Pesticides In Soil Samples Research Articles

Determination of 239 pesticide residues in soil by ultra performance liquid chromatography-tandem mass spectrometry

A method for the determination of 239 pesticides in soil samples by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) is presented. The sample was prepared with AOAC (Association of Official Analytical Chemists) QuEChERS method for the extraction (acetonitrile, anhydrous MgSO4, CH3 COONa). After filtered with a 0.2 microm membrane, the sample was separated and detected by UPLC-MS/MS performing on positive/ negative electrospray ionization (ESI +/-) and the multiple reaction monitoring (MRM) mode. In this study, 236 of the 239 pesticides' correlation coefficients were above 0.99, which counted 99% of all the analytes. The limits of detection (LODs) ranged in 0.69 - 29.04 microg/kg (S/N = 3). The recoveries of all the pesticides at 40 microg/kg spiked level were in the range of 50% - 150%, and the relative standard deviations (RSDs) were below 20%. In addition, the recoveries of 209 pesticides were in the range of 70% - 120%, and RSDs of 161 pesticides were less than 10%. The method is efficient, fast, simple, and accurate. The procedure is suitable for the determination of multi pesticide residues in soil.

Analysis of Organochlorine Pesticides in Soil Using Optimized FMAE-GC/MS

A focused microwave-assisted extraction (FMAE) was optimized and coupled to gas chromatography–mass spectrometry for the determination of organochlorine pesticides in soil samples. According to the result, the combination of 20 min extraction time at 48 °C and a mixture of 1+1 of n-hexane-acetone as extraction solvent is the best conditions. The recovery values is 72.8%～96.4% in the above conditions. The relative standard deviation was 4.39%~13.18%. We have good recovery values when spiked 20ng, 40ng and 60ng standard into 5.00g soil sample.

Optimization of extractants, purifying packings, and eluents for analytical extraction of organochlorine pesticides in Hydragric Acrisols

In this study, we screened for an economic, rapid, and efficient hypotoxic pretreatment method for organochlorine pesticides in soil samples for gas chromatography (GC) analysis. The analytical extraction efficiencies of 11 different extractants, nine types of solid-phase purification (SPP) cartridge packings, and three types of eluents for 13 organochlorine pesticides (OCPs) in spiked and natural Chinese red soil (Hydragric Acrisols) were evaluated using an ultrasonic extraction and solid-phase purification method. High percent recoveries (85-106%) were obtained for the 13 organochlorine pesticides in soil when petroleum ether/acetone/water (10:5:2, v/v) was used an extractant. They were purified using celite SPP cartridge packing and eluted with 9 mL of dichloromethane/petroleum ether (1:9, v/v). The OCPs purification pretreatment of Hydragric Acrisols, using the above method, meets the GC analysis requirements. Compared with other traditional pretreatment methods for OCPs in soil samples, this method has several advantages, such as a short extraction time, reducing the amount of solvent, having no emulsion phenomenon, and hypotoxicity to the laboratory technicians. The concentrations of 1,1,1,-trichloro-2(p-chlorophenyl)-2-(o-chlorophenyl) ethane (DDTs; 3.42-8.08 ng g(-1)) in field soils were higher than the hexachlorocyclohexane concentration (2.94-6.12 ng g(-1)). The 1,1-dichloro-2,2-bis(p-chlorophenyl) ethylene (p,p'-DDE) + 1,1-dichloro-2,2-bis(p-chlorophenyl)-ethane (p,p'-DDD)/p,p'-DDT ratio in this field soil was approximately 2.7, suggesting that no new DDT pollution source was introduced into the sampling site.

