Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Solid phase extraction with pyrenebutyric acid-bonded silica for analysis of polychlorinated biphenyls in sewage water by gas chromatography-mass spectrometry

A solid phase extraction (SPE) method using pyrenebutyric acid-bonded silica (PYB) as sorbent was developed to determine 23 polychlorinated biphenyls (PCBs) in sewage water by gas chromatography-mass spectrometry (GC-MS). Factors were optimized in SPE procedures including elution solvent, pH, and cartridge burden. The recoveries of 23 PCB congeners were 69.44-111.91% under optimized conditions. Comparisons were also conducted among PYB-SPE, C(18)-SPE and United States Environmental Protection Agency 608 (USEPA608) methods in the analysis of PCBs in sewage water samples. The results showed that the performance of PYB-SPE method was similar with USEPA608 method and better than C(18)-SPE method. Both PYB-SPE and USEPA608 methods were then employed to analyze PCBs in real spiked sewage water samples. The recoveries of PCB congeners determined by PYB-SPE method ranged from 70.6% to 92.4% in real spiked sewage water samples which were identified to be in accordance with USEPA608 method. Limits of detection (LOD) were in the range of 0.06-0.22ngL(-1) for PCB congeners. The optimized PYB-SPE method was successfully applied to the determination of PCBs in sewage water samples.     

Determination of organochlorine and organophosphorus pesticide residues in low moisture, nonfatty products using a solid phase extraction cleanup and gas chromatography

A multiresidue solid-phase extraction (SPE) method for the isolation and subsequent gas chromatographic determination of organochlorine and organophosphorus pesticide residues in low-moisture, nonfatty products is described. Residues are extracted from samples with an acetonitrile/water mixture. Cleanup of the extract is performed using graphitized carbon black and anion exchange SPE columns, and analysis is performed by gas chromatography with Hall electrolytic conductivity and flame photometric detection. Recovery data was obtained by fortifying corn, oats and wheat with pesticides. The average recoveries were 79-123% for eight organochlorine and 51-122% for 28 organophosphorus pesticide residues. The limit of quantitation for chlorpyriphos was 0.05 ppm using the Hall electrolytic conductivity detector and < 0.005 ppm using the flame photometric detector.     

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.     

Determination of organochlorine and organophosphorus pesticide residues in low moisture,nonfatty products using a solid phase extraction cleanup and gas chromatography

Abstract

A multiresidue solid‐phase extraction (SPE) method for the isolation and subsequent gas Chromatographie determination of organochlorine and organophosphorus pesticide residues in low‐moisture, nonfatty products is described. Residues are extracted from samples with an acetonitrile/water mixture. Cleanup of the extract is performed using graphitized carbon black and anion exchange SPE columns, and analysis is performed by gas chromatography with Hall electrolytic conductivity and flame photometric detection. Recovery data was obtained by fortifying corn, oats and wheat with pesticides. The average recoveries were 79–123% for eight organochlorine and 51–122% for 28 organophosphorus pesticide residues. The limit of quantitation for chlorpyriphos was 0.05 ppm using the Hall electrolytic conductivity detector and <0.005 ppm using the flame photometric detector.     

Persistent chlorinated pesticides and polychlorinated biphenyls in selected fish species from Lake Tanganyika, Burundi, Africa

Concentrations of selected organochlorine pesticides and PCBs in seven fish species (cichlids) from the north end of the Lake Tanganyika, Burundi, Africa were determined. Results were compared to previous work on the Lake Tanganyika and other water bodies and to the European Community maximum residue levels (MRLs) in edible fat. The analytical method included a hot Soxhlet extraction with a mixture of acetone: hexane (1:3, v/v), gravimetrically lipid determination, and a single step clean-up. For PCBs and stable pesticides, the clean-up was done on activated silica gel impregnated with concentrated sulfuric acid, while for non acid-stable pesticides superposed layers of alumina, silica and florisil impregnated with 15% methanolic solution of KOH were successively used. Recoveries of organochlorine pesticides from certified reference material (CRM 430) were ranging from 86% for p,p'-DDT to 107% for endrin, while recoveries from blank fat spiked fortified at three different levels were between 65% for alachlor at the lowest fortification level and 107% for mirex at the highest fortification level. The limits of detection for each analyte were ranging from 0.1 ng/g to 0.5 ng/g fat. All chlorinated pesticides were found in the analyzed species but at low concentrations. Boulengerochromis microlepis contained the highest concentrations of HCHs (288.2 +/- 15.5 ng/g fat) and DDTs (909.1 +/- 42.5 ng/g fat), while the highest PCB levels (166.7 +/- 37.4 ng/g fat for the sum of 12 congeners) were found in Oreochromis niloticus. However, there is no evidence that Lake Tanganyika is more contaminated with pesticides than other African water bodies.     

