Application of TLC for confirmation and screening of pesticide residues in fruits, vegetables, and cereal grains: Part 2. Repeatability and reproducibility of Rf and MDQ values

This paper illustrates the effect of major factors influencing the reproducibility of thin layer chromatography (TLC) separation and detection under largely differing environmental and laboratory conditions. The optimum conditions for reproducibility and detection sensitivity was obtained on 20 x 20 cm layer in the retention factor (Rf) range of 0.2-0.7 by applying the sample in spots of 3-4 mm diameter at 2 cm from the edge of the plate. The reproducibility rapidly decreased below Rf = 0.2. Above Rf = 0.2 the within-laboratory reproducibility of 219 pesticides obtained in ethyl acetate silica gel elution system by several laboratories was typically below 10%. The among-laboratories reproducibility of the average retention factors was generally below 12%. The minimum detectable quantities (MDQ) of 219 pesticide residues were determined with nine detection methods. The MDQ values largely varied depending on the mode of detection. Bioassay methods enabled the detection down to 0.1-10 ng, while 20-100 ng could be achieved with the chemical reagents. Higher MDQ values are also reported in order to assist the identification of compounds potentially present. The between-laboratories reproducibility of MDQ values was typically 1-5 MDQmin.     

Removal of pesticides from rinsate by adsorption using agricultural residuals as medium

Abstract

The feasibility of using agricultural residual with highly organic matter content ‐ spent mushroom compost (SMC) as adsorption medium for removal of pesticides including carbaryl, carbofuran, and aldicarb with a concentration range of 0–30 mg/L from rinsate was investigated. Bottle‐point method was used to determine adsorption isotherms for single‐pesticide and multi‐pesticides. It was found that SMC might potentially be used for on‐farm treatment of pesticide rinsate. The adsorption capacity of SMC was increased compared to most soils, possibly related to the increased organic matter content. The rapid equilibrium of pesticide solution and SMC was consistent with a physical type of adsorption mechanism. The adsorption of carbamate pesticides on SMC was found to exhibit nonlinear “favorable”; adsorption behavior that could be characterized well by the Freundlich isotherm model. In addition, the multi‐pesticide adsorption tests displayed the characteristics of competitive behavior. The competitive ability of these three pesticides in multi‐components adsorption was in the order carbaryl > carbofuran > aldicarb, which was consistent with the adsorbability of pesticides.     

Absorption of current use pesticides by snapping turtle (Chelydra serpentina) eggs in treated soil

Reptiles often breed within agricultural and urban environments that receive frequent pesticide use. Consequently, their eggs and thus developing embryos may be exposed to pesticides. Our objectives were to determine (i) if turtle eggs are capable of absorbing pesticides from treated soil, and (ii) if pesticide absorption rates can be predicted by their chemical and physical properties. Snapping turtle (Chelydra serpentina) eggs were incubated in soil that was treated with 10 pesticides (atrazine, simazine, metolachlor, azinphos-methyl, dimethoate, chlorpyrifos, carbaryl, endosulfan (I and II), captan, and chlorothalonil). There were two treatments, consisting of pesticides applied at application rate equivalents of 1.92 or 19.2 kg a.i/ha. Eggs were removed after one and eight days of exposure and analyzed for pesticides using gas chromatography coupled with a mass selective detector (GC-MSD) or high performance liquid chromatography (HPLC). Absorption of pesticides in eggs from soil increased with both magnitude and duration of exposure. Of the 10 pesticides, atrazine and metolachlor generally had the greatest absorption, while azinphos-methyl had the lowest. Chlorothalonil was below detection limits at both exposure rates. Our preliminary model suggests that pesticides having the highest absorption into eggs tended to have both low sorption to organic carbon or lipids, and high water solubility. For pesticides with high water solubility, high vapor pressure may also increase absorption. As our model is preliminary, confirmatory studies are needed to elucidate pesticide absorption in turtle eggs and the potential risk they may pose to embryonic development.     

Porous cups for pesticides monitoring in soil solution — Laboratory tests

In this study, preliminary tests were conducted aiming to validate the use of ceramic porous cup for collecting soil water samples and monitoring pesticides contents, as usually made for nitrates. Interactions between porous cup and pesticides were examined under different experimental conditions for three herbicides (atrazine, isoproturon, 2,4-D) and one insecticide (carbofuran).

