Determination Of Pesticides In Soil Research Articles

Concomitant determination of pesticides in soil and drainage water over a potato cropping season reveal dissipations largely in accordance with respective models

Pesticides are widely used in agriculture where they do not only reach their targets but also distribute to other environmental compartments and negatively affect non-target organisms. To prospectively assess their environmental risk, several tools and models using pesticide persistence (DT50) and leaching potential (groundwater ubiquity score (GUS), EXPOSIT) have been developed. Here, we simultaneously quantified 18 pesticides in soil and drainage water during a conventionally grown potato culture at field scale with high temporal resolution and compared our findings with predictions of the above models. Overall dissipations of all freshly applied compounds in soil were in line with published DT50 field values and their occurrences in drainage water were generally consistent with GUS and EXPOSIT models, respectively. In contrast, soil concentrations of the legacy pesticide atrazine and one of its transformation products (atrazine-2-hydroxy) were constant during the entire sampling campaign. Moreover, during peak discharge atrazine concentrations in drainage water were diluted whereas those of freshly applied pesticides were maximal. This difference demonstrates that the applied risk assessment tools were capable of predicting environmental concentrations and dissipation of pesticides at the short and medium time scale of a few half-lives after application, but fell short of capturing long-term trace residues.

Regularities of transformation of dimethoate in apple agrocenoses

The aim of the research was to identify the regularities of dimethoate transformation in apple agrocenoses under the influence of protection technologies.Methods. The work was done in Toxicological laboratory of the North Caucasus Federal scientific center of horticulture, viticulture, winemaking. The research was conducted in field and laboratory conditions with using of methodological approaches based on modern methods and techniques. The pilot territory was laid in close corporation PPF Central. The extraction of analyzed compounds by plant and soil material is carried out according to the "Guidelines for the determination of micro-quantities of pesticides in plants, processed products, soil and water".Results. The background determination of organophosphate pesticides in soil before the planned treatments during this year revealed: the substance of dimethoate is higher the hygienic regulations in 1.3-1.4 times in 53% of the examined samples. During the harvest period, the content of dimethoate in all soil samples exceeded the permissible concentration, in the control version includes 0.3-0.5 PC of dimethoate. The accumulation of dimethoate is associated with its ability to react with complexing metal ions, which count in our soils is sufficient.Conclusion. Compiling the apple protection system is recommended to take into account that the annual using of dimethoates implying a violation of hygienic standards in soil and apple fruits. If there is a single application, residual amounts of dimethoate are in apple fruits, and their concentrations are exceeding or staying in the maximum permissible level. The samples were taken after 40 days of treatment. We recommend to exclude these insecticides (including D. V. dimetoate) from the apple tree protection system or use single application every 2 years in the first half of growing season.

Polymeric ionic liquid sorbent coatings in headspace solid-phase microextraction: A green sample preparation technique for the determination of pesticides in soil

In this work, a green approach utilizing novel polymeric ionic liquid (PIL) coatings for headspace solid-phase microextraction (HS-SPME) of four current-use pesticides from soil samples was studied for the first time. Epoxiconazole, fluroxypyr, metribuzin, and oxyfluorfen were the target pesticides. Three PIL coatings containing 1-vinylbenzyl-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide (PIL1 and PIL2) and 1-vinyl-3-(10-hydroxydecyl)imidazolium bis[(trifluoromethyl)sulfonyl]imide (PIL3) monomers, and 1,12-di(3-vinylbenzylimidazolium)dodecane bis[(trifluoromethyl)sulfonyl]imide (PIL1) and 1,12-di(3-vinylbenzimidazolium)dodecane bis[(trifluoromethyl)sulfonyl]imide (PIL2 and PIL3) crosslinkers were employed in this study. The performance of these PIL coatings was evaluated and compared with commercial SPME coatings based on polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polydimethylsiloxane (PDMS) at the different extraction temperatures (50–90 °C) and sampling times (15–60 min). HS-SPME at 90 °C for 60 min provided the highest sensitivity and adequate reproducibility for the majority of analytes. Despite having a lower thickness, PIL2 and PIL3 coatings provided similar extraction effectiveness of analytes, and 24–247% higher coating volume-normalized responses compared to the commercial PDMS/DVB coating. The use of the PIL1 sorbent coating resulted in excellent linearity (R2 = 0.995–0.999) and lower detection limits (0.06–0.4 ng g−1) for all analytes. The optimized method provides acceptable recoveries of spiked concentrations with better performance (84–112%) achieved with the PIL1 coating. Compared to other known methods for target pesticides in soil, the proposed method provides the highest compliance with the principles of green analytical chemistry evaluated using Analytical Eco-Scale and Green Analytical Procedure Index tools.