Mutagenicity assessment of contaminated soil in the vicinity of industrial area

In the industrial area of Chinhat, Lucknow (India) wastewater coming from pesticide manufacturing and other industries is used to irrigate the agricultural crops. This practice has been polluting the soil and pollutants might reach the food chain. Gas chromatographic analysis revealed the presence of certain organochlorine pesticides in soil samples. Samples were extracted using different solvents, i.e., hexane, acetonitrile, methanol, chloroform, and acetone (all were HPLC-grade, SRL, India). Soil extracts were assayed for mutagenicity using Ames Salmonella/mammalian microsome test. Mutagenicity was observed in the test samples and TA98 was the most responsive strain for all the soil extracts (irrigated with wastewater) in terms of mutagenic index in the presence (+S9) and absence (-S9) of metabolic activation. In terms of slope (m) of linear dose-response curve for the most responsive strain TA98 exhibited highest sensitivity against the soil extracts in the presence and absence of S9 fraction. Hexane-extracted soil sample (wastewater) exhibited maximum mutagenicity in terms of net revertants per gram of soil in the presence and absence of S9 mix as compared to the other soil extracts. Groundwater-irrigated soil extracts displayed low level of mutagenicity as compared to wastewater-irrigated soil. The soil is accumulating a large number of pollutants due to wastewater irrigation and this practice of accumulation has an adverse impact on soil health.

Development and validation of a multiresidue method for determination of 37 pesticides in soil using GC‐NPD

In this study, a multiresidue analytical method for the detection of 37 pesticides in a soil matrix was developed and validated. The soil sample was fortified with a known quantity of pesticides at two different concentration levels (0.1 and 0.01 µg/g) and the analytes were extracted via a liquid-solid extraction method. The pesticides were separated on an HP5 capillary column and were analyzed with a gas chromatograph coupled to a nitrogen-phosphorous detector (GC-NPD). Method validation was accomplished with good linearity (r(2) = 0.994-0.999) within a considerable range of concentrations. Satisfactory recoveries (70.5-110.4%) were obtained with 32 pesticides at both spiking concentration levels, whereas five pesticides-dimepiperate, buprofezin, prometryn, pirimicarb, and fludioxonil-were recovered at relatively low levels (43.6-61.8%). The applicability of the method was demonstrated by analyzing field samples collected from 24 different sites around Yeongsan and Sumjin rivers in the Republic of Korea. No residues of the selected pesticides were detected in any of the samples. The developed method could be employed as a simple and cost-effective method for the routine detection and analysis of 37 pesticides in soil samples.

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.

Biota uptake of pesticides by selected plant species; the case study of Kilombero sugarcane plantations in Morogoro Region, Tanzania

This paper reports on biota uptake of pesticides by selected plant species from soil in which they are grown. The study was conducted at Kilombero sugarcane plantations and environs, Morogoro Region, Tanzania. Three species of the plant materials were collected namely sugarcane ( Saccharum officinarum), guinea grass ( Panicum maximum) and mango leaves ( Mangifera indica). The sugarcane and guinea grass were used to reveal the plant uptake in the plantations whereas mango leaves were used to represent the environs. GPC cleaned sample extracts were analysed by GC–ECD and GC–NPD and the results confirmed using GC–MS. A total of 16 different pesticide residues were detected in soil samples and only 11 pesticide residues were detected in flora samples. o, p′-DDT had the highest concentration of all detected pesticides in soil samples with a mean concentration of 21.04 μg/kg d.w. whereas the highest concentrations of 17.16 μg/kg d.w. was recorded for p, p′-DDD in flora samples. The other DDT metabolites detected in soil samples were p, p′-DDT, p, p′-DDE, o, p′-DDE, p, p′-DDD and o, p′-DDD with concentration ranging from 2.00 to 18.30 μg/kg d.w. whereas the other pesticides detected in flora samples were p, p′-DDT α-endosulfan and γ-HCH with a mean concentration range of 3.21 to 13.54 μg/kg d.w. The paired sample t-test showed no significant difference between the concentrations of pesticides in flora and those found in soil.