The results showed that ceramic was not inert for pesticides : as much as 80% of the applied pesticide could be retained during the flowing of the first tenth milliliters of solution. Interactions were attributed to sorption and “screening” of molecules by the porous walls and were related to the ionic character of pesticides. However, retention was not irreversible, since pesticides were quickly released by rinsing with distilled water.

After these tests, porous ceramic cups could be considered as suitable samplers for pesticide determinations in soil solution, contingent on gaining further informations about soil - porous cup - pesticide interactions.     

UV-ozonation of eleven major pesticides as a waste disposal pretreatment

The time required to destroy 3 concentrations (10, 100, and 1000 ppm) of 9 formulated herbicides (alachlor, atrazine, bentazon, butylate, cyanazine, 2, 4-D, metolachlor, metribuzin, and trifluralin) and two formulated insecticides (carbofuran and malathion) by ultraviolet (UV)-ozonation (O₃) was measured in a 66 UV lamp unit. The time required for 90% destruction was dependent on the concentration and increased as the concentration of pesticide increased. UV irradiation in the presence of ozone rapidly photooxidized all pesticides at 10 and 100 ppm and averaged 22 and 61 min, respectively. Longer times were required for pesticides at 1000 ppm.     

Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.     

Persistence and biodegradation of carbaryl in soils

Abstract

The persistence of the methylcarbamate pesticide carbaryl was studied in four soils under flooded conditions. A substantial portion of the pesticide was recovered from all soils even after 15 days of its application, with the recovery ranging from 37% in an alluvial soil to 73% in an acid sulfate soil. The degradation of carbaryl was more rapid under flooded conditions than under nonflooded conditions. A bacterium, Pseudomonas cepacia, isolated from a flooded soil amended with a related methylcarbamate pesticide carbofuran, degraded carbaryl in a mineral medium supplemented with yeast extract.     

Tropical surface water quality studies: Implications for the aquatic fate of N-methyl carbamate pesticides

Water quality assessment was conducted on the Ruiru River, a tributary of an important tropical river system in Kenya, to determine baseline river conditions for studies on the aquatic fate of N-methyl carbamate (NMC) pesticides. Measurements were taken at the end of the long rainy season in early June 2013. Concentrations of copper (0.21–1.51 ppm), nitrates (2.28–4.89 ppm) and phosphates (0.01–0.50 ppm) were detected at higher values than in uncontaminated waters, and attributed to surface runoff from agricultural activity in the surrounding area. Concentrations of dissolved oxygen (8–10 ppm), ammonia (0.02–0.22 ppm) and phenols (0.19–0.83 ppm) were found to lie within normal ranges. The Ruiru River was found to be slightly basic (pH 7.08–7.70) with a temperature of 17.8–21.2°C. The half-life values for hydrolysis of three NMC pesticides (carbofuran, carbaryl and propoxur) used in the area were measured under laboratory conditions, revealing that rates of decay were influenced by the electronic nature of the NMCs. The hydrolysis half-lives at pH 9 and 18°C decreased in the order carbofuran (57.8 h) > propoxur (38.5 h) > carbaryl (19.3 h). In general, a decrease in the electron density of the NMC aromatic ring increases the acidity of the N-bound proton removed in the rate-limiting step of the hydrolysis mechanism. Our results are consistent with this prediction, and the most electron-poor NMC (carbaryl) hydrolyzed fastest, while the most electron-rich NMC (carbofuran) hydrolyzed slowest. Results from this study should provide baseline data for future studies on NMC pesticide chemical fate in the Ruiru River and similar tropical water systems.     

Air and groundwater pollution in an agricultural region of the Turkish Mediterranean coast