HYGIENIC SIGNIFICANCE OF THE DETERMINATION OF PESTICIDES IN SEDIMENTATION TESTS

Introduction. The use of pesticides creates the danger of contamination of the soil as a result of demolition outside the treatment area, which is assessed by comparing the actual pesticide content in the soil (mg/kg) with the maximum allowable / estimated allowable concentration (MAC/APC). Methods for the quantitative determination of pesticides in soil are labor-intensive; an alternative method for them may be an indirect method - determining the amount of drift to the soil using sedimentation samples (sedimentation - subsidence). The purpose of the study is a hygienic estimate of the amount of propiconazole deposited on the soil outside the cultivated area. The research objectives are to determine the content of propiconazole in the atmospheric air and on the soil outside the treatment area; to give a hygienic assessment of the amount of substance detected. Material and methods. Air samples were taken on aerosol paper filters, soil contamination was assessed using sedimentation samples by measuring the amount of substance deposited on the filters (about 40 cm2) in Petri dishes placed on the leeward side of the processing area. Results. Propiconazole was found in sedimentation samples at a level of 0.012-0.484 mg/m2 and was not identified in atmospheric air. Discussion. An algorithm is proposed for recalculating the results of measurements in filters for filters (mg/m2) for soil concentration (mg/kg), taking into account information on the mobility of the substance and the bulk density of the soil. It has been established: when using the drug in the form of an emulsion concentrate on field crops, the amount of propiconazole in demolitions on the soil can exceed the APC up to 10 times; the drug in the form of a nanoemulsion concentrate on garden crops ODC exceeded 17 times. The increased content of the substance in the soil is the reason for prohibiting the use of the drug using this technology. Conclusions. Sedimentation tests, being cumulative, confirm or refute the results of analytical control of atmospheric air, increasing the reliability of hygienic studies, further guaranteeing the safety of pesticide use for the population.

Gold Nanoparticles with Different Particle Sizes for the Quantitative Determination of Chlorpyrifos Residues in Soil by SERS.

Chlorpyrifos (CPF) is widely used in the prevention and control of crop pests and diseases in agriculture. However, the irrational utilization of pesticides not only causes environmental pollution but also threatens human health. Compared with the conventional techniques for the determination of pesticides in soil, surface-enhanced Raman spectroscopy (SERS) has shown great potential in ultrasensitive and chemical analysis. Therefore, this paper reported a simple method for synthesizing gold nanoparticles (AuNPs) with different sizes used as a SERS substrate for the determination of CPF residues in soil for the first time. The results showed that there was a good linear correlation between the SERS characteristic peak intensity of CPF and particle size of the AuNPs with an R2 of 0.9973. Moreover, the prepared AuNPs performed great ultrasensitivity, reproducibility and chemical stability, and the limit of detection (LOD) of the CPF was found to be as low as 10 μg/L. Furthermore, the concentrations ranging from 0.01 to 10 mg/L were easily observed by SERS with the prepared AuNPs and the SERS intensity showed a good linear relationship with an R2 of 0.985. The determination coefficient (Rp2) reached 0.977 for CPF prediction using the partial least squares regression (PLSR) model and the LOD of CPF residues in soil was found to be as low as 0.025 mg/kg. The relative standard deviation (RSD) was less than 3.69% and the recovery ranged from 97.5 to 103.3%. In summary, this simple method for AuNPs fabrication with ultrasensitivity and reproducibility confirms that the SERS is highly promising for the determination of soil pesticide residues.

Cold column trapping-headspace micro-solid phase extraction for efficient preconcentration and GC-MS determination of pesticides in soil

A new cold column trapping-headspace microsolid-phase extraction (CCT-HS-μSPE) system was developed and used for the preconcentration and GC-MS determination of three pesticides (diazinon, malathion and permethrin) in soil samples.

The QuEChERS Approach for the Determination of Pesticide Residues in Soil Samples: An Overview.

