PAHs analysis of fish whole gall bladders and livers from the Natural Reserve of Camargue by GC/MS

Traces of parent polycyclic aromatic hydrocarbons (PAH) in fish whole gall bladders and livers from the Natural Reserve of Camargue were determined from three different species: cels, goldfishes and catfishes by capillary gas chromatography-mass spectrometry (GC/MS) after Soxhlet extraction and florisil column cleanup. Results have been successfully correlated with biological fish parameters in order to identify adequate biomarkers of PAHs contamination.     

Evaluation of activated carbon fiber filter for sampling of organochlorine pesticides in environmental water samples

A simple method for quantitative analyses of organic chlorine pesticides (OCPs) in environmental water samples such as rainwater, river water and seawater using activated carbon fiber filters (ACFF) is described. ACFF was used as adsorbent to collect the chemicals in water samples. The collection of OCPs was completed almost for one day by stirring the mixture of the sample and the ACFF chips at room temperature. The adsorbed OCPs on the ACFF could be extracted easily with toluene-ethanol (4:1) mixed solvent. The purified extract by a florisil column chromatograph was followed by the analysis using high-resolution gas chromatograph/high-resolution mass spectrometer. Recoveries of OCPs spiked to actual samples such as rainwater, river water and seawater samples were approximately more than 80%, and the coefficients of variations were within 10%. This method was applied to the actual samples and was confirmed to be applicable for monitoring sub-ng/l level OCPs in environmental water samples.     

Persistent chlorinated pesticides in fish species from Qiantang River in East China

Thirteen organochlorine pesticides (OCPs) in 18 fish species from Qiantang River were firstly determined by GC-ECD. To elucidate the sources and the environment fate of these pollutants, water and sediment samples were also analyzed for OCPs contents. Total concentrations of OCPs in fish muscles ranged from 7.43 to 143.79 ng g(-1) wet weight (ww) with highest concentration recorded in sole fish (Cynoglossus abbreviatus), a benthic carnivore. The results indicated that carnivore fish have higher OCPs concentration than other fish with different feeding modes. OCPs concentration in fish was in the range of 1.86-5.85, 2.65-133.51 and 1.94-12.48 ng g(-1) for HCHs (alpha-, beta-, gamma-, delta-HCH), DDTs (p,p'-DDD, p,p'-DDE, p,p'-DDT, o,p'-DDD) and other OCPs (aldrin, diedrin, endrin, heptachlor, heptachlor expoide), respectively. The highest OCPs concentration in fish organs of four big fish species was found in brain of silver carp (Hypophthalmichthys molitrix), 289.26 ng g(-1) ww followed by kidney, liver, heart and gill. Among the OCPs analyzed, DDE, gamma-HCH and heptachlor were the predominant contaminants in fish muscle, which indicated that there was recent input of lindane. Significant correlation was observed between concentrations of DDTs and lipid content as well as between OCPs and lipid contents in fish species. Both field water bioconcentration factors (BCF) and sediment BCF showed a positive correlation with octanol-water partition coefficients (Kow) in the sole fish.     

GC/MS法测定润滑油基础油中多环芳烃

对润滑油基础油中多环芳烃的气相色谱/质谱(GC/MS)测定方法进行了研究,探讨了样品的提取,固相萃取柱净化等前处理方法,同时也对仪器测定条件进行了优化.结果表明,在检测润滑油基础油中多环芳烃时,经优化的GC/MS法的加标回收率和精密度均达到较满意的水平.     