Headspace ionic liquid-based microdrop liquid-phase microextraction followed by microdrop thermal desorption-gas chromatographic analysis

Headspace microdrop liquid-phase microextraction (LPME) using ionic liquids as extracting solvents, followed by gas chromatography-electron capture detection was successfully developed to determine organochlorine pesticides in soil samples. A feature of the developed procedure is the simple handling of the ionic liquid extract in a normal, unmodified gas chromatograph injection port such that no special provision was needed to ensure that the ionic liquid did not contaminate it. This was achieved by only exposing the ionic liquid extract in the injection port while it was still attached to the syringe needle tip (i.e. mirroring the extraction configuration) to permit volatilization of the analytes, instead of injecting the extract. In this way, the spent ionic liquid could be recovered from the injection port, obviating the need to clean the port. Four 1-butyl-3-methylimidazolium-based ionic liquids were investigated, and 1-butyl-3-methylimidazolium hexafluorophosphate was finally selected as the most suitable extracting solvent. Parameters that affect the extraction and determination of the organochlorine pesticides were studied. Under the optimal conditions, the proposed method produced good linearity over a concentration range of 5-250 ng/g. Limits of detection ranging from 0.25 to 0.5 ng/g were achieved.

Genotoxicity of agricultural soils in the vicinity of industrial area

Soil samples from agricultural fields (cultivated) in the vicinity of industrial area of Ghaziabad City (India) were collected. In this city, wastewater coming from both industrial and domestic sources and without any treatment is used to irrigate the food crops. This practice has been polluting the soil and pollutants might reach the food chain. Gas chromatographic analysis show the presence of certain organochlorine (DDE, DDT, dieldrin, aldrin and endosulfan) and organophosphorus (dimethoate, malathion, methylparathion and chlorpyrifos) pesticides in soil samples. Samples were extracted using different solvents, i.e. methanol, chloroform, acetonitrile, hexane and acetone (all were HPLC-grade, SRL, India), and the extracts were assayed for genotoxic potential using Ames Salmonella/microsome test, DNA repair defective mutants and bacteriophage λ systems. TA98 and TA100 were found to be the most sensitive strains to all the soil extracts tested. Methanol extracts exhibited a maximum mutagenicity with TA98 strain {540 (−S9) and 638 (+S9) revertants/g of soil} and 938 (−S9) and 1008 (+S9) revertants/g of soil with TA100 strain. The damage in the DNA repair defective mutants was found maximum with methanolic extract followed by acetonitrile, chloroform, hexane and acetone at the dose level of 40 μl/ml culture after 6 h of treatment. The survival was 25, 30, 32, 33 and 35% in polA strain after 6 h of treatment when tested with wastewater irrigated soil extracts of methanol, acetonitrile, chloroform, hexane and acetone, respectively. A significant decrease in the plaque forming units of bacteriophage λ was also observed when treated with 40 μl of test samples. Present results showed that methanolic extracts of soil were more toxic than other soil extracts. The soil is accumulating a large number of pollutants due to wastewater irrigation and this practice of accumulation has an impact on soil health.

Effects of organic matter and clay content in soil on pesticide adsorption processes

The effect of organic matter and clay content on the adsorption of atrazine, acetochlor, clomazone, pendimethalin and oxyfluorfen in soil samples was studied. In order to determine whether and to what degree different soil properties affect the process of determination of selected pesticides, three soils with different clay and organic matter contents were used. An optimized liquid-solid extraction procedure followed by SPME measurement was applied to analyze the selected pesticides in soil samples. Detection and quantification were done by gas chromatography-mass spectrometry (GC/MS). Relative standard deviation (RSD) values for multiple analyses of soil samples fortified at 30 ?g/kg of each pesticide were below 19%. Limits of detection (LODs) for all compounds studied were less than 2 ?g/kg. The results indicate that soils with different physic-chemical properties have different effects on the adsorption of most pesticides, especially at higher concentration levels.

Determination of carbamate pesticides using micro-solid-phase extraction combined with high-performance liquid chromatography

We describe a simple and sensitive porous polypropylene membrane-protected micro-solid-phase extraction (μ-SPE) approach for the sample preparation and determination of carbamate pesticides in soil samples by high-performance liquid chromatography. The μ-SPE device consisted of C 18 sorbent held within a porous polypropylene envelope. In order to achieve optimum performance, several extraction parameters were optimized. Under the most favorable conditions, the extraction efficiency of the μ-SPE was very high, with detection limits in the range of 0.01–0.40 ng g −1. This is more than two orders of magnitude lower than the limits obtained by the United States Environmental Protection Agency Methods 8321A and 8318. A linear relationship was obtained for each analyte in the range of 2 and 200 ng g −1. The relative standard deviation for the analysis of aged soil samples spiked at 5 ng g −1 was ≤11%. The reproducibility of separate μ-SPE device used for experiments was satisfactory (relative standard deviations ranged from 4 to 11%), indicating that the method is reliable for routine environmental analysis.

