within EU Member States (MS), the Authorisations Directive will gradually replace existing national systems. Discussion is concentrated on this directive, looking in particular at the Uniform Principles therein and the possible ways that these decision-making guidelines could be developed into a regulatory framework. The aim in this process of negotiated development is to identify any questions or data requirements that will be needed for persistent pesticides, over and above those generally required for all compounds. The present European regulatory position on soil non-extractable or bound residues is discussed. Finally, a brief mention of pesticide persistence in water and sediment is made.     

Insecticide residues in cotton crop soil

Dimethoate, monocrotophos, triazophos, deltamethrin, cypermethrin and endosulfan were applied to a cotton crop soil located at Nurpur village, Punjab, India. The insecticides were applied sequentially at recommended dosages in cotton fields by foliar application in 1995, 1996 and 1998. Soil samples were collected from the cotton crop farms and extracted with acetone. The extracted material was analysed by a gas liquid chromatograph (GLC) equipped with an 63Ni electron-capture detector (ECD-63Ni). Recovery data was obtained by fortifying soil with insecticide. The average recoveries from the fortified soil samples were 76-92% for organophosphorous compounds and 90-98% for synthetic pyrethroids and organochlorines. The results showed that the insecticide residues under study were present in the range of 1.16 to 41.97 ng g(-1) d.wt.soil. The pattern of dissipation of the insecticides used was similar for the duration of the crop. Half lives of the insecticides ranged from 7 to 22 days. Except endosulfan none of the other insecticides used were leached below 15 cm. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite. Persistence and dissipation pattern in soils with history of exposure to the insecticide compared to non-history soils were similar.     

Concentration and dissipation of chlorantraniliprole and thiamethoxam residues in maize straw,maize, and soil

To study the dissipation rates and final residual levels of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil, two independent field trials were conducted during the 2014 cropping season in Beijing and Anhui Provinces of China. A 40% wettable powder (20% chlorantraniliprole?+?20% thiamethoxam) was sprayed onto maize straw and soil at an application rate of 118 g of active ingredient per hectare (g a.i.ha^?1). The residual concentrations were determined by ultra-high-performance liquid chromatography–tandem mass spectrometry. The chlorantraniliprole half-lives in maize straw and soil were 9.0–10.8 and 9.5–21.7 days, respectively. The thiamethoxam half-lives in maize straw and soil were 8.4–9.8 and 4.3–11.7 days, respectively. The final residues of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil were measured after the pesticides had been sprayed two and three times with an interval of 7 days using 1 and 1.5 times the recommended rate (72 g a.i. ha^?1 and 108 g a.i. ha^?1, respectively). Representative maize straw, maize, and soil samples were collected after the last treatment at pre-harvest intervals of 7, 14, and 28 days. The chlorantraniliprole residue was below 0.01 mg kg^?1 in maize, between 0.01 and 0.31 mg kg^?1 in maize straw, and between 0.03 and 1.91 mg kg^?1 in soil. The thiamethoxam residue concentrations in maize, maize straw, and soil were <0.01, <0.01, and 0.01–0.03 mg kg^?1, respectively. The final pesticide residues on maize were lower than the maximum residue limit (MRL) of 0.02 mg kg^?1 after a 14-day pre-harvest interval. Therefore, a dosage of 72 g a.i. ha^?1 was recommended, as it can be considered safe to human beings and animals.     

Behaviour and redox sensitivity of pharmaceutical residues during bank filtration - Investigation of residues of phenazone-type analgesics

The behaviour of residues of phenazone-type pharmaceuticals during bank filtration was investigated at a field site in Berlin, Germany, where bank-filtered water is used for drinking water production. The concentrations of the pharmaceutical residues in the shallow, young bank filtrate (travel times相似文献   

Effect of decontamination and processing on insecticide residues in grape (Muscat Hamburg)

Environmental Science and Pollution Research - Field and laboratory experiments were conducted to study the effect of simple decontamination methods and processing on imidacloprid, dimethoate, and...     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

Distribution of pesticide residues in soil and uncertainty of sampling

Pesticide residues were determined in about 120 soil cores taken randomly from the top 15 cm layer of two sunflower fields about 30 days after preemergence herbicide treatments. Samples were extracted with acetone-ethyl acetate mixture and the residues were determined with GC-TSD. Residues of dimethenamid, pendimethalin, and prometryn ranged from 0.005 to 2.97 mg/kg. Their relative standard deviations (CV) were between 0.66 and 1.13. The relative frequency distributions of residues in soil cores were very similar to those observed in root and tuber vegetables grown in pesticide treated soils. Based on all available information, a typical CV of 1.00 was estimated for pesticide residues in primary soil samples (soil cores). The corresponding expectable relative uncertainty of sampling is 20% when composite samples of size 25 are taken. To obtain a reliable estimate of the average residues in the top 15 cm layer of soil of a field up to 8 independent replicate random samples should be taken. To obtain better estimate of the actual residue level of the sampled filed would be marginal if larger number of samples were taken.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

Persistent organochlorine pesticide residues in fish, sediments and water from Lake Bosomtwi, Ghana