Soil samples are complex matrixes; therefore, soil sample preparation is a critical step, and one that is usually expensive, time-consuming, and labor intensive. The quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, originally developed for the determination of pesticides in fruits and vegetables, has been recently modified and adopted for the analysis of pesticides in soil. This paper reviews all aspects of sample preparation, including extraction and clean-up, and describes the applications of conventional and modified QuEChERS techniques. It also presents a comparison of the QuEChERS method with other methods used for sample preparation for determination of pesticides in soil.

The QuEChERS Approach for the Determination of Pesticide Residues in Soil Samples: An Overview.

Soil samples are complex matrixes; therefore, soil sample preparation is a critical step, and one that is usually expensive, time-consuming, and labor intensive. The quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, originally developed for the determination of pesticides in fruits and vegetables, has been recently modified and adopted for the analysis of pesticides in soil. This paper reviews all aspects of sample preparation, including extraction and clean-up, and describes the applications of conventional and modified QuEChERS techniques. It also presents a comparison of the QuEChERS method with other methods used for sample preparation for determination of pesticides in soil.

Validation and application of a multi-residue method, using accelerated solvent extraction followed by gas chromatography, for pesticides quantification in soil.

A multi-residue method was developed to determine different types of pesticides in soils. An extraction with pressure and temperature, through accelerated solvent extraction (dichloromethane:acetone, 50:50, v/v). The pesticides were determined by gas chromatography with several selective detectors: electron capture detector, pulsed flame photometric detector and thermionic specific detector. The following parameters were determined: limit of detection, limit of quantification, equipment linearity (working interval), method linearity as well as, method accuracy and precision. The average recoveries ranged between 76 and 106%, with the exception of chlorothalonil, which had an average recovery of 46%. Additionally, detection limits from 0.9 to 7.6ng g -: (1) and the quantification limits from 3.00 to 25.47ng g -: (1) were estimated. In terms of linearity and precision, the results obtained were in the ranges considered adequate (R(2) ≥ 0.98 and coefficient of variation (CV) ≤ 20%), with the exception of aldrin (R(2) = 0.946, CV = 35.79%), lindane (R(2) = 0.917, CV = 32.91%) and chlorothalonil (R(2) = 0.8184, CV = 81.35%). The proposed method was used to evaluate pesticides in real soil samples, detecting concentrations over 1000ng g -: (1) for some pesticides. The method was correctly validated and provided for the rapid determination of pesticides in soil.

Determination of Pesticides in Soil Using a Hyphenated Extraction Technique

A new method for the extraction of pesticide residues from soil was developed, optimized, validated and applied to real samples. The technique consisted of combining single-drop microextraction and solid-liquid extraction with low temperature partitioning (SLE/LTP-SDME) followed by analysis using gas chromatography with electron capture detection (GC/ECD). This method was used to determine the presence of alachlor, methyl parathion, trifluralin, endrin, lindane, dieldrin and dichloro-diphenyl-trichloroethane (4,4’-DDT) in soil samples. Recoveries ranging from 67.2 to 122.5% were achieved, coefficients of variation (repeatability) were lower than 22.4% and limits of detection ranged from 0.18 to 0.59 µg kg-1. Recovery from soils fortified with different concentrations of the pesticides ranged from 61.5 to 123.5%. The new method combines the primary advantages of the two techniques: purification of the sample using SLE/LTP and preconcentration using SDME. The new method also enables the determination of low volatility compounds without requiring the sample to be heated.

Determination of Pesticides in Soil by Mechanical Stirring-Assisted Extraction Coupled with Gas Chromatography-Mass Spectrometry

This work describes the development of an analytical method for determining the mobility of some organophosphorus and azole group pesticides. The chromatographic and mass spectrophotometric parameters were optimized. The target pesticides were recovered quantitatively (79.3–95.6%) with a relative standard deviation less than 8.5% at the optimum conditions of the extraction. The limits of detection of the target pesticides were found to be in the range of 0.16 to 1 . 14 µ g kg − 1 with a correlation coefficient ( r) > 0 . 9955 . The method was validated in the target environmental matrices by the analysis of a spiked soil sample. The proposed method was successfully applied for the determination of pesticides in vineyard soil samples and statistically evaluated.