Air pollution and groundwater pollution in conjunction with agricultural activity were investigated in Antayla province on the Turkish Mediterranean coast. The air pollution was investigated in terms of gas-phase nitric acid (HNO3), sulfur dioxide (SO2), ammonia (NH3), and particulate matter for a 6-month period in the atmosphere using a "filter pack" system, which was developed and optimized in our laboratory. Ozone was measured by using an automated analyzer. Among all of the gas-phase pollutants, HNO3 had the lowest concentration (0.42 microg x m(-3)) followed by NH3. Agricultural activities seem to be the major source of observed NH3 in the air. The current state of water pollution was investigated in terms of organochlorine and organophosphorus pesticides around the greenhouses, in which mainly tomato, pepper, and eggplant are cultivated. Water samples were collected from 40 points, 28 of which were wells and 12 of which were surface water. The pesticide concentrations in water samples were determined by means of solid-phase extraction (SPE) followed by a gas chromatography (GC)-electron capture detector (ECD)/nitrogen phosphorus detector (NPD) system. In general, surface water samples were more polluted by the pesticides than groundwater samples. The most frequently observed pesticides were chlorpyriphos (57%) and aldrin (79%) in groundwater, and chlorpyriphos (75%), aldrin, and endosulfan sulfate (83%) in surface water samples. The highest concentrations were observed for fenamiphos (394.8 ng/L) and aldrin (68.51 ng/L) in groundwater, and dichlorvos (322.2 ng/L) and endosulfan sulfate (89.5 ng/L) in surface water samples. At least one pesticide had a concentration above the health limit in 38% of all the water samples analyzed.     

A cost-effective screening method for pesticide residue analysis in fruits, vegetables, and cereal grains

This paper reports the results of studies performed to investigate the potential of applying thin layer chromatography (TLC) detection in combination with selected extraction and cleanup methods, for providing an alternative cost-effective analytical procedure for screening and confirmation of pesticide residues in plant commodities. The extraction was carried out with ethyl acetate and an on-line extraction method applying an acetone-dichloromethane mixture. The extracts were cleaned up with SX-3 gel, an adsorbent mixture of active carbon, magnesia, and diatomaceous earth, and on silica micro cartridges. The Rf values of 118 pesticides were tested in eleven elution systems with UV, and eight biotest methods and chemical detection reagents. Cabbage, green peas, orange, and tomatoes were selected as representative sample matrices for fruits and vegetables, while maize, rice, and wheat represented cereal grains. As an internal quality control measure, marker compounds were applied on each plate to verify the proper elution and detection conditions. The Rf values varied in the different elution systems. The best separation (widest Rf range) was achieved with silica gel (SG)--ethyl acetate (0.05-0.7), SG--benzene, (0.02-0.7) and reverse phase RP-18 F-254S layer with acetone: methanol: water/30:30:30 (v/v) (0.1-0.8). The relative standard deviation of Rf values (CV(Rf)) within laboratory reproducibility was generally less than 20%, except below 0.2 Rf, where the CVRf rapidly increased with decreasing Rf values. The fungi spore inhibition, chloroplast inhibition, and enzyme inhibition were found most suitable for detection of pesticides primarily for confirming their identity or screening for known substances. Their use for determination of pesticide residues in samples of unknown origin is not recommended.     

Identification and quantification of polychlorinated biphenyls and some endocrine disrupting pesticides in human adipose tissue from Finland

Organochlorine pesticides and polychlorinated biphenyls (PCBs) were analysed in extracts of human adipose tissue. The samples consisted of abdominal, mammary, and perirenal fat tissue of 27 Finnish adult males and females. Lipids were separated from the low-molecular compounds by preparative gel permeation chromatography (GPC) and the extracts were further cleaned-up using Florisil chromatography. The compounds were analysed in the extracts by gas chromatography (GC) using electron capture detection and by GC-mass spectrometry in the selected ion monitoring mode. Of the 23 analysed pesticide residues only seven could be detected in the extracts. All the extracts contained the DDT metabolite 4,4'-DDE, hexachlorobenzene, and PCBs. Other compounds found in the extracts were 4,4'-DDT, 4,4'-DDD, pentachlorobenzene, and beta- and gamma-hexachlorocyclohexane (HCH). The antiandrogenic 4,4'-DDE was the most abundant pesticide with concentration levels ranging from 3.5 to 3229 ng/g lipids (ppb). The mean concentration of DDE was 567 ppb, of pesticides in all 1008 ppb and of PCBs 504 ppb. Several of the identified compounds have been shown to exhibit endocrine disrupting effects. Statistical analysis showed a positive age correlation of DDE in females and hexachlorobenzene in males. No statistically significant differences were found for concentrations of individual compounds between sexes.     

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.     