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。     

Biota–sediment accumulation factor (BSAF), bioaccumulation factor (BAF), and contaminant levels in prey fish to indicate the extent of PAHs and OCPs contamination in eggs of waterbirds

Samples of pond sediment, fish, and shrimp were collected from the Ramsar site at Mai Po marshes, Hong Kong (south China), and samples of pond sediment, fish, and shrimp, as well as eggs of water birds (Chinese Pond Herons (Ardeola bacchus) and Little Egrets (Egretta garzetta)), were collected from two smaller wetland sites at Jiangsu Province (mid-China), between 2004 and 2007. Accumulation levels of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in the biota were used to calculate biota–sediment accumulation factor (BSAF) and bioaccumulation factor (BAF). For fish and shrimp, BSAFs of OCPs (3.8–56) were greater than those of PAHs (0.12–6.3). BSAFs and BAFs of 11–79 and 4–34, respectively, were registered for OCPs in eggs of the birds and were greater than those for PAHs (0.11–1.5 and 0.02–1.3, respectively). Assuming that fish were the main prey of the birds, greater bioaccumulation of OCPs was detected for both bird species (BAFs?=?4.5–34), while accumulation of PAHs was only detected in Little Egret (BAF?=?1.3). A significant linear relationship (p?<?0.01) was observed between concentrations of OCPs in bird eggs and in the prey fish. The present study provides a new possibility of using OCP levels detected in prey fish to predict the extent of OCPs contamination in eggs of waterbirds including the endangered species, as a noninvasive method.     

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.     

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.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

A novel pretreatment approach for fast determination of organochlorine pesticides in biotic samples

Recent studies have focused on enantiomeric behaviors of chiral organochlorine pesticides (OCPs) in biotic matrix because they provide insights into the biotransformation processes of chiral OCPs. In the present paper, a double in-line column chromatographic method was developed to effectively remove the lipid impurity in different biotic samples for clean-up of OCPs. After an initial Soxhlet extraction of OCPs from the biotic samples by a mixture of acetone and dichloromethane (DCM), dimethyl sulfoxide (DMSO) was directly added to the extract, and low boiling point solvents (acetone and DCM) were then evaporated. OCPs remained in DMSO were eluted via column 1 filled with silicon gel, and subsequently passed through column 2 packed with 15% deactivated florisil. This novel method was characterized by significant time and solvent savings. The recovery rates of alpha-HCH (hexachlorocyclohexane), beta-HCH, gamma-HCH and delta-HCH were 78.5+/-3.1%, 72.4+/-7.7%, 72+/-4.0% and 70.0+/-8.7%, respectively, and 92.5+/-3.8%, 79.7+/-6.7% and 83.4+/-6.5% for 1,1-dichloro-2-(2-chlorophenyl)-2-(4- chlorophenyl) ethylene (o,p'-DDE), 1,1-dichloro-2-(2-chlorophenyl)-2-(4-chloro phenyl)ethane (o,p'-DDD) and 1,1,1-trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl) ethane (o,p'-DDT), separately. In addition, the separation efficiencies of the target compounds by both achiral and chiral gas chromatographic columns were satisfactory using the established method. Therefore, the double in-line column chromatography was a useful alternative method for pretreatment of OCPs in different biotic samples.     

A novel pretreatment approach for fast determination of organochlorine pesticides in biotic samples

Recent studies have focused on enantiomeric behaviors of chiral organochlorine pesticides (OCPs) in biotic matrix because they provide insights into the biotransformation processes of chiral OCPs. In the present paper, a double in-line column chromatographic method was developed to effectively remove the lipid impurity in different biotic samples for clean-up of OCPs. After an initial Soxhlet extraction of OCPs from the biotic samples by a mixture of acetone and dichloromethane (DCM), dimethyl sulfoxide (DMSO) was directly added to the extract, and low boiling point solvents (acetone and DCM) were then evaporated. OCPs remained in DMSO were eluted via column 1 filled with silicon gel, and subsequently passed through column 2 packed with 15% deactivated florisil. This novel method was characterized by significant time and solvent savings. The recovery rates of α -HCH (hexachlorocyclohexane), β -HCH, γ -HCH and δ -HCH were 78.5 ± 3.1%, 72.4 ± 7.7%, 72 ± 4.0% and 70.0 ± 8.7%, respectively, and 92.5 ± 3.8%, 79.7 ± 6.7% and 83.4 ± 6.5% for 1,1-dichloro-2-(2-chlorophenyl)-2-(4- chlorophenyl) ethylene (o,p′-DDE), 1,1-dichloro-2-(2-chlorophenyl)-2-(4-chloro phenyl)ethane (o,p′-DDD) and 1,1,1-trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl) ethane (o,p′-DDT), separately. In addition, the separation efficiencies of the target compounds by both achiral and chiral gas chromatographic columns were satisfactory using the established method. Therefore, the double in-line column chromatography was a useful alternative method for pretreatment of OCPs in different biotic samples.     