QuEChERS and solid phase extraction methods for the determination of energy crop pesticides in soil, plant and runoff water matrices

QuEChERS and solid phase extraction (SPE) methods were applied for determining four herbicides (metazachlor, oxyfluorfen, quizalofop-p-ethyl, quinmerac) and one insecticide (α(±)-cypermethrin) in runoff water, soil, sunflower and oilseed rape plant matrices. Determination was performed using gas chromatography mass spectrometry (GC-MS), whereas high-pressure liquid chromatography mass spectrometry (HPLC-MS) was used for quinmerac. In all substrates linearity was evaluated using matrix-matched calibration samples at five concentration levels (50–1000 ng L−1 for water, 5–500 μg kg−1 for soil and 2.5–500 μg kg−1 for sunflower or oilseed rape plant). Correlation coefficient was higher than 0.992 for all pesticides in all substrates. Acceptable mean recovery values were obtained for all pesticides in water (65.4–108.8%), soil (70.0–110.0%) and plant (66.1–118.6%), with intra- and inter-day RSD% below 20%. LODs were in the range of 0.250–26.6 ng L−1 for water, 0.10–1.8 μg kg−1 for soil and 0.15–2.0 μg kg−1 for plants. The methods can be efficiently applied for field dissipation studies of the pesticides in energy crop cultivations.

Determination of Pesticides in Soil by Accelerated Solvent Extraction-Liquid Chromatography Tandem Mass Spectrometry

A rapid and accurate method based on accelerated solvent extraction liquid chromatography tandem mass spectrometry(LC-MS/MS) was developed for the determination of 9 kinds of pesticides in soil.The analytes were extracted by accelerated solvent extraction using acetonitrile as the extraction solvent.The extract was concentrated by evaporation.Qualitative and quantitative analysis for the analytes was carried out by the multiple reaction monitoring mode after the chromatographic separation using acetonitrile-water solution as mobile phase.The linear range of detection for nine pesticides was between 0.5-500 μg/kg,and the limits of detection were between 0.2-2.0 μg/kg.The recoveries and relative standard deviations were 90.0%-105.0% and 1.0%-5.9%,respectively.This method is rapid,sensitive and suitable to the determination of pesticides in soil.

Liquid–Solid Sample Preparation Followed by Headspace Solid-Phase Microextraction Determination of Multiclass Pesticides in Soil

This paper describes development and validation of a multiresidue method for the determination of five pesticides (terbufos, prochloraz, chloridazon, pendimethalin, and fluorochloridone) belonging to different pesticide groups in soil samples by GC/MS, followed by its application in the analysis of some agricultural soil samples. The method is based on a headspace solid-phase microextraction method. Microextraction conditions, namely temperature, extraction time, and NaCI content, were tested and optimized using a 100 microm polydimethylsiloxane fiber. Three extraction solvents [methanol, methanol-acetone (1 + 1, v/v), and methanol-acetone-hexane (2 + 2 + 1, v/v/v)] and the optimum number of extraction steps within the sample preparation stage were optimized for the extraction procedure. LOD values for all the studied compounds were less than 12 microg/kg. Recovery values for multiple analyses of soil samples fortified at 30 microg/kg of each pesticide were higher than 64%. The method was proven to be repeatable, with RSD lower than 15%.

Determination of trace organochlorine pesticides in soil using isotope dilution-high resolution gas chromatography-high resolution mass spectrometry

A method for the determination of trace organochlorine pesticides (OCPs) in soil using isotope dilution and high resolution gas chromatography-high resolution mass spectrometry (ID-HRGC-HRMS) was developed. The sample was extracted by accelerated solvent extractor (ASE) and cleaned-up by a Florisil solid phase extraction (SPE) cartridge. The analytes were separated by HRGC on a DB-5MS column (30 mx 0.25 mm x 0.25 microm) and determined by HRMS. The identifications of OCPs were based on the retention time of 13C-labelled standard and the abundance ratio of the two exact mass-to-charge ratios. The quantitative analysis was performed using the ratios of the integrated areas of the 13C-labelled standards. This method has the recoveries ranging from 77.3% to 114.5% and the relative standard deviations (RSD) less than 10.81% (n=5). The limits of detection (LODs) of this method for all OCPs were lower than 0.04 pg/g. The results indicated that the method is rapid, selective and sensitive for precise determination requirements of organochlorine pesticides at trace level in soil.