Levels of organochlorine pesticide residues in marine-, surface-, ground- and drinking waters from the Eastern Cape Province of South Africa

Persistent organochlorine pesticides (OCPs) such as DDT and its metabolites (DDDs and DDEs). chlordane, hexachlorobenzene (HCB), heptachlor and endosulfan were determined in drinking-, ground-, surface- and marine waters from the Eastern Cape Province of South Africa. Percentage recoveries of the OCPs from spiked river water ranged from 71.03 +/- 8.15% (dieldrin) to 101.25 +/- 2.17% (alpha-BHC). The levels of OCPs ranged from 5.5 ng/L (2,4-DDD) to 160 ng/L (HCB) in the water samples. Some endocrine disrupting OCPs such as DDT, DDE, heptachlor, endosulfan and chlordane were detected.     

Solid‐phase extraction and GC analyses of select agricultural pesticides and metabolites in stream water

Abstract

The occurrence of agricultural pesticides in surface waters around the USA has created a concern over the status of safe drinking water. Solid‐phase extraction (SPE) or liquid‐liquid extraction (LLE) is usually employed to concentrate trace levels of pesticides in water samples to concentrations that are measurable with advanced chromatographic instruments. We describe here a SPE and capillary gas chromatographic (GC) procedure to extract and concentrate trace levels of select agricultural pesticides and metabolites from stream water. Our SPE and GC method provides high sensitivity, with recoveries between 85% to 95%, and high reproducibility for 9 of the pesticides studied. The described method provided marginal recoveries of 19 and 60% for the atrazine metabolites.     

Levels of Organochlorine Pesticide Residues in Marine-, Surface-, Ground- and Drinking Waters from the Eastern Cape Province of South Africa

Abstract

Persistent organochlorine pesticides (OCPs) such as DDT and its metabolites (DDDs and DDEs), chlordane, hexachlorobenzene (HCB), heptachlor and endosulfan were determined in drinking-, ground-, surface- and marine waters from the Eastern Cape Province of South Africa. Percentage recoveries of the OCPs from spiked river water ranged from 71.03 ± 8.15% (dieldrin) to 101.25 ± 2.17% (α-BHC). The levels of OCPs ranged from 5.5 ng/L (2,4-DDD) to 160 ng/L (HCB) in the water samples. Some endocrine disrupting OCPs such as DDT, DDE, heptachlor, endosulfan and chlordane were detected.     

Trace analysis of dissolved polychlorinated organic compounds in the water of the Yangtse River (Nanjing, China)

Eighteen organochlorine contaminants from the water samples of the Yangtse River have been qualitatively and quantitatively analyzed. The analysis of polychlorinated organic compounds (PCOCs) extracted by C18 Solid Phase Extract (SPE) was performed using HP6890 gas chromatograph coupled by ECD detector. The analytical results demonstrate that the analytical methods are reliable based on the fact that most of the recoveries for the targeted compounds are 60-90%. Most of the concerned contaminants, i.e. chlorinated pesticides and PCBs were found in the water samples of the Yangtse River, but their concentration was very low, <2.97 ng l(-1), which is far less than 1 microg l(-1)--the standard of drinking water of China. It is apparent that the PCOCs were in high concentration during the dry season, and in low concentration during the rainy season. The situation of PCOCs contamination in the water of the Yangtse River in 1999 was greatly improved in comparison with 10 years ago.     