西溪湿地底泥中有机氯农药分布特征及风险评价

以西溪湿地为主要研究区域,采集了西溪湿地主要河口的表层和柱状底泥样品,以气相色谱(GC)/电子捕获检测器(ECD)定量测定样品中滴滴涕(DDTs)、六六六(HCHs)的含量,并对其进行生态风险评价.结果表明:(1)西溪湿地底泥样品中DDTs浓度明显比HCHs高.有机氯农药(OCPs)在研究区域内的底泥表层样品中残留呈现...     

Development,validation and matrix effect of a QuEChERS method for the analysis of organochlorine pesticides in fish tissue

This study aims to develop and validate a method to determine OCPs in fish tissues, minimizing the consumption of sample and reagents, by using a modified QuEChERS along with ultrasound, d-SPE and gas chromatography with an electron capture detector (GC-ECD), refraining the pooling. Different factorial designs were employed to optimize the sample preparation phase. The validation method presented a recovery of around 77.3% and 110.8%, with RSD lower than 13% and the detection limits were between 0.24 and 2.88 μgkg^?1, revealing good sensitiveness and accuracy. The method was satisfactorily applied to the analysis of tissues from different species of fish and OCPs residues were detected. The proposed method was shown effective to determine OCPs low concentrations in fish tissues, using small sample mass (0.5 g), making the sample analyses viable without the need for grouping (pool).     

Spatial distribution of organochlorine contaminants in soil, sediment, and fish in Bikini and Enewetak Atolls of the Marshall Islands, Pacific Ocean

Several nuclear tests were performed at Enewetak and Bikini Atolls in the Marshall Islands between 1946 and 1958. The events at Bikini Atoll involved several ships that were tested for durability during nuclear explosions, and 24 vessels now rest on the bottom of the Bikini lagoon. Nine soil samples were collected from different areas on the two islands of the atoll, and eighteen sediment, nine fish, and one lobster were collected in the vicinity of the sunken ships. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polychlorinated terphenyls (PCTs) in these samples were analyzed using gas chromatography/ion trap mass spectrometry (GC/ITMS). The average recoveries ranged from 78% to 104% for the different PCB congeners. The limits of detection (LOD) for PCBs, PCTs, DDE, DDT, and dieldrin ranged 10-50 pg g⁻¹. Some fish from Enewetak contained PCBs at a concentration range of 37-137 ng g⁻¹, dry weight (dw), and most of the soils from Enewetak showed evidence of PCBs (22-392 ng g⁻¹ dw). Most of the Bikini lagoon sediment samples contained PCBs, and the highest was the one collected from around the Saratoga, an aircraft carrier (1555 ng g⁻¹ dw). Some of the fish samples, most of the soil samples, and only one of the sediment samples contained 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and PCBs. In addition to PCBs, the soils from Enewetak Atoll contained PCTs. PCTs were not detected in the sediment samples from Bikini Atoll. The results suggest local pollution sources of PCBs, PCTs, and OCPs.     

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.     

