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.     

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 alpha -, beta -, gamma -, and delta -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.     

Formation of organochlorine by-products in bleached laundry

Laundering fabrics with chlorine bleach plays a role in health and hygiene as well as aesthetics. However, laundry bleaching may create chlorinated by-products with potentially adverse human health effects. Studies have shown that toxic chlorinated gases are produced in the headspace of washing machines when hypochlorite-containing bleach is used. Laundry bleaching has also been implicated in contributing dissolved organochlorine to municipal wastewater. However, there have been no reports of organochlorines produced and retained in fabric as a result of laundry bleaching. We have used a chlorine-specific X-ray spectroscopic analysis to demonstrate the formation of organochlorine by-products in cotton fabrics laundered with chlorine bleach under typical household conditions. Organochlorine formation increases at higher wash temperature. At least two pools of organochlorine are produced in bleached fabric: a labile fraction that diminishes over several months of storage time as well as a more stable fraction that persists after more than 1 year. Our results also suggest that residual hypochlorite remains in fabric after laundering with bleach, presenting the possibility of direct and sustained dermal contact with reactive chlorine. This study provides a first step toward identifying a new risk factor for elevated organochlorine body burdens in humans.     

Analysis of organophosphorus pesticides in whole milk by solid phase microextraction gas chromatography method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-microm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30 degrees C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 microgL-1 to 1.75 microgL-1 for coumaphos and 0.69 microgL-1 to 6.90 microgL-1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 microgL-1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 microgL-1 for dichlorvos and 0.066 microgL-1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

(汍)汊湖水体和表层沉积物中有机氯农药分布特征

用GC/ECD内标法定量测定了(汍)汉湖水体和表层沉积物中的有机氯农药(OCPs).(汍)汊湖水样和表层沉积物中20种OCPs均有检出.表层沉积物上层中(0～2 cm)的OCPs明显高于下层(2～10 cm),这是(汍)汉湖具有稳定的水动力条件所致.氯丹在表层沉积物中浓度最高,与该化合物在环境中的强稳定性以及在该地区的大量使用有关.表层沉积物样品DCHsO2上层OCPs中o,p'-DDT主要成分,表明近期可能有新的DDTs,特别是含大量o,p'-DDT的三氯杀螨醇的使用.DDD/DDE则显示表层沉积物上层DDTs的降解主要处在厌氧条件下,而下层处在好氧条件下.     

Evaluation of chloroform/methanol and dichloromethane/hexane extractable lipids as surrogate measures of sample partition capacity for organochlorines in fish tissues

Organic contaminant concentration data are often lipid normalized to provide an indication of the chemical fugacity in the sample or to compare the relative equilibrium status of samples from the same environment. This study compared lipid normalized PCB and organochlorine concentration data for tissues of individual fish when lipids were measured using chloroform/methanol (CM) or dichloromethane/hexane (DH) extractions. The CM extraction produced higher lipid yields for dorsal muscle (8-fold difference) and carcass (1.7-fold difference) compared to DH extractions, while both methods yielded comparable lipid contents for liver and adipose tissue. Lipid normalized tissue/carcass PCB and organochlorine concentration ratios were variable across tissue types when lipid contents from the CM technique were used, whereas, tissue/carcass concentration ratios approached the expected value of unity for each tissue when DH-derived lipids were used. These data suggest that the tissue lipid content as derived using the DH extraction provided a better surrogate measure of sample partition capacity than tissue lipids determined using the CM technique.     

The use of potassium dichromate and ethyl alcohol as blood preservatives for analysis of organochlorine contaminants

The "gold standard" for preserving and shipping of human tissue samples for analysis of organochlorine contaminants is freezing. This method can be difficult, costly if using heavy dry ice for shipping, and often unfeasible, especially in less developed countries where electricity and dry ice are frequently rare or absent. Therefore, it is essential that more convenient and practical methods for preservation of blood samples are found. As an alternative to freezing, there have been studies employing potassium dichromate as a preservative for human or cow's milk or ethyl alcohol preservation of blood for dioxin analysis. In this study, four methods were compared to investigate the effectiveness of ethyl alcohol and potassium dichromate as blood preservatives for analysis of dioxins, dibenzofuran, and polychlorinated biphenyl (PCB) congeners. Samples of whole blood from a Dallas, Texas hospital were collected and pooled. Freezing, ethyl alcohol in two concentrations (20% and 40% per volume of sample), and potassium dichromate were used for blood preservation. The blood samples containing potassium dichromate or ethyl alcohol were stored and sent to ERGO laboratory for dioxin analysis and comparison with results from the frozen sample, which was kept frozen at all times until analyzed. This study suggests that potassium dichromate is a suitable alternative to freezing for preservation of whole blood for dioxin, dibenzofuran, and PCB measurements when either lipid or wet weight based results are reported. Potassium dichromate tablets were very easy and convenient to use--two 100 mg tablets (with a dichromate content of about 33 mg each) were added to each bottle containing 65 ml of blood. However, ethyl alcohol at 20% and 40% concentration under the conditions of this pilot study and the analytical method employed did not