Application of the QuEChERS method for the determination of organochlorine pesticide residues in Brazilian fruit pulps by GC-ECD

The Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method was applied to the extraction of 14 organochlorine pesticides (OCPs) residues from commercial fruit pulps available in supermarkets in Fortaleza, Northeastern Brazil. The analyses were carried out by gas chromatography (GC), coupled to an electron-capture detector (ECD), and were confirmed by GC-tandem mass spectrometry (MS). The parameters of the analytical method, such as accuracy, precision, linear range, limits of detection and quantification, were determined for each pesticide. The results showed good linearity (R² ≥ 0.9916) and the overall average recoveries were considered satisfactory obtaining values between 69 and 110%, RSD of 2–15 %, except for hexachlorobenzene (HCB) in açai, acerola and guava pulp samples. The OCPs were detected in guava (α–HCH; lindane) and soursop (α, β–HCH isomers) samples. The QuEChERS method and GC–ECD were successfully used to analyze OCPs in commercially available Brazilian fruit pulps and can be applied in routine analytical laboratories.     

Development,validation of QuEChERS-based method for simultaneous determination of multiclass pesticide residue in milk,and evaluation of the matrix effect

Extraction and quantification of pesticide residue from the milk matrix at or below the established maximum residue limit (MRL) is a challenging task for both analytical chemists and the regulatory institutions to take corrective actions for the human health and safety. The main aim of the study is to develop a simple rapid and less expensive QuEChERS extraction and cleanup method for simultaneous analysis of 41 multiclass pesticide residue in milk by gas chromatography-electron capture detector (GC-ECD), followed by confirmation of the residues with gas chromatography-mass spectrometer (GC-MS). Effect of sorbent type, temperature, spiking concentration, matrix effect (ME), measurement uncertainty (MU), inter- and intra-assay repeatability, reproducibility of recovery, and trueness of the results were investigated to validate the effectiveness of the method. Limit of determination (LOD) and limit of quantitation (LOQ) for all the analytes ranged within 0.001–0.02 and 0.002–0.05 µg mL^?1, respectively. The % recovery of all the pesticides ranged between 91.38 and 117.56% with relative standard deviation (RSD) below 2.79%. The MU for all the analytes was ≤29% of respective LOQs, and except for few pesticides, the ME was largely negative. The method fulfilled all the SANTE guidelines and thus can be extended for routine analysis of multiclass pesticide residue in milk.     

Residues of legacy organochlorine pesticides and DDT metabolites in highly consumed fish from the polluted Guanabara Bay,Brazil: distribution and assessment of human health risk

Abstract

Organochlorine (OCP) pesticides were determined in samples of sardine (Sardinella brasiliensis), whitemouth croaker (Micropogonias furnieri), and mullet (Mugil liza) from Guanabara Bay (state of Rio de Janeiro, Brazil). OCP concentrations and fish consumption were linked with acceptable daily intake values in order to assess the human health risk for the Brazilian population. The total concentrations of OCPs (Σ OCP) was 6.6?ng/g f.w., 7.5?ng/g f.w., and 2.8?ng/g f.w. for sardines, corvina, and mullet, respectively. There was a significant difference (P?<?0.05) among the species related to o,p’-DDD and o,p’-DDT concentrations. Both DDT-related compounds were 5 and 76 times more abundant in sardines than in whitemouth croaker and mullet. Newly discovered DDT metabolite, o-Cl-DDMU, was frequently detected in the fish. None of the samples exceeded the maximum limits for acceptable levels of OCP residues. According to the data of average intake of Brazilian population, none of three species exceeded toxicological parameter. The investigated fishes are considered as safe for human consumption in regard to exposure of the studied OCPs. However, fish may be a intake source of OCP metabolites such as o-Cl-DDMU whose toxicity is still unknown.     

Application of a novel cold activated carbon fiber-solid phase microextraction for analysis of organochlorine pesticides in soil

A novel and simple analytical procedure using cold activated carbon fiber-solid phase microextraction (CACF-SPME) was applied to determine organochlorine pesticides (OCs) in soil samples. The pesticides in this study consist of α -, β -, γ -, and δ -hexachlorocyclohexane (HCH). By heating the sample while cooling the fiber, the developed method not only provides better performance in terms of sensitivity, linearity and recovery but also offers shorter adsorption procedure than that of traditional headspace-solid phase microextraction (HS-SPME). The experimental conditions such as the amount of water, adsorption time and adsorption temperature were optimized. Matrix effects were investigated with different types of soils. We concluded that using the standard addition method was required for quantification purposes. The limits of detection obtained using the proposed method range from 0.01 to 0.05 ng/g, and the recoveries for CACF-SPME are in the range of 80.01% to 89.68% with relative standard deviation (RSDs) better than 8.60%. The proposed method was further applied to determine OCs in real agricultural soil. The results are in good agreement with those obtained using traditional ultrasonic extraction. The research demonstrates the suitability of the CACF-SPME for the analysis of OCs in soil.     