Simultaneous determination of acidic pesticides in vegetables and fruits by liquid chromatography—tandem mass spectrometry

A sensitive and efficient method has been developed for the simultaneous determination of 73 multi-class acidic pesticides, such as phenoxy acid and sulfonylurea herbicides, in vegetables and fruits. The sample preparation procedure was carefully optimized for the efficient removal of co-extracted matrix components. The method involves extraction of acidic pesticides with acetonitrile containing hydrochloric acid, removal of water from crude extract by salting out, and sequential cleanup by octadecylsilyl silica gel and silica gel columns. For samples containing high amounts of pigments, such as spinach, additional cleanup using a graphitized carbon column was performed prior to liquid chromatography–mass spectrometry (LC–MS/MS) analysis. Recovery tests were performed for five times for each sample of cabbage, spinach, potato, eggplant, orange, and apple fortified at 0.01 mg kg?1. Out of the 73 tested pesticides, 70 for cabbage, 67 for spinach, 69 for potato, 67 for eggplant, 64 for orange, and 70 for apple were within the range of 70–120%, with relative standard deviations below 25%. Nitenpyram and pyrasulfotole showed low recoveries for all the samples tested, probably due to low recoveries from silica gel column. The developed method effectively removed co-extracted matrix components and was highly selective, with no interfering peaks found in the chromatograms of blank samples. The overall results indicate that the developed method is suitable for the quantitative analysis of acidic pesticide residues in vegetables and fruits.     

Sequestration of priority pollutant PAHs from sediment pore water employing semipermeable membrane devices

Semipermeable membrane devices (SPMDs) were employed to sample sediment pore water in static exposure studies under controlled laboratory conditions using (control pond and formulated) sediments fortified with 15 priority pollutant polycyclic aromatic hydrocarbons (PPPAHs). The sediment fortification level of 750 ng/g was selected on the basis of what might be detected in a sediment sample from a contaminated area. The sampling interval consisted of 0, 4, 7, 14, and 28 days for each study. The analytical methodologies, as well as the extraction and sample cleanup procedures used in the isolation, characterization, and quantitation of 15 PPPAHs at different fortification levels in SPMDs, water, and sediment were reported previously (Williamson, M.S. Thesis, University of Missouri-Columbia, USA; Williamson et al., Chemosphere (This issue--PII: S0045-6535(02)00394-6)) and used for this project. Average (mean) extraction recoveries for each PPPAH congener in each matrix are reported and discussed. No procedural blank extracts (controls) were found to contain any PPPAH residues above the method quantitation limit, therefore, no matrix interferences were detected. The focus of this publication is to demonstrate the ability to sequester environmental contaminants, specifically PPPAHs, from sediment pore water using SPMDs and two different types of fortified sediment.     

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.     

Sediment dioxin levels as the basis for risk assessment and human health criteria

Methods for assessing human health risks and establishing water quality criteria under the Clean Water Act are based on the assumption that fish accumulation of dioxin is correlated with the dissolved phase of the dioxin in the water column by a water-to-fish predictive factor called a bioconcentration factor. However, dioxin does not remain dissolved in the water column to any significant degree, but sorbs to organic matter in the water column and sediment. Under Toxic Substances Control Act regulations, dioxin's hydrophobicity is recognised, and fish dioxin levels are predicted with a solids-to-fish factor. These two different predictive methods can result in extremely variable predictions of fish contaminant levels. A methodology for establishing criteria under the Clean Water Act, which considers fish uptake of sorbed hydrophobic compounds by way of ingestion of contaminated sediment, is offered as an alternative to the methods used today.     

Measurements of selected PCBs in open urban ambient air of Madrid (Spain)

The focus of this study was to characterize the concentration levels of selected PCBs and compare them to compiled data in order to contribute to the international database. The sampling site is located in the outskirts of Madrid and can be considered an open urban area. 32 samples of air were taken from February 1998 to June 1998 by using a high volume air sampler. Glass fiber filters and polyurethane foam (PUF) were used to collect the paniculate and gas phase material, respectively. PUF plugs were Soxhlet extracted and filters were ultrasonically extracted by using pesticide-grade hexane and dichloromethane, respectively. The cleanup procedure was carried out on a florisil column with hexane and hexane/dichloromethane as elution solvents. GC/MS in a selected ion monitoring mode was used for quantification and 29 selected PCBs congeners were analyzed.