Comparison of gas and high performance liquid chromatography with selective detection for determination of triazine herbicides and their degradation products extracted ultrasonically from soil

GC and HPLC with selective detectors were compared for simultaneous determination of triazine herbicides simazine, atrazine, propazine, terbuthylazine, cyanazine, ametryn, prometryn, and atraton, and of their dealkylated degradation products in soil. The compounds were ultrasonically extracted from spiked agricultural soil samples (organic matter content < 5%) with a 2:1 acetone:n‐hexane mixture. High efficiency of GC capillary column and high selectivity of the thermionic sensitive detector (TSD) and ion trap detector (ITD) made it possible to directly analyse uncleaned soil extracts and determine all 12 compounds in one run. In reversed‐phase HPLC with diode‐array detector (DAD), the co‐elution of soil matrix components interfered with the determination of methylthiotriazines and terbuthylazine. The recovery of triazine compounds, determined by GC‐TSD, from a silty sand soil (organic matter content 1.82%, pH 6.22) spiked at levels of 15–600 ng g^–1, were 70–90% (RSD 9–19%), except for deisopropylatraton (38%). GC‐TSD analysis with detection limits of 5–15 ng g^–1 for chloro‐ and methylthiotriazines and 30 ng g^–1 for methoxytriazines was more sensitive than GC‐MS(ITD). GC analysis with electron capture detection was sensitive for some chlorotriazines, but a reliable compound quantification in complex chromatograms of uncleaned soil of extracts was not possible. For all compounds save didealkylatrazine, HPLC‐DAD was at least two times less sensitive than GC‐TSD. Soil/sediment organic matter, clay and silt content, and pH were identified as matrix characteristics which might affect ultrasonic extraction recovery of a particular compound.     

Microwave assisted solvent extraction and coupled-column reversed-phase liquid chromatography with UV detection use of an analytical restricted-access-medium column for the efficient multi-residue analysis of acidic pesticides in soils.

A screening method has been developed for the determination of acidic pesticides in various types of soils. Methodology is based on the use of microwave assisted solvent extraction (MASE) for fast and efficient extraction of the analytes from the soils and coupled-column reversed-phase liquid chromatography (LC-LC) with UV detection at 228 nm for the instrumental analysis of uncleaned extracts. Four types of soils, including sand, clay and peat, with a range in organic matter content of 0.3-13% and ten acidic pesticides of different chemical families (bentazone, bromoxynil, metsulfuron-methyl, 2,4-D, MCPA, MCPP, 2,4-DP, 2,4,5-T, 2,4-DB and MCPB) were selected as matrices and analytes, respectively. The method developed included the selection of suitable MASE and LC-LC conditions. The latter consisted of the selection of a 5-microm GFF-II internal surface reversed-phase (ISRP, Pinkerton) analytical column (50 x 4.6 mm, I.D.) as the first column in the RAM-C18 configuration in combination with an optimised linear gradient elution including on-line cleanup of sample extracts and reconditioning of the columns. The method was validated with the analysis of freshly spiked samples and samples with aged residues (120 days). The four types of soils were spiked with the ten acidic pesticides at levels between 20 and 200 microg/kg. Weighted regression of the recovery data showed for most analyte-matrix combinations, including freshly spiked samples and aged residues, that the method provides overall recoveries between 60 and 90% with relative standard deviations of the intra-laboratory reproducibility's between 5 and 25%; LODs were obtained between 5 and 50 microg/kg. Evaluation of the data set with principal component analysis revealed that the parameters (i) increase of organic matter content of the soil samples and (ii) aged residues negatively effect the recovery of the analytes.     