粉末活性炭对水中农药的吸附性能研究

研究了粉末活性炭对2,4-滴、呋喃丹、甲萘威和莠去津的吸附过程和吸附规律以及投炭量和水质对粉末活性炭吸附性能的影响。结果表明,粉末活性炭能有效去除4种农药;吸附规律符合Freundlich吸附等温线和Langmuir吸附等温线;吸附时间为30 min时,去离子水中的去除率已达到80%以上;随着投炭量的增加,去除率提高,粉末活性炭的吸附容量降低;在不同水质条件下,粉末活性炭的吸附等温线可能不同,因此在应急处理中,首先应该确定该水质下的吸附等温线,然后求出投炭量。     

Analysis of pesticide runoff from mid-Texas estuaries and risk assessment implications for marine phytoplankton

During 1993, estuarine surface water samples were collected from the mid-Texas coast (Corpus Christi to Port Lavaca, TX). Agricultural watershed areas as well as tidal creeks immediately downstream were chosen as sampling sites along with adjoining bay sampling stations. Collections were made throughout the growing season (February to October 1993) before and after periods of significant (> 1.25 cm) rainfall. All samples were initially screened for the presence of pesticides using enzyme-linked immunosorbent assay (ELISA) test kits (EnviroGard) for triazine herbicides and carbamate insecticides. All samples were extracted and then analyzed using gas chromatography (GC) for quantification of atrazine. Only samples testing positive for carbamate insecticides via ELISA were further extracted for GC analysis to quantify aldicarb and carbofuran. Additionally, laboratory toxicity tests using phytoplankton were examined from published, peer-reviewed literature and compared with the atrazine field levels found in Texas. Results of ELISA screening indicated the presence of triazine herbicides in nearly all samples (>93%). GC analysis further confirmed the presence of atrazine concentrations ranging from <0.01-62.5 microg/L. Screening tests also found detectable levels of carbamate insecticides (aldicarb and carbofuran) that were also confirmed and quantified by GC. Comparison of measured concentrations of atrazine compared with published toxicity tests results indicated that there was a potential environmental risk for marine/estuarine phytoplankton in surface waters of Texas estuaries, particularly when the chronic nature of atrazine exposure is considered.     

Atrazine,chlorpyrifos, and iprodione effect on the biodiversity of bacteria,actinomycetes, and fungi in a pilot biopurification system with a green cover

The use of biopurification systems can mitigate the effects of pesticide contamination on farms. The primary aim of this study was to evaluate the effect of pesticide dissipation on microbial communities in a pilot biopurification system. The pesticide dissipation of atrazine, chlorpyrifos and iprodione (35 mg kg^?1 active ingredient [a.i.]) and biological activity were determined for 40 days. The microbial communities (bacteria, actinomycetes and fungi) were analyzed using denaturing gradient gel electrophoresis (DGGE). In general, pesticide dissipation was the highest by day 5 and reached 95%. The pesticides did not affect biological activity during the experiment. The structure of the actinomycete and bacterial communities in the rhizosphere was more stable during the evaluation than that in the communities in the control without pesticides. The rhizosphere fungal communities, detected using DGGE, showed small and transitory shifts with time. To conclude, rhizosphere microbial communities were not affected during pesticide dissipation in a pilot biopurification system.     

A field study to compare performance of stainless steel research monitoring wells with existing on-farm drinking water wells in measuring pesticide and nitrate concentrations

Existing drinking water wells are widely used for the collection of ground water samples to evaluate chemical contamination. A well comparison study was conducted to compare pesticide and nitrate-N data from specially designed stainless steel research monitoring wells with data from nearby existing on-farm drinking water wells. Results could help to determine whether adequate information concerning ground water contamination can be obtained from existing drinking water wells for use in making pollutant control decisions. The study was conducted during 1993-1994 in the Little Coharie Watershed, a 158 square mile area located in the coastal plain of eastern North Carolina. Statistical analysis indicated that research monitoring wells provided a greater probability of detecting pesticides in ground water than existing on-farm wells. Atrazine was the most frequently detected pesticide found in all wells, followed in order by fluometuron, carbofuran, metolachlor, alachlor, carbaryl, butylate, chlorothalonil, linuron and simazine. Ninety-seven percent of all wells had observed concentrations of nitrate-N, ranging from 0.1 to 30.1 mg/L. There was not a significant difference between research wells and existing wells for monitoring nitrate-N. Based on results of this study, existing drinking water wells can be used for monitoring nitrate; however, specialized stainless steel monitoring wells should be used for monitoring pesticides in ground water.     