Adaptation and validation of QuEChERS method for the analysis of trifluralin in wind-eroded soil

This study was carried out to develop and validate a reliable analytical procedure for trifluralin analysis in wind-eroded sediments. Soil sediments trapped in BEST sediment traps were subjected to QuEChERS extraction method, incorporating a simple simultaneous cleanup step, followed by trifluralin analysis with GC-ECD. Results revealed that QuEChERS method offered a potential alternative technique for pesticide extraction from soil samples. The validity of analytical method was performed by the method-performance criteria such as, recovery, LOD, LOQ repeatability, precision, and all found to be within the required limits. It was also observed in this study that herbicide concentrations in the wind-eroded sediment did not vary with the time and trap height. Trifluralin concentrations of surface soil after four erosion events were higher (626.05 μg/kg) than wind-eroded soil (450.08 μg/kg).     

The health risk assessment of organochlorine pesticides in smoked fish products available in Szczecin,Poland

The aim of this study was to determine the concentration of organochlorine pesticides [HCH and isomers (α, β, γ), aldrin, dieldrin, endrin, heptachlor and heptachlor epoxide and DDT and its metabolites (op’-DDD, pp’-DDD, op’-DDT, pp’-DDE, pp’-DDT] in smoked fish. Analysis was made of 12 typical smoked fish products that are the most popular among customers from the city of Szczecin, Poland. Pesticide residues were found in all samples of smoked fish. The smoked sprat and cold-smoked Baltic salmon were the most contaminated smoked fish products in terms of chlorine pesticides. The sum of DDT metabolites ranged from 1.48 (smoked mackerel) to 35.53 ng/g wet weight (smoked sprat), with the lowest concentrations found for op’-DDT and the highest for pp’-DDE. The level of heptachlor epoxide isomer B was low and ranged from 0.06 ± 0.01 (smoked eel) to 0.27 ± 0.07 ng/g w.w. (smoked sprat). The content of heptachlor was 0.48–1.99 ng/g w.w. Concentration of endrin was higher compared to other pesticides, ranged from 1.50 (cold-smoked salmon fillet) to 16.84 ng/g w.w (hot-smoked warehou). The contamination of smoked products was significantly low and poses no risk to the health of consumers provided that they eat a diverse diet. The concentration of organochlorine pesticides in the analysed products was below the standards accepted in European countries.     

Validation of a QuEChERS-based gas chromatographic method for analysis of pesticide residues in Cassia angustifolia (senna)

A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy–precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01–1.0 μg mL^?1 for OCs and OPs and 0.05–2.5 μg mL^?1 for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70–120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg^?1, and the LOQs were determined as 0.01-0.049 mg kg^?1. The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.     

Land-based sources of marine pollution: organochlorine pesticides in stream systems

BACKGROUND: Organochlorine pesticides (OCPs) have been dispersed ubiquitously in the environment. Bottom sediments act as sinks for these compounds and their concentrations often reflect the degree of anthropogenic pollution. This study was designed to evaluate the occurrence and distribution of OCPs in superficial streambed sediments and their relation to land use in two creeks that contribute to the coastal pollution of the southeastern region of Argentina. METHODS: Sampling sites were selected by a combination of land use and stream type. Las Brusquitas creek, which passes through vast agricultural areas, and La Tapera creek which originates in a natural wetland and passes through horticultural farming and urban areas. OCPs quantification was carried out by GC-ECD. RESULTS AND DISCUSSION: Results showed similar total OCP concentrations in sediments from both creeks in the range of 6-25 ng/g dry wt. However, when OCPs were expressed in ng/g total organic carbon (TOC), La Tapera creek presented 4-fold higher total levels as a consequence of a higher OCP input during the recent past in that watershed. La Tapera outfall showed 4-fold higher levels than that seen in Las Brusquitas, although both values were below the sediment quality criteria demanded to protect wildlife. Sigmaendosulfans, sigmaDDTs and sigmachlordanes were the main OCP group in all samples, with Endosulfan sulfate being the most frequent and abundant compound. The predominance of metabolites with respect to parent compounds suggests a contamination mainly by runoff from aged and weathered agricultural soils. CONCLUSIONS: Despite OCPs being banned, they still exist in creek sediments from the studied region, representing continuous contributions of land-based source contaminants to the marine environment. OUTLOOK: Future research on OCP levels in suspended sediments is recommended in order to determine the total OCP concentrations in the selected stream systems.     