Analysis of phenoxyalkanoic acid herbicides and their phenolic conversion products in soil by microwave assisted solvent extraction and subsequent analysis of extracts by on-line solid-phase extraction-liquid chromatography

A multiresidue method for the determination of phenoxyalkanoic acid herbicides and their phenolic conversion products in soil was developed. The method was based on microwave-assisted solvent extraction (MASE) of soil samples by an aqueous methanolic mixture and subsequent analysis of extracts by automated solid-phase extraction followed by on-line high-performance liquid chromatography and diode array detection. MASE parameters (extraction temperature and time, composition of the extraction mixture and extraction volume) were optimized with respect to analyte recoveries. The method was validated with two types of soils containing 1.5 and 3.5% organic matter, respectively, both types containing fresh and aged residues of sought analytes. Under the selected analytical conditions when soils with fresh residues were analyzed all target analytes were recovered above 80% from the soil containing 1.5% organic matter, while limits of identification at the level of 20-40 ng/g were achieved. From the soil containing 3.5% organic matter the least polar phenolic analytes exhibited slightly reduced recoveries, while identification limits of 30-50 ng/g were achieved. Samples with aged residues exhibited reduced recoveries for some analytes, the reduction amounting up to 6-12% within 1 month of aging period depending on soil organic matter.     

Determination of linuron and related compounds in soil by microwave-assisted solvent extraction and reversed-phase liquid chromatography with UV detection

The combination of microwave-assisted solvent extraction (MASE) and reversed-phase liquid chromatography (RPLC) with UV detection has been investigated for the efficient determination of phenylurea herbicides in soils involving the single-residue method (SRM) approach (linuron) and the multi-residue method (MRM) approach (monuron, monolinuron, isoproturon, metobromuron, diuron and linuron). Critical parameters of MASE, viz, extraction temperature, water content and extraction solvent were varied in order to optimise recoveries of the analytes while simultaneously minimising co-extraction of soil interferences. The optimised extraction procedure was applied to different types of soil with an organic carbon content of 0.4-16.7%. Besides freshly spiked soil samples, method validation included the analysis of samples with aged residues. A comparative study between the applicability of RPLC-UV without and with the use of column switching for the processing of uncleaned extracts, was carried out. For some of the tested analyte/matrix combinations the one-column approach (LC mode) is feasible. In comparison to LC, coupled-column LC (LC-LC mode) provides high selectivity in single-residue analysis (linuron) and, although less pronounced in multi-residue analysis (all six phenylurea herbicides), the clean-up performance of LC-LC improves both time of analysis and sample throughput. In the MRM approach the developed procedure involving MASE and LC-LC-UV provided acceptable recoveries (range, 80-120%) and RSDs (<12%) at levels of 10 microg/kg (n=9) and 50 microg/kg (n=7), respectively, for most analyte/matrix combinations. Recoveries from aged residue samples spiked at a level of 100 microg/kg (n=7) ranged, depending of the analyte/soil type combination, from 41-113% with RSDs ranging from 1-35%. In the SRM approach the developed LC-LC procedure was applied for the determination of linuron in 28 sandy soil samples collected in a field study. Linuron could be determined in soil with a limit of quantitation of 10 microg/kg.     

Dependence of <Superscript>210</Superscript>Po activity on organic matter in the reverine environs of coastal Kerala

This paper deals with the distribution of ²¹⁰Po in the river bank soil samples of three major rivers namely Bharathapuzha, Periyar and Kallada river of Kerala. The dependence of ²¹⁰Po activity on organic matter content in the samples was also studied. The soil samples were collected and analyzed for ²¹⁰Po radionuclide using standard radiochemical analytical method. Activity of ²¹⁰Po increases with increase in organic matter content in samples. Along the Bharathapuzha river bank the ²¹⁰Po activity ranges from 2.96 to 12.48 Bq kg⁻¹ with mean 5.62 Bq kg⁻¹. The organic matter percentage in the samples ranges from 0.4 to 2.8 and a good correlation with correlation coefficient 0.9 was found between activity and organic matter percentage. In the Periyar river environs ²¹⁰Po activity ranges from 3.47 to 13.39 Bq kg⁻¹ with mean value 9.27 Bq kg⁻¹. Organic matter percentage in these samples ranges from 1.20 to 4.10 and the correlation coefficient between ²¹⁰Po activity and organic matter percentage was found to be 0.8 In the Kallada river bank soil samples ²¹⁰Po activity ranges from 4.46 to 6.45 Bq kg⁻¹. The organic matter percentage ranges from 1.4 to 3. The correlation coefficient between ²¹⁰Po activity and organic matter percentage in the samples was found to be 0.9.     