Comparison of four extraction methods for the analysis of 24 pesticides in soil samples with gas chromatography–mass spectrometry and liquid chromatography–ion trap–mass spectrometry

With a view to analyse multiresidues of pesticides in soil samples, a new ultrasonic solvent extraction (USE) was compared to the European Norm DIN 12393 for foodstuff (extraction with acetone, partitioning with ethylacetate/cyclohexane and clean-up with gel permeation chromatography (GPC)), the QuECheRS method and a pressurised liquid extraction (PLE) method. Pesticides were analysed with both GC-MS and HPLC-MS/MS. The reference materials were the EUROSOIL 7 and its subsoil SO26 as well as a sea sand. All the substances were observed to be linear in the range of 4–800 ng g −1 for the European Norm DIN 12393, 7–1400 ng g −1 for the USE method and 20–4000 ng g −1 for the QueCheRS and the PLE methods. Limits of detection (LOD) and limits of quantification (LOQ) were with HPLC between 0.006 and 0.23 ng g −1 and between 0.022 and 0.77 ng g −1, respectively, with the exception of diuron (LOD up to 11.8 ng g −1; LOQ up to 39.2 ng g −1). With GC they ranged from 3.0 to 87.5 ng g −1 and from 10 to 292 ng g −1, respectively. All substances could be recovered with USE as well as with the QuECheRS method; the European Norm DIN 12393 could not recover carbendazim and metamitron; the PLE carbendazim, metamitron and monolinuron. For the remaining substances, recoveries at a 500 ng g −1 fortification level ranged from 10.9 to 96.3% with the USE. In comparison, the QuECheRS method was the most efficient extraction method with recoveries from 27.3 to 120.9%. It was followed by the European Norm DIN 12393 with recoveries between 6.8 and 108.1% and the PLE with recoveries from 12.2 to 153.2%. Recoveries were higher from the EUROSOIL 7 than from the SO 26. The repeatability expressed in term of standard deviation was below 20% for all substances and all materials.

Sample Extraction Method Combining Micellar Extraction−SPME and HPLC for the Determination of Organochlorine Pesticides in Agricultural Soils

A method for the determination of organochlorine pesticides in soil samples combining microwave assisted micellar extraction (MAME) with solid-phase microextraction (SPME) and high-performance liquid chromatography-UV has been developed. A mixture of two nonionic surfactants (polyoxyethylene 10 lauryl ether and polyoxyethylene 10 stearyl ether) was used for the extraction of pesticides from agricultural soils, and different types of SPME fibers were compared. The different parameters which affect extraction efficiency in the SPME procedure were optimized such as extraction time and temperature. The method developed involves extraction and preconcentration for the target analytes in soil samples. The analytical parameters were also studied and good recoveries obtained, RSD being lower than 10% and detection limits ranging between 36 and 164 ng g(-1) for the pesticides studied. The proposed method was successfully applied to the determination of some organochlorine pesticides in several kinds of agricultural soil samples with different characteristics.

Microwave assisted micellar extraction coupled with solid phase microextraction for the determination of organochlorine pesticides in soil samples

Microwave assisted micellar extraction (MAME) coupled with solid phase microextraction (SPME) and HPLC-UV determination have been used for the determination of five organochlorine pesticides from agricultural soil samples. A non-ionic surfactant, Polyoxyethlylene 10 Lauryl Ether was used, and the different variables for the optimization of MAME and SPME procedures were studied. This method was applied successfully to the determination of these pesticides in several kinds of agricultural soil samples with different characteristics. Most of the compounds studied can be recovered in good yields with R.S.D. lower than 9% and detection limit ranged between 56–96 ng g −1 for the pesticides studied.