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.     

Tissue distribution of organochlorine pesticides in fish collected from the Pearl River Delta, China: implications for fishery input source and bioaccumulation

Fish tissues from different fishery types (freshwater farmed, seawater farmed and seawater wild) were analyzed for organochlorine pesticides (OCPs), with the aim to further our understanding of bioaccumulation, and reflect the state of different fishery environments. Significantly higher SigmaOCP levels were found in seawater farmed fish than others, and among three freshwater farmed species, the lowest levels occurred in filter-feeding fish (bighead carp). Liver contained the highest SigmaOCP levels, while no significant differences were found among other tissues. Among DDT components, p,p'-DDT was abundant in seawater fish, while for freshwater fish, p,p'-DDE was the predominant congeners, except for northern snakehead (34% for p,p'-DDE and 30% for p,p'-DDT). The new source of DDTs to freshwater fish ponds was partly attributed to dicofol, whereas sewage discharged from the Pearl River Delta and anti-fouling paint were likely the DDTs sources to seawater farmed fish.     

Presence of DDT metabolites in water,sediment and fish muscle tissue from Lake Prespa,Republic of Macedonia

Organochlorine pesticides were determined in water and sediment samples collected from the littoral zone of Lake Prespa, as well as from its three main tributaries (the rivers Golema, Brajcinska and Kranska), during the period 2004 to 2006. In addition, muscle tissue samples of barbus fish (Barbus prespensis Karaman, 1928) collected from the littoral zone of Lake Prespa were also analysed. The obtained results give an overview of the contamination levels of these problematic compounds at their potential sources in the river mouths, in the potentially affected, species-rich littoral section of the lake and in the muscle tissue of one selected fish species, collected near the rivers’ deltas. Special attention was paid to the presence of some DDT metabolites (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p′–DDE); (1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (p,p′–DDD) and 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (p,p′–DDT). The extraction of pesticides from water samples was done by liquid-liquid partition in dichloromethane. For the sediment and fish tissue we used solid-liquid extraction. The extracted residues were analyzed on a gas chromatograph equipped with an electron capture detector (GC-ECD). The results of the respective studies indicated the presence of DDT metabolic forms in the samples of the three analysed matrixes. The highest levels of presence for these pollutants were found in the muscle tissue of the fish samples. The total DDTs content in the analysed muscle tissue samples range from 11.67 to 13.58 μg kg^?1of fresh tissue. The average total DDTs content for the sediment samples were within the range of 2.32 to 4.17 μg kg^?1 of dry sediment. Higher DDT metabolites content were found in the sediments collected from the rivers than in the samples from the littoral zone. The lowest average total concentrations of DDTs, on the other hand, were recorded in the water samples and ranged between 0.036 and 0.057 μg L^?1. The obtained results indicated that the dominant metabolic form in the samples of the three investigated matrixes (water, sediment and fish tissue) from Lake Prespa was p,p′-DDE. There was a very good linear correlation in this study between the content of DDT's (total DDT metabolites) detected and the percentage of total organic material in the sediment. The detected concentrations are clearly below the toxicity thresholds; consequently, severe effects on the endemic species of Lake Prespa are not very likely.     

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。     

Enantiomer fractions of chiral organochlorine pesticides and polychlorinated biphenyls in standard and certified reference materials

Enantiomeric ratios (ERs) and enantiomeric fractions (EFs) of a number of chiral organochlorine pesticides and PCB atropisomers were measured by chiral gas chromatography/mass spectrometry (GC/MS) in five standard (SRM) and certified (CRM) reference materials: SRM 1588a (organics in cod liver oil), SRM 1945 (organics in whale blubber), Marine Mammal Quality Assurance Exercise Control Material IV (NIST IV, organics in whale blubber), CRM trout, and CRM EC-5 (sediment). Target analytes were cis- and trans-chlordane, heptachlor exo-epoxide, oxychlordane, U82, MC5, MC6, MC7, o,p^′-DDT, and PCB congeners 91, 95, 136, 149, 174, 176, and 183. Measured ERs and EFs are in close agreement with the few literature values reported for some of these analytes in SRMs and CRMs. Chiral PCB ERs and EFs measured by one-dimensional chiral GC/MS were similar to values measured using multidimensional chiral GC/MS. Non-racemic chiral compositions are in agreement with known uptake and biotransformation in the respective environmental matrices. These values should aid in the quality assurance/quality control methodologies for chiral environmental chemistry using standardized reference materials.     