Application of liquid phase microextraction based on solidification of floating organic drop for the determination of triazine herbicides in soil samples by gas chromatography with flame photometric detection

A simple and efficient liquid phase microextraction based on solidification of floating organic drop coupled with gas chromatography–flame photometric detection was developed for the extraction and determination of some triazine herbicides (metribuzin, simetryn, ametryn and prometryn) in soil samples. The type and volume of the extraction solvent, sample solution temperature, salt addition, stirring rate, and the extraction time were optimized. Under the optimal conditions, the linear response was observed over the range of 10–2000?µg?kg^?1 for metribuzin and 2–500?µg?kg^?1 for simetryn, ametryn, and prometryn, respectively, with the correlation coefficients (r) varying from 0.9990 to 0.9992. The limits of detection were in the range between 0.2 and 1.0?µg?kg^?1 (S/N?=?3?:?1). The recoveries of the target analytes for the spiked soil samples ranged from 75.5% to 97.3%, with the relative standard deviation values less than 7.2% (n?=?5). The enrichment factors were achieved ranging from 122 to 336. The developed method was applied for the preconcentration and determination of triazine herbicides in real soil samples and a satisfactory result was obtained.     

A Review of Analytical Methods for Sulfonylurea Herbicides in Soil

Abstract

The sulfonylurea herbicides are a group of about twenty compounds used for the control of broad-leaved weeds and some grasses in cereal crops. These herbicides are non-volatile, and their water solubilities are pH dependent being greater in alkaline than in acidic solutions. Their soil adsorption is generally low, with leaching potential in alkaline field soils. Sulfonylurea herbicides are degraded in soils by both chemical and biochemical mechanisms. Chemical degradation is particularly important in acidic soils where herbicide degradation is considerably more rapid that in soils of pH > 7. Application rates in the order of 10 g ha^?1 necessitate analytical techniques capable of quantifying soil based residues in the sub μ kg^?1 levels. Analytical methodologies based on plant bioassays, and chemical extraction followed by gas chromatographic (GC), high performance liquid chromatographic (HPLC), and enzyme immunoassay techniques are described and discussed.     

Determination of triazine herbicides by capillary gas chromatography with large-volume on-column injection

Summary This paper describes a study of the potential of large-volume on-column injection for the determination of triazine herbicides in clean water samples (ground-water). The sensitivity of chromatographic determination has been increased by two orders of magnitude by injection of up to 200 μL of pesticide solutions and nitrogen-phosphorus detection. Analytical characteristics expressed as precision, linear range and limit of detection have been determined, the results indicating adequate analytical performance and the ruggedness of the injection technique. As an application, gas chromatography with large-volume on-column injection and nitrogen-phosphorus detection was combined with off-line liquid-liquid micro-extraction with hexane (1 mL water/1 mL hexane). The procedure was applied to spiked groundwater samples at two concentration levels (1 and 10 μg L⁻¹) with good recoveries (between 81 and 103%, except for deethylatrazine) and repeatability (better than 15% at the 1 μg L⁻¹ level). Limits of detection of the triazine herbicides studied ranged from 0.08 to 0.16 μgL⁻¹.     

Determination of tetracycline residues in soil by pressurized liquid extraction and liquid chromatography tandem mass spectrometry

An optimized extraction and cleanup method for the analysis of chlortetracycline (CTC), doxycycline (DC), oxytetracycline (OTC) and tetracycline (TC) in soil is presented. Soil extraction in a pressurized liquid extraction system, followed by extract clean up using solid-phase extraction (SPE) and tetracycline determination by liquid chromatography tandem mass spectrometry (LC-MS/MS) provided appropriate efficiency and reproducibility. Different dispersing agents and solvents for soil extraction and several SPE cartridges for cleanup were compared. The best extraction results were obtained using ethylenediamine tetraacetic acid-treated sand as dispersing agent, and water at 70 °C. The most effective cleanup was obtained using Strata-X^TM sorbent in combination with a strong anion exchange cartridge. Recoveries ranged from 71% to 96% and precision, as indicated by the relative standard deviations, was within the range of 8–15%. The limits of quantification (LOQs) by using LC-MS/MS, based on signal-to-noise ratio (S/N) of 10, ranged from 1 μg kg⁻¹ for TC to 5 μg kg⁻¹ for CTC. These results pointed out that this technique is appropriate to determine tetracyclines in soils. Analysis of 100 samples taken in the Valencian Community revealed that, in soil, up to 5 μg kg⁻¹ CTC, 15 μg kg⁻¹ OTC, 18 μg kg⁻¹ TC, and 12 μg kg⁻¹ DC could be detected. Detection of the analytes in several samples, which typify great part of the Spanish agricultural soils, should be outlined as most important result of this study. Electronic supplementary material  The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