Method development for determination of fluroxypyr in water

Improved methods for extraction and clean up of fluroxypyr residue in water have been established. Two methods of fluroxypyr extraction were used, namely, Direct Measurement of fluroxypyr and Concentration of fluroxypyr onto A Solid Phase Extraction (SPE) Adsorbent, followed by elution with solvent before determination of fluroxypyr. The recovery for Direct Measurement of fluroxypyr in water containing 8-100 microg L(-1), ranged from 86 to 110% with relative standard deviation of 0.7 to 2.15%. For the second method, three types of SPE were used, viz. C18, C18 end-capped and polyvinyl dibenzene (ISOLUTE ENV+). The procedure involved concentrating the analyte from fluroxypyr-spiked water at pH 3, followed by elution of the analyte with 4 mL of acentonitrile. The recovery of fluroxypyr from the spiked sample at 1 to 50 microg L(-1) after eluting through either C18 or C18 end-capped ranged from 40-64% (with relative standard deviation of 0.7 to 2.15) and 41-65% (with standard deviation of 1.52 to 11.9). The use of ISOLUTE ENV+, gave better results than the C18, C18 end-capped or the Direct Measurement Methods. The recovery and standard deviation of fluroxypyr from spiked water using ISOLUTE ENV+ ranged from 91-102% and 2.5 to 5.3, respectively.     

Simultaneous analysis of triasulfuron, metsulfuron-methyl and chlorsulfuron in water and alkaline soils by high-performance liquid chromatography

A method capable of simultaneously detecting residues of three sulfonylurea herbicides at microgram/l and microgram/kg level in water and alkaline soils has been described. The method is based on solid phase extraction and HPLC with UV detection. In alkaline soils especially those containing low organic carbon it was possible to extract the herbicides with de-ionised water and no clean up step was needed. Soil samples spiked with technical grade triasulfuron, metsulfuron-methyl and chlorsulfuron were extracted twice by shaking with de-ionised water for one hour and centrifuging at 10,000 rpm for 15 minutes. Supernatants filtered through glass micro-fibre filters were passed through C18 cartridges previously pre-conditioned with methanol and de-ionised water at a flow rate of < 20 ml/min. Residues of the herbicides retained on the cartridge were eluted with acidified methanol. The eluate was analysed by HPLC. A C18 column was used with a mobile phase of methanol/water (40 + 60, V/V for for the herbicide residues were 1.0 microgram/l and 3 micrograms/kg in water and soil, respectively. The average recoveries for water samples ranged from 73-94%, while for soil samples recoveries were 77-97% for the three compounds studied.     

Assessment of organochlorine pesticide residues in Atlantic Rain Forest fragments, Rio de Janeiro, Brazil

A superficial water quality survey in a watershed of the Paraíba do Sul River, the main water supply for the most populated cities of southeastern Brazil, was held in order to assess the impact of the expansion of agricultural activity in the near border of the Atlantic Rain Forest. The aim of this study was to investigate the presence of priority organochlorine pollutants in soils and superficial waters of Atlantic rainforest fragments in Teresópolis, Rio de Janeiro State. Soil sample preparations were compared by using ultrasound, microwave assisted extraction and Soxhlet extraction. Recoveries of matrix spiked samples ranged from 70 to 130%. Analysis of a certified soil material showed recoveries ranging from 71 to 234%. Although low concentrations of organochlorine residues were found in water and soil samples, this area is of environmental importance and concern, thus demanding a monitoring program of its compartments.     

Comparison of two sample preparation methods for analysis of organochlorine pesticides residues in fish muscle

The aim of this study was to compare recoveries of organochlorine pesticides (heptachlor, α-HCH, β-HCH, γ-HCH, op'-DDD, pp'-DDD, pp'-DDE, op'-DDT, pp'-DDT) from fish muscle dried by two alternative methods: (i) grinding with anhydrous sodium sulphate and (ii) freeze drying. Pesticide residues content was determined by gas chromatography-mass spectrometry (GS-MS) method. For four pesticides (γ-HCH, α-HCH, heptachlor and pp;-DDD) in four of five fish species, higher recoveries were obtained from the freeze-dried samples. For five remaining pesticides, correlations between fish species and drying method were not found. The results of this study do not clearly indicate which drying method caused lower losses of analytes. Recoveries from the freeze-dried samples ranged from 69.9 to 117.6 %, while recoveries from the samples ground with sodium sulphate varied from 64.4 to 126.7 %. Either of the methods gave satisfactory recoveries and they both can be used interchangeably.     