Residues of organochlorine pesticides and PCBs in some Brazilian municipal solid waste compost

Persistent organic pollutants (POPs), organochlorine pesticides and polychlorinated biphenyls (PCBs), listed as per the Stockholm Convention (α -HCH, β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, p,p′-DDE, aldrin, endrin, dieldrin, PCBs 28, 52, 118, 138, 153, and 180), were analyzed in municipal solid waste (MSW) compost samples from three different Brazilian composting plants located in three São Paulo State cities: Araras, Araraquara and São Paulo (Vila Leopoldinha). Quantitative and qualitative analyses were carried out using gas chromatography electron capture detection (GC-ECD) and gas chromatography mass spectrometry (GC-MS) (Ion Trap, electron impact ionization), respectively. The samples were analyzed in triplicate and the target POPs were not detected by GC-ECD. Twelve pollutants were identified in two samples when qualitative analysis (GC-MS) was used (β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, and p,p′-DDE, PCBs 28, 118, 138, 153 and 180). The composting process has advantages such as urban solid waste reduction and landfill life-span increase, however the MSW compost quality, which can be utilized for agricultural purposes, should be evaluated and be controlled. This kind of study is the first step in making available information to answer questions regarding MSW compost for sustainable agricultural use, such as the pollutants accumulation in soil and in groundwater, and plants uptake.     

球磨硫化零价铁活化过硫酸盐降解水体中有机氯农药

利用球磨技术制备了不同硫铁(S/Fe)摩尔比的硫化零价铁(S-mZVI),并与过硫酸钠(PS)组成复合氧化体系(S-mZVI/PS),用于降解水体中的4,4′-DCBP和β-HCH,探索了制备参数和环境因子对有机氯农药降解效果的影响。结果表明：球磨过程中硫的加入不仅可以实现零价铁的硫化,还能提高零价铁的球磨效率。与球磨零价铁相比,S-mZVI的颗粒分散更均匀,呈不规则球状,且S/Fe摩尔比越大颗粒表面越平滑,更接近于球形。S-mZVI/PS体系较mZVI/PS体系对4,4′-DCBP和β-HCH的催化降解活性更高,且随着S/Fe摩尔比的增大,mZVI的腐蚀速率越高,其对污染物的降解效果越好。当S/Fe摩尔比为0.10、PS/Fe投加量配比为1/2时,4,4′-DCBP和β-HCH的降解效果最好,反应120 min后两者的最终降解率分别为92.4%和93.0%。而且,随着pH的升高,4,4′-DCBP和β-HCH降解效率逐渐降低,但二者最终降解率之间的差异较小。腐殖酸和$ {{\rm{HC}}{{\rm{O}}^ -_3} }$的存在会降低4, 4′-DCBP和β-HCH的降解效率,且随着腐殖酸和${ {\rm{HC}}{{\rm{O}}^ -_3}} $浓度的增加,对其降解效果的抑制作用增强;而$ {{\rm{N}}{{\rm{O}}^ -_3}} $的存在及浓度变化对S-mZVI/PS体系中4,4′-DCBP和β-HCH的降解影响较小。因此,S-mZVI可显著提高PS的活化效率及其对有机氯农药的降解速率,适合用作有机氯农药污染水体的修复。     

Analysis of some organochlorine pesticides in an urban atmosphere (Strasbourg, east of France)

High volume samples of urban air have been collected in Strasbourg, a big city situated in the east of France, for the evaluation of the contamination by organochlorine pesticides. Pesticides (p,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, dieldrin, endrin, gamma-HCH, cis-chlordane, trans-chlordane, alpha-endosulfan, beta-endosulfan, hexachlorobenzene, heptachlor and some of their metabolites: alpha-HCH, 2,4'-DDT, 2,4'-DDD and 2,4'-DDE) were analysed by GC-ECD. Prior to analysis, samples were Soxhlet extracted with a mixture of n-hexane/methylene chloride. The analysis of samples collected in 2001 (n = 6), 2002 (n = 7) and 2003 (n = 5) shows that alpha-HCH and gamma-HCH were detected in all samples (between 0.05 and 4 ng m(-3) and between 0.01 and 1 ng m(-3), respectively) along with aldrin and dieldrin at lower concentrations (between 0.01 and 0.08 ng m(-3) and between 0.02 and 0.09 ng m(-3), respectively). Other pesticides were detected very randomly at very low concentrations. The calculation of the alpha/gamma-HCH ratio shows that hexachlorocyclohexane measured in the atmosphere have a local origin and come probably from contaminated soil by volatilisation. alpha and beta-endosulfan were practically not detected in samples collected in 2001 and 2002 while they were always measured in the gas phase in samples from 2003. This observation can be explained by an increase of volatilisation with the increase of the air temperature. In July, temperature were higher (between 17 and 30 degrees C in climatic station) than in March-May 2001 and 2002 (between 2 and 19 and between 2 and 10, respectively).     