Determination of 24 pesticides residues in mineral and peat soils by modified QuEChERS method and gas chromatography

A simple extraction and cleanup procedure has been developed for the analysis of 24 organophosphorus (OP), organochlorine (OC) and pyrethroid (PY) pesticides in mineral and peat soils using modified QuEChERS method. The pesticides were extracted from the soil with acidified acetonitrile. The water was removed from the extract by salting out with sodium chloride and addition of magnesium sulfate. For OP pesticides, the extracts were cleaned up with 0.2 g of primary secondary amine packed in glass Pasteur pipette and determined by gas chromatography with flame photometric detector. For OC and PY pesticides, the extracts were cleaned up with 0.2 g of silica gel packed in a glass Pasteur pipette and determined by gas chromatography with electron capture detector. After the cleanup, the extracts had lower colour intensity and reduced matrix interferences. The recovery of the OP and OC pesticides for mineral and peat soils determined at 0.01–1.0 mg kg^?1 fortification levels ranged from 79.0–120.0% and 82.2–117.6%, respectively. The detection limits for OP and OC pesticides were 0.001–0.01 and 0.002–0.005 mg kg^?1, respectively. The recovery of the PY pesticides ranged from 87.5–111.7% at the detection limits of 0.002–0.010 mg kg^?1. The relative standard deviations for all pesticides studied were below 10.8%. The modified method was simple, fast, and had utilized less reagents than the conventional methods. The method was applied to the determination of the pesticide residues in mineral and peat soil samples collected from the vegetable farms.     

A study on 210Po activity concentration in soil at different depths along coastal Kerala

The paper presents systematic studies on the vertical profiles of ²¹⁰Po, an important decay product of ²³⁸U, in soils along coastal Kerala. Soil samples collected from different depth intervals 0–10, 10–20, 20–30 cm were analyzed for ²¹⁰Po activity concentration by radiochemical methods. The activity ²¹⁰Po in soil samples were counted using a ZnS(Ag) alpha scintillation counting system. The mean values of activity concentrations of ²¹⁰Po in soil of various depths were found to be 8.66, 5.63 and 4.95 Bq kg⁻¹ for depth intervals of 0–10, 10–20 and 20–30 cm, respectively. The overall activity concentration of ²¹⁰Po in soil was found to vary from 2.26 ± 0.19 to 14.02 ± 0.12 Bq kg⁻¹ with a mean value of 6.43 Bq kg⁻¹. Maximum activity concentration was found in soil samples of Kollam region with the mean value of 10.08 ± 0.92 Bq kg⁻¹. The activity of ²¹⁰Po was found to be comparatively high in surface soil. The variation of ²¹⁰Po activity concentration with organic matter contents was studied. ²¹⁰Polonium activity concentration was found to increase with increasing organic matter content.     

Determination of sulfonylurea herbicides in soil extracts by solid-phase extraction and capillary zone electrophoresis

Summary Sulfonylurea herbicides in soil extracts were concentrated using off-line solid-phase extraction (SPE), and determined by capillary zone electrophoresis (CZE) and UV detection. The method involves extraction of soils with 0.1 M NaHCO₃ solution and subsequent preconcentration by using C₁₈ cartridges prior to separation of the pesticide using CZE. The results show that a C₁₈ cartridge is suitable for the purification of sulfonylurea herbicides in soil extracts with the recoveries ranging from 65–103%. The separation conditions affecting the resolution and detection sensitivity was systematically investigated. The sulfonylureas were resolved well using 30 mM sodium acetate (NaAc)/acetic acid (HAc)+10% acetonitrile (ACN) buffer at pH 4.80. The calibration plots for the test solutes in the concentration of 0.2–50 mg L⁻¹ were linear with detection limits in the range of 0.05–0.10 mgL⁻¹. The proposed method has been successfully demonstrated for the determination of sulfonylurea herbicides in soil samples.     