Some organochlorine pesticide residues in tilapia fish (Tilapiazilli), sediment and water samples from Lake Bosomtwi (the largest natural lake in Ghana) were determined to find out the extent of pesticide contamination and accumulation in the lake. The extracted residues were analyzed on a micro-capillary gas chromatograph equipped with electron capture detector. DDE (p,p'-1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene) was the predominant residue in all the samples analyzed; detected in 82% of water samples, 98% of sediment samples and 58% of fish samples at concentrations of 0.061+/-0.03 ng g(-1), 8.342+/-2.96 ng g(-1) and 5.232+/-1.30 ng g(-1), respectively. DDT (p,p'-1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane) was detected in 78% at a mean concentration 0.012+/-0.62 ng g(-1) of water samples analyzed. The mean concentrations of DDT in sediments and fish were 4.41+/-1.54 ng g(-1) and 3.645+/-1.81 ng g(-1), respectively. The detection of lower levels of DDT than its metabolite, DDE, in the samples implies that the presence of these contaminants in the lake is as result of past usage of the pesticides.     

Behaviour of [ring-C] hydroxy-simazine in a parabraun soil

[Ring-¹⁴C] hydroxy-simazine was incubated in a parabraun soil for 102 days at 22°C and 65 % of the maximum water-holding capacity. Soil samples were analyzed according to two different extraction methods on the day of application as well as after 13, 62 and 102 days. Furthermore, the influence of air-drying the soil specimens on the extraction yield was also studied. Hydroxy-simazine was converted to ¹⁴CO₂ only up to 0.2 % of the applied radioactivity. A rapid bonding of the radioactivity to the organic mass of the soil was observed, especially in the fulvic acid and humin fractions. 62 days after beginning conversion these two fractions already altogether contained up to 85 % of the labelled ring carbon applied. Whereas in the humic acids only a maximum of 4.5 % was discovered.     

Causes of phytotoxicity of metsulfuron-methyl bound residues in soil

The bioavailability and phytotoxicity of bound residues of metsulfuron-methyl were studied using 14C-labeling and bioassay with oil rape (Brassica napus L.). Soil bound residues at the concentration of 0.27 and 0.53 nmol g(-1) resulted in significant inhibition of oil rape seedling growth. The biologically active component of the bound residues was identified to be metsulfuron-methyl parent compound. Other metabolites, including the hydrolysis product 2-methylformate-benzenesulfonamide, showed no toxicity to the test species. This study suggests that residues of metsulfuron-methyl bound previously to the soil matrix could be again released upon planting. The phytotoxicity of metsulfuron-methyl bound residues was mainly caused by the metsulfuron-methyl parent compound that became available during plant growth.     

Monitoring of pesticide residues in a cotton crop soil

This paper reports on the residues of methyl parathion (O,O-dimethyl O-4-nitrophenyl phosphorothioate), trifluralin (alpha, alpha, alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine), endosulfan [(1, 4, 5, 6, 7, 7-hexachloro-8, 9, 10-trinorborn-5-en-2, 3-ylenebismethylene) sulfite] and dimethoate (O, O-dimethyl S-methylcarbamoylmethyl phosphorodithioate) in a cotton crop soil. Soil samples (0-15 cm) were collected at different periods from the cotton crop farm and subjected to Soxhlet extraction. The extracted material was analysed after clean-up by a HP5890 II gas chromatograph equipped with a 63Ni electron-capture detector (ECD-63Ni) and fitted with a 25 m x 0.2 mm i.d. fused silica capillary column [Ultra-2 (5% phenylmethyl polysiloxane)]. The recoveries of the pesticide residues from the spiked control soil were determined after Soxhlet extraction and C18 cartridges clean-up by using radiotracer techniques with the corresponding 14C-pesticides. The results show that in the cotton crop soil the pesticide residues under study were present in the range of 0.1 to 0.4 mg.kg-1. Endosulfan was found to be rapidly degraded in the soil and formed a sulfate metabolite.     

Analysis and residue levels of forchlorfenuron (CPPU) in watermelons

This paper describes the application of liquid chromatography-tandem mass spectrometry (LC/MS-MS) for analysis of residues of forchlorfenuron (CPPU), a new plant growth regulator, in watermelons, after a sample preparation step based on the buffered Quick, Easy, Cheap, Effective, Rugged and Safe extraction method. Analytical determinations were carried out in a triple quadrupole system fitted with an electrospray interphase operating in the positive ionisation mode (ESI+). Three simultaneous MS-MS transitions of the quasi-molecular ion m/z 248 (precursor ion) were monitored for data adquisition (248 > 129, 248 > 155, and 248 > 248), using the transition 248 > 129 for quantitation. Recovery studies on watermelons at levels of 1–200 μ g/kg, performing five replicates at each level and using bracketing single-level calibration with matrix-matched standards for quantitation, gave forchlorfenuron mean recoveries ranging from 82 to 106% with relative standard deviations (RSD) lower than 18%. The limit of determination was established at 1 μ g/kg. The method was applied to evaluate the persistence of forchlorfenuron residues in watermelons grown in plastic greenhouses, after applying an individual spray treatment to the flower ovary at the anthesis stage (45 μ g/flower and 60 μ g/flower for cv “Extazy” and cv “reina de corazones” watermelons, respectively). One month after treatment, 20 “Extazy” watermelon units (1.5–2 kg/unit) and 20 “Reina de corazones” watermelon units (4–5 kg/unit) were collected and analyzed individually. None of the samples contained forchlorfenuron residues higher than 1 μ g/kg.