Concentration and fate of persistent organochlorine pesticides in estuarine sediments using headspace solid-phase microextraction

The concentration and fate of persistent organochlorine pesticides (OCPs) in estuarine surface sediments in Erh-jen and Lan-yang rivers, Taiwan were investigated using headspace solid-phase microextraction (HSSPME) method to evaluate the possible pollution potential and guideline for OCP concentrations in Taiwan. The HSSPME method exhibits a good analytical performance with low detection limits for OCP determination in sediment. In addition, results obtained using the developed HSSPME method were in good agreement with those obtained using Soxhlet extraction in a certified sample. The developed analytical method was further applied to the determination of concentrations of OCP residues in surface sediments from the estuaries of the selected rivers in Taiwan. A total of 20 surface sediments from each river was collected from 10 sampling stations. The total OCP concentrations in sediments from Erh-jen River ranged from 0.17 to 5.04 ng/g-dw with the mean values of 0.25–1.24 ng/g-dw for HCHs, 0.10–0.89 ng/g-dw for cyclodienes and 0.16–0.64 ng/g-dw for DDTs. The concentrations of OCPs in sediments from Lan-yang River were in the range 0.37–0.9 ng/g-dw with an average of lower than 0.5 ng/g-dw. HCHs and DDTs were abundant in the estuarine sediments from the selected rivers. Results obtained in this study show that the origin of OCPs in the surface sediments from Erh-jen River is a combination of erosion of the weathered soils and long-range atmospheric transport, while the OCP concentrations found in Lan-yang River could be regarded as the background levels of OCPs in Taiwan.     

Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties

This study was undertaken to validate the “quick, easy, cheap, effective, rugged and safe” (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.     

微米Cu／Fe对污染土壤洗脱液中有机氯农药的降解

以表面活性剂TritonX-100（TX-100）为洗脱剂,某有机氯农药（organochlorinepesticides,OCPs）污染场地土壤为对象,七氯、氯丹和灭蚁灵为目标污染物,研究微米Cu／Fe双金属对污染土壤洗脱液中OCPs的降解效果。考察了洗脱液中OCPs初始浓度、洗脱液pH值、微米零价铁加入量和cu负载量对Cu／Fe去除OCPs效果的影响。结果表明,微米Cu／Fe可以有效的去除土壤洗脱液中目标污染物。当微米零价铁加入量为1．0g（25g／L）,cu负载量为1．0％,洗脱液pH值为6．89时,Cu／Fe对2号土壤洗脱液中七氯、γ-氯丹、α-氯丹和灭蚁灵的去除效果最好,去除率分别为100．0％、99．3％、80．8％和71．1％。洗脱液中OCPs初始浓度越低,微米零价铁加入量越大,Cu／Fe对OCPs去除率越高;偏酸性条件有利于Cu／Fe对γ-氯丹和灭蚁灵的去除,而α-氯丹在中性条件下去除效果最好;1号土壤和2号土壤洗脱液的最佳铜负载量分别为2．O％和1．0％。     

Sample purification for analysis of organochlorine pesticides in sediment and fish muscle

The methods of sample purification for determinations of organochlorine pesticides (OCPs) in sediment and fish muscle were investigated in this study. A two-step procedure with preliminary cleanup and florisil column fraction was adopted. The working conditions of florisil column were firstly optimized. As to preliminary cleanup, liquid-liquid extraction by mixture of dimethyl formamide (DMF) and hexane and sulphonation by concentrated sulfuric acid were applied respectively and compared for the studied samples. The results indicated that liquid-liquid distribution could effectively separate lipids from fish muscle extracts, while failed in elimination of chlorophyll extracted from the relicts of hydrophytes in the sediment sample. In view of the sample appearance and clarity of gas chromatogram, sulphonation was more suitable to purify the sediment sample, however, the recoveries of the spiked standards were poor. The use of eluting solvent with stronger polarity could improve the corresponding recoveries significantly. Due to complete loss of Dieldrin, Endrin, and Endrin aldehyde after sulphonation, this pretreatment was improper to the three components. Sulfur, as the particular disturbing element in sediment, could be removed sufficiently by addition of activated copper powder. The relevant detection limits of the selected methods for OCPs in the studied substrates were also provided.