Biodegradation of mixed pesticides by mixed pesticide enriched cultures

This paper discusses the degradation kinetics of mixed (lindane, methyl parathion and carbofuran) pesticides by mixed pesticide enriched cultures (MEC) under various environmental conditions. The bacterial strains isolated from the mixed microbial consortium were identified as Pseudomonas aeruginosa (MTCC 9236), Bacillus sp. (MTCC 9235) and Chryseobacterium joostei (MTCC 9237). Batch studies were conducted to estimate the biokinetic parameters like the maximum specific growth rate (μ_max), Yield Coefficient (Y_T), half saturation concentration (K_s) and inhibition concentration (Ki) for individual and mixed pesticide enriched cultures. The cultures enriched in a particular pollutant always showed high growth rate and low inhibition in that particular pollutant compared to MEC. After seven weeks of incubation, mixed pesticide enriched cultures were able to degrade 72% lindane, 95% carbofuran and 100% of methyl parathion in facultative co-metabolic conditions. In aerobic systems, degradation efficiencies of lindane methyl parathion and carbofuran were increased by the addition of 2g L^{? 1} of dextrose. Though many metabolic compounds of mixed pesticides were observed at different time intervals, none of the metabolites were persistent. Based on the observed metabolites, a degradation pathway was postulated for different pesticides under various environmental conditions.     

The destruction of ground water threatening pesticides using high intensity UV light

Abstract

A high‐intensity short‐wavelength UV light system was studied for its ability to degrade the pesticides carbofuran, fenamiphos sulfoxide (nemacur sulfoxide), and propazine in aqueous solutions. Half‐lives, rate constants, and breakdown products were determined for all chemicals. The presence of hydrogen peroxide, an oxidant and potential source of hydroxyl radicals, had no effect on the rate of breakdown of any of the chemicals investigated. Short‐wavelength UV light appears to be solely responsible for the observed pesticide breakdown. The breakdown of all three pesticides followed first order kinetics. Carbofuran, nemacur sulfoxide, and propazine had half lives of 3.9, 1.1, and 3.9 minutes, respectively. Breakdown product analysis was performed using capillary gas chromatography/mass spectrometry.     

Grab and passive sampling applied to pesticide analysis in the São Lourenço river headwater in Campo Verde – MT,Brazil

In this study, the quality of surface water in the headwaters of São Lourenço River in Mato Grosso, Brazil, was evaluated in relation to contamination by pesticides. For this purpose, samples were collected between December 2015 and June 2016 by grab sampling and by passive sampling using an integrative polar organic compound sampler installed in the field during four 14-day cycles between March and June 2016. The analyses were performed by gas chromatography (CG/MS) and by liquid chromatography (UPLC-MS/MS). The results showed the detection of two pesticides (atrazine and pyraclostrobin) of the five analyzed by passive sampling and eight active principles among the 20 analyzed (malathion, diuron, carbofuran, carbendazim, trifluralin, imidacloprid, metolachlor, and acetamiprid) by grab sampling. The detection of 10 pesticides, even almost a decade after the beginning of a recovery process of the ciliary forest, confirms the headwaters' vulnerability to these contaminants and passive sampling proved to be an important tool in capturing small concentrations of pesticides constituting an interesting complement to grab sampling.     

Pesticide distribution in an agricultural environment in Argentina

An assessment of the off-site migration of pesticides from agricultural activity into the environment in the Neuquen River Valley was performed. The aim of this study was to evaluate the distribution of pesticides in several compartments of a small agricultural sub-catchment. Soil, surface water, shallow groundwater and drift deposition were analyzed for pesticide residues. Results showed the presence of some pesticide residues in soil, surface water and shallow groundwater compartments. The highest detection frequencies in water (surface and subsurface) were found for azinphos-methyl and chlorpyrifos (>70%). In terms of concentration, the highest levels were observed in shallow groundwater for azinphos methyl (22.5 μg/L) and carbaryl (45.7 μg/L). In the soil, even before the application period had started, accumulation of residues was present. These residues increased during the period studied. Spray drift during pesticide application was found to be a significant pathway for the migration of pesticide residues in surface water, while leaching and preferential flows were the main transport routes contributing to subsurface contamination.