气相色谱法同时测定玉米中12种三嗪类除草剂的残留量

建立了气相色谱-氮磷检测器同时检测玉米中12种三嗪类除草剂（西玛通、西玛津、阿特拉津、扑灭津、特丁通、特丁津、环丙津、西草净、扑草净、特丁净、甲氧丙净、环嗪酮）残留量的方法。玉米样品用乙腈萃取,强阳离子交换(SCX)固相萃取柱净化后,用DB-5弹性石英毛细管柱(30 m×0.25 mm i.d.×0.25 μm)分离样品,氮磷检测器测定。12种三嗪类除草剂在0.01～2.0 mg/L范围内线性关系关系良好,相关系数均大于0.998;最低检测限为0.01 mg/kg;添加回收率为84.0%～106.8%;相对标准偏差为0.9%～4.7%。     

A simplified method for the determination of fenpropathrin residues in fruits

Summary A simple and efficient method is described for the determination of fenpropathrin in oranges, pears, apples and strawberries. The procedure is based on the extraction of each homogenized fruit sample with hexane:acetone (1∶1, v/v) mixture, followed by a cleanup technique on a column packed with florisil, using a hexane:ethyl ether (7∶3, v/v) mixture, and gas chromatographic analysis with electron capture detection (ECD). The fortification levels (0.5;1.0;2.0 mg kg⁻¹) were selected according to the maximum residue limits (MRLs) established for fenpropathrin by Brazilian legislation. Mean recoveries from five replicates of fortified fruit samples ranged from 83 % to 98%, with coefficients of variation from 1.4 to 13.5 and detection limits varying from 0.1 to 0.2 mg kg⁻¹.     

Lead concentration in soil from an old mining town

Lead concentration in soils has been measured in Vetagrande, an old mining town located at the state of Zacatecas in México. Eighty nine soils samples were analyzed using Energy Dispersive X-ray Fluorescence. The lead concentrations were treated with the Kriging method in order to estimate the lead concentration distribution in the studied area. Pb levels in soils were from 8 to 7730 μg kg⁻¹, where 28.1% of soil samples have less than 400 μg kg⁻¹, 71.9% is above 400 μg kg⁻¹ which is the maximum level recommended by the EPA for residential use of soil. Lead concentration measured around public sites represent a risk of lead intake in the population.     

Determination of polybrominated diphenyl ethers in domestic dust by microwave-assisted solvent extraction and gas chromatography-tandem mass spectrometry

In this paper, a rapid and simple method for the analysis of polybrominated diphenyl ethers (PBDEs) in house dust samples based on microwave-assisted solvent extraction (MASE) and gas chromatography-tandem mass spectrometry (GC-MS/MS) is presented. Extraction conditions were optimized using a multifactorial experimental design approach. The use of an aqueous NaOH phase in combination with a non-polar organic phase (hexane) to extract the target analytes from dust allowed an efficient extraction and reduced chromatographic background. The final hexane extracts could be analyzed after a simple one-step cleanup procedure using Florisil. The validation of the method was performed in terms of accuracy, linearity, and repeatability. The limits of detection (LODs) ranged from 0.29 to 0.55 ng/g for all compounds. The target PBDEs were found in several real dust samples collected in urban and rural houses of Northwestern Spain.     

Geographical and vertical distribution of radiocesium levels in coniferous forest soils in Izmir

Preliminary picture of ¹³⁷Cs radioactivity levels in forested areas in and around Izmir is illustrated. Both activity concentrations and activity depositions of ¹³⁷Cs in soil samples were determined. Their values varied from 8.29±0.27 to 445±3.16 Bq.kg⁻¹ (d.w.) and 0.63±0.01 to 11.6±0.08 kBq.m^–2 (d.w.), respectively. It was found that while activity deposition of ¹³⁷Cs is normally distributed, activity concentration of ¹³⁷Cs is log-normally distributed in forest soils and the activity deposition is less variable than the activity concentration. Cesium-137 activities in soils increase with increasing elevation, annual average rainfall and soil organic matter.     