Development of a multiresidue method for the determination of multiclass pesticides in soil using GC

The principal objective of the present study was to develop a multiresidue analytical method for 62 pesticides in a soil matrix. Soil samples were fortified with known quantities of pesticides at two different concentration levels (0.1 and 0.01 microg/g) and the analytes were extracted via a liquid-solid extraction method. The pesticides were separated on an HP5 capillary column and were detected by gas chromatography coupled to an electron capture detector (GC-ECD). The method was validated, considering its good linearities (r(2) = 0.978-0.999), specificity and recovery characteristics. Recoveries were found between 70.3 and 113.4% for all pesticides except edifenphos (67.5%) and dichlobenil (69.5%) spiked at a 0.1 microg/mL concentration level and 74.5-117% except ethalfluralin (63.3%) and dichlobenil (51.9%) spiked at a concentration of 0.01 microg/mL. The developed method could be utilized as a simple and cost-effective method for the routine analysis of 62 pesticides in soil samples.

ChemInform Abstract: Quantitative Determination of Pesticides in Soil by Thin-Layer Chromatography and Video Densitometry.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Macroporous Diatomaceous Earth Column for the Separation and Simultaneous Determination of Pesticides in the Soil of Golf Courses

A macroporous diatomaceous earth column was applied to the separation and simultaneous determination of pesticides in soil on a golf course. Two analytical procedures were used for this technique. One was GC/MS determination of cyproconazole, propiconazole, tetraconazole and triflumizole, and the other was HPLC/UV determination of azoxystrobin, flazasulfuron, halosulfuron-methyl and siduron. One enormous advantage of this column technique was the fact that surfactants sprayed together with pesticides produced no emulsion formation. It also made the separation process very simple and rapid in comparison with liquid-liquid extraction technique with a separating funnel. The recoveries of the pesticides spiked to the soil of a golf course were 84.4∼93.5 %, and the relative standard deviations were 0.7∼5.8 % by the proposed methods.

Determination of pesticides in soil by liquid-phase microextraction and gas chromatography–mass spectrometry

Trace amounts of pesticides in soil were determined by liquid-phase microextraction (LPME) coupled to gas chromatography–mass spectrometry (GC–MS). The technique involved the use of a small amount (3 μl) of organic solvent impregnated in a hollow fiber membrane, which was attached to the needle of a conventional GC syringe. The organic solvent was repeatedly discharged into and withdrawn from the porous polypropylene hollow fiber by a syringe pump, with the pesticides being extracted from a 4 ml aqueous soil sample into the organic solvent within the hollow fiber. Aspects of the developed procedure such as organic solvent selection, extraction time, movement pattern of plunger, concentrations of humic acid and salt, and the proportion of organic solvent in the soil sample, were optimized. Limits of detection (LOD) were between 0.05 and 0.1 μg/g with GC–MS analysis under selected-ion monitoring (SIM). Also, this method provided good precision ranging from 6 to 13%; the relative standard deviations were lower than 10% for most target pesticides (at spiked levels of 0.5 μg/g in aqueous soil sample). Finally, the results were compared to those achieved using solid-phase microextraction (SPME). The results demonstrated that LPME was a fast (within 4 min) and accurate method to determine trace amounts of pesticides in soil.

Multiresidue determination of pesticides in soil by gas chromatography-mass spectrometry detection.

An analytical multiresidue method for the simultaneous determination of various classes of pesticides in soil was developed. Pesticides were extracted from soil with ethyl acetate. Soil samples were placed in small columns, and the extraction was carried out assisted by sonication. Pesticides were determined by gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode. Spiked blank samples were used as standards to counteract the matrix effect observed in the chromatographic determination. Pesticides were confirmed by their retention times, their qualifier and target ions, and their qualifier/target abundance ratios. Recovery studies were performed at 0.2, 0.1, and 0.05 microg/g fortification levels of each pesticide, and the recoveries obtained ranged from 87.0 to 106.2% with a relative standard deviation between 2.4 and 10.6%. Good resolution of the pesticide mixture was achieved in approximately 41 min. The detection limits of the method ranged from 0.02 to 1.6 microg/kg for the different pesticides studied. The developed method is linear over the range assayed, 25-1000 microg/L, with determination coefficients >0.999. The proposed method was used to determine pesticide levels in real soil samples, taken from different agricultural areas of Spain, where several herbicides and insecticides were found.