有机改性剂对水中有机氯农药提取效率的影响研究

通过有机改性剂在液液萃取和固相萃取条件下水中有机氯农药的提取效率比对分析,首次探讨了有机改性剂对水中有机氯农药提取效率的影响。结果表明,(1)液液萃取前处理水样中不加有机改性剂、固相萃取前处理水样中添加一定量有机改性剂时,水中有机氯农药的提取效率较高;(2)采用正交实验优化水中有机氯农药固相萃取的提取效率实验表明,有机改性剂添加量对其影响大于有机改性剂种类对其影响;最佳优化方案为水样中添加1%甲醇时,提取效率最高。     

Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis

A new analytical method has been developed for the quantification of 59 different persistent organohalogen compounds, such as polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), PCB metabolites, organochlorine pesticides (OCPs) in biological organ tissues. The optimum extraction and cleanup procedures were examined using accelerated solvent extraction (ASE), automated gel permeation chromatography (GPC) on Biobeads S-X3 and automated solid phase extraction (SPE) on silica-gel. The target compounds were divided into two fractions, non-polar compounds and more polar compounds, which in the latter fraction was subsequently methylated using diazomethane. Detection can be achieved by GC/MS in negative chemical ionization (NCI) mode. The average recoveries of the compounds spiked in swine liver, heart, kidney, and cattle adipose tissues were considered satisfactory, and it was confirmed that the method could be used in routine analysis.     

Organic contaminant loads into the Western Mediterranean Sea: estimate of Ebro River inputs

Annual input estimates for several organic contaminants from the Ebro River into the Northwestern Mediterranean Sea were carried out on the basis of monthly sampling from November 2002 to October 2003. Some organochlorine compounds (DDT and its degradation products, DDD and DDE, PCBs (9 congeners), HCB and gamma-HCH) were selected due to their reported occurrence in the river. Furthermore, some polar pesticides used in the Ebro Delta were also determined (atrazine, simazine, diazinon, fenitrothion and molinate). Concentrations ranged from 0.4 to 19.5 ng l(-1) for the organochlorine compounds (sum of particulate and dissolved phases) and from not detected (ND) to 170 ng l(-1) for the more polar pesticides, which were only found in the dissolved phase. The sum of PCB congeners (mean 8.9 ng l(-1)) showed the highest concentrations among the organochlorine compounds and atrazine (mean 82 ng l(-1)) among the polar pesticides. Based on the contaminant concentrations and on hydrological data, contaminant discharges into the sea were estimated amounting in total to 167 and 1,258 kg year(-1) of organochlorine compounds and polar pesticides, respectively. Furthermore, it was observed that PCBs, DDTs and HCB inputs were basically influenced by spate periods due to an increase in suspended particulate matter associated to runoff and sediment resuspension. Whereas for more water soluble contaminants, such as the agrochemicals, their seasonal use had a higher incidence in contaminant fluxes. Bulk chemical parameters such as SPM, DOC, POC, %OC, %ON and C/N ratio provided additional information on the organic matter sources. This provides a better understanding of the temporal variability of the contaminant concentrations.     

Comparison of two sample preparation methods for analysis of organochlorine pesticides residues in fish muscle

The aim of this study was to compare recoveries of organochlorine pesticides (heptachlor, α-HCH, β-HCH, γ-HCH, op′-DDD, pp′-DDD, pp′-DDE, op′-DDT, pp′-DDT) from fish muscle dried by two alternative methods: (i) grinding with anhydrous sodium sulphate and (ii) freeze drying. Pesticide residues content was determined by gas chromatography-mass spectrometry (GS-MS) method. For four pesticides (γ-HCH, α-HCH, heptachlor and pp;-DDD) in four of five fish species, higher recoveries were obtained from the freeze-dried samples. For five remaining pesticides, correlations between fish species and drying method were not found. The results of this study do not clearly indicate which drying method caused lower losses of analytes. Recoveries from the freeze-dried samples ranged from 69.9 to 117.6 %, while recoveries from the samples ground with sodium sulphate varied from 64.4 to 126.7 %. Either of the methods gave satisfactory recoveries and they both can be used interchangeably.     

百菌清农药残留的SPE-GC检测

对环境水样中百菌清农药残留进行了SPE-GC分析方法研究。环境水样通过Florisil柱富集、净化,3 mL乙酸乙酯洗脱,GC-ECD进行分析检测。实验表明,百菌清农药残留在0.01~10 mg/L范围内线性关系良好,相关系数为0.9993。外标法定量,检出限为0.0035 mg/L,对实际水样进行加标回收,回收率范围在93.47%~100.14%之间,6次重复测定相对标准偏差在3.97%~4.96%之间,并将方法应用于周边环境地表水的检测。该方法具有简便,快速,准确,灵敏度高等特点,能满足环境水样中农药残留分析要求。     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.