Optimization of supercritical fluid extraction of pesticide residues in soil by means of central composite design and analysis by gas chromatography–tandem mass spectrometry

An environmentally friendly methodology is proposed for the analysis of pesticides in soil samples based on supercritical fluid extraction (SFE) and analysis at high selectivity and sensitivity, by gas chromatography–tandem mass spectrometry (GC–MS–MS). The pesticides investigated are among the most commonly used in intensive horticulture activities comprising organochlorine and organophosphorous insecticides, triazine and acetanilide herbicides, amongst others. An experimental design approach was used for modelling SFE and optimised extraction conditions were derived for the total pesticides extraction or for specific sub-groups of interest. Pesticide residues could be detected in soils in the sub-ppb range (0.1–3.7 μg kg −1), with quite good precision (4.2–15.7%) and extraction efficiency (80.4–106.5%). The analysis of soil samples from an intensive horticulture area in Póvoa de Varzim, north of Portugal, revealed the presence of persistent pesticides, parent compounds and degradation products among the following: endosulfan, endosulfan sulfate, dieldrin, 4,4′-DDE, 4,4′-DDD, atrazine, alachlor, metolachlor, chlorpyrifos, pendimethalin and lindane. The important features to point out are the easy interpretation of chromatograms and straightforward confirmation of analytes that greatly facilitates the analyst judgement on the contamination of the sample.

Analysis of triazolopyrimidine herbicides in soils using field-enhanced sample injection-coelectroosmotic capillary electrophoresis combined with solid-phase extraction

In this work, a combined methodology using off-line solid-phase extraction (SPE), on-line field-enhanced sample injection (FESI) and coelectroosmotic capillary electrophoresis with UV detection (CE-UV) is developed for the trace analysis of five triazolopyrimidine sulfonanilide pesticides (i.e., flumetsulam, florasulam, cloransulam-methyl, diclosulam and metosulam). An adequate background electrolyte (BGE) was obtained for the separation of these pesticides using hexadimethrine bromide (HDB) as electroosmotic flow (EOF) modifier. This BGE consisted of 0.00042% HDB, 11 mM formic acid, 16 mM ammonium carbonate and 2.5 mM α-CD solution at pH 7.6. The use of this running buffer together with the FESI preconcentration method provided limits of detection (LODs) in the low μg/L range (i.e., between 13.0 and 31.5 μg/L). The optimized FESI-CE-UV method was combined with off-line SPE using C 18 cartridges and applied to the determination of the selected group of pesticides in soil samples. Recovery percentages ranged between 50 and 84% in these samples with LODs between 18 and 34 μg/kg. This work shows the great possibilities of the combined use of SPE-FESI-CE-UV to improve CE sensitivity allowing the achievement of LODs similar to other analytical techniques as GC or HPLC.

Combination of microwave assisted micellar extraction and liquid chromatography for the determination of organophosphorous pesticides in soil samples

A new methodology based on the microwave assisted micellar extraction (MAME) technique has been optimised, using soil samples, to extract and determine a mixture of the eight organophosphorous pesticides mainly used in agriculture. The pesticides under study have been extracted using the non-ionic surfactants polyoxyethylene 10 lauryl ether (POLE) and oligoethylene glycol monoalkyl ether (Genapol X-080). The optimal extraction variables, such as surfactant concentration, pH, radiation time and microwave power were determined for each surfactant. The results show the advantage of using POLE instead of Genapol X-080 for the extraction of the organophosphorus pesticides with recoveries higher than 70% for most of the compounds and relative standard deviations (RSD) below 2.6%. This method was successfully applied to fresh samples as well as to aged samples for the analysis of soils with different characteristics and compared with the traditional Soxhlet technique.