Rapid analysis of organic farming insecticides in soil and produce using ultra-performance liquid chromatography/tandem mass spectrometry

A new method for the analysis of three ecological insecticides, namely azadyrachtin, spinosad (sum of spinosyn A and spinosyn D) and rotenone, in produce and soil samples is presented. Investigated compounds are one of the most significant insecticides authorized for organic farming crop protection in many countries. Extraction of the pesticides from plant and soil matrices was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The method entailed a single extraction of the investigated compounds with acidified acetonitrile followed by a dispersive solid-phase extraction cleanup step prior to the final determination by reverse-phase ultra-performance liquid chromatography/tandem quadrupole mass spectrometry (UPLC-MS/MS). Validation studies were carried out on cabbage, tomato and soil samples. Recoveries of the spiked samples were in the range between 67% and 108%, depending on the matrix and the spiking level. Relative standard deviations for all matrix–compound combinations did not exceed 12%. The limits of quantification were ≤0.01 mg kg⁻¹ in all cases, except for azadirachtin. The developed method was applied to the analysis of real samples originating from organic farming production.     

Determination of herbicide residues in soil in the presence of persistent organochlorine insecticides

Summary A rapid and reproducible gas-chromatographic method has been developed for determination of residues in soil of some widely used herbicides such as trifluralin, metribuzin, alachlor, acetochlor, metolachlor, pendimethalin, simazine, atrazine, prometryne, in the presence of persistent organochlorine insecticides (p,p-DDT, o,p-DDT, p,p-DDE, alpha-HCH, gamma-HCH, heptachlor). Determination of some herbicides by GC/ECD is difficult since their relative retention times on packed columns usually used for pesticide analysis are equal or close to those of some persistent organochlorine insecticides which can still be found almost everywhere, especially in cultivated soils. A 1.8 m column of 3% OV-225 + 5% SE-52 in a ratio of 1.4:0.9 gave good separation of all herbicides and insecticides mentioned. The influence of 6 solvents and solvent systems applied most frequently for soil extraction of pesticide residues on recovery of the compounds under study was examined. Acetonitrile was the most suitable extractant as it rendered highest residue recoveries and minimal amount of co-extractives. Residues of simazine, atrazine, and prometryne were determined in the same extracts by the use of NP-detector and a column of 5% Carbowax 20M. Recoveries of the compounds under study were in the interval of 86–103% without cleanup and 78–94% when cleanup was carriet out. The method can be used in pesticide monitoring of soil as it offers an opportunity for rapid determination of soil applied herbicides and persistent organochlorine insecticides which are some of the most common pollutants in cultivated soils.     

Influence of the solvent on the gas chromatographic behaviour of urea herbicides

Summary Degradation products of chlorsulfuron, chlortoluron, diuron, fluometuron, isoproturon, linuron, metabenzthiazuron, metobromuron, and monuron formed in the gas chromatographic injector have been used for identification of the respective herbicides. Mass spectra of the derived compounds were obtained with a quadrupole mass spectrometric detector working in scan mode (20–450 amu). The compounds generated often depended on the solvent used for phenylurea herbicide injection (ethanol, methanol, dichloromethane, and acetonitrile). When methanol and ethanol were used as solvents the major products formed from phenylureas were carbamic acid esters. When acetonitrile or dichloromethane were used the main derivatives were phenylisocyanates. Chlorsulfuron and metabenzthiazuron, however, generated a triazine plus a phenylsulfonamide and a benzothiazolamine, respectively, irrespective of the solvent used. Linuron and diuron behaved similarly and gave degradation products with the same mass spectra. The thermal reactions occurred instantaneously in the injector block and were promoted by the high temperature selected (300°C). Detemination of the compounds derived from urea herbicides, by use of a 30 m BP10 column and a selected ion registering (SIR) program based on two or three ions, can be used for sensitive detection of the presence of urea herbicides in environmental extracts. With standards in methanol instrument detection limits ranged from 0.1 pg for chlorsulfuron (detected as 2-chlorobenzensulfonamide) to 1 pg for monuron and metobromuron (both detected as their carbamic acid methyl esters).RSD were below 9% at the 5 ng L⁻¹ level. The response was linearly dependent on quantily (r>0.9986) in the 5 ng L⁻¹ to 25 μg L⁻¹ range. Unequivocal identification of some phenylurea herbicides was not always possible because some herbicides with similar structures, for example diuron and linuron, gave the same derivative.