Electrochemical studies and square wave stripping voltammetry of five common pesticides on poly 3,4-ethylenedioxythiophene modified wall-jet electrode

The cyclic voltammetric behavior of five common pesticides such as dicofol (DCF), cypermethrin (CYP), monocrotophos (MCP), chlorpyrifos (CPF) and phosalone (PAS) was investigated at a poly 3,4-ethylenedioxythiophene modified glassy carbon electrode (PEDOT/GCE). A method was developed for the detection and determination of these pesticides in trace level flowing stream, based on their redox behavior. The square wave stripping voltammetric principle was used to analyze the selected pesticides on PEDOT/GCE. Varying the accumulation potential and accumulation time, the best accumulation conditions were found out. Effects of initial scan potential, square wave pulse amplitude, step potential and frequency were examined for the optimization of stripping conditions. The peak current responses of analyte under optimum conditions were correlated over flow rate by using wall-jet PEDOT/GCE assembly. The calibration plots were linear over the pesticide's concentration range 0.10–72.60 μg l −1 for DCF, 0.41–198.24 μg l −1 for CYP, 0.22–220.95 μg l −1 for MCP, 0.35–259.69 μg l −1 for CPF and 1.07–141.46 μg l −1 for PAS. The limit of detection was obtained between <0.09 and <1.0 μg l −1 for five pesticides. It is low enough for trace pesticide determination in real samples. This method is applied for the determination of the five pesticides in soil samples. The recovery values obtained in spiked soil samples are 95.4 ± 5.4% for DCF, 93.7 ± 4.2% for CYP, 85.3 ± 8.4% for MCP, 94.6 ± 6.6% for CPF and 93.5 ± 4.9% for PAS.

Solid-phase microextraction method for the determination of atrazine and four organophosphorus pesticides in soil samples by gas chromatography

A simple and rapid solid-phase microextraction (SPME) based method is presented for the simultaneous determination of atrazine and four organophosphorus (i.e. parathion-methyl, chlorpyriphos, methidathion and carbophenothion) in soils. After optimisation of the different experimental variables affecting the SPME of the target compounds from aqueous solutions by using an experimental design, a consensus strategy was adopted which allowed the use of the SPME method developed for the simultaneous screening of all the analytes selected. The complete analytical procedure finally proposed consisted of a 15-min ultrasonic extraction of the target compounds from a 0.5-g soil sample with 5 ml of methanol and the dilution of this extract to up 10% methanol followed by the addition of NaCl to a final concentration of 10% (w/v). The analytes in this aqueous extract were preconcentrated for 30 min in the SPME fiber and subsequently desorbed by heating of the fiber at 260°C for 5 min in the gas chromatograph injection port. Final determination was carried out with an electron-capture detector. The recoveries of the pesticides studied in soils ranged from 72 to 123%, except for atrazine, and the SDs were below 16%. The feasibility of the procedure finally proposed for the screening of the endogenous pesticides irrespective of the properties of the soil selected has been shown.

Development of a method based on accelerated solvent extraction and liquid chromatography/mass spectrometry for determination of arylphenoxypropionic herbicides in soil

A sensitive and specific analytical procedure for determining arylphenoxypropionic herbicides in soil samples, using Ionspray ionization (ISI) liquid chromatography/mass spectrometry (LC/MS), is presented. Arylphenoxypropionic acids are a new class of herbicides used for selective removal of most grass species from any non-grass crop, commercialized as herbicide esters. Previous studies have shown that the esters undergo fast hydrolysis in the presence of vegetable tissues and soil bacteria, yelding the corresponding free acid. The feasibility of rapidly extracting arylphenoxypropionic herbicides from soil by accelerated solvent extraction (ASE) techniques was evaluated. Four different soil samples were fortified with target compounds at levels of 5 and 20 ng/g by following a procedure able to mimic weathered soils. Herbicides were extracted by a methanol/water (80:20 v/v) solution (0.12 M) of NaCl at 90 degrees C. After clean-up using graphitized carbon black (GCB) as absorbent, the extract was analyzed by HPLC/ISI-MS. The effect of concentration of acid in the mobile phase on the response of ISI-MS was investigated. The effects of varying the orifice plate voltage on the production of diagnostic fragment ions, and on the response of the MS detector, were also investigated. The ISI-MS response was linearly related to the amounts of analytes injected between 1 and 200 ng. The limit of detection (signal-to-noise ratio = 3) of the method for the pesticides in soil samples was estimated to be less than 1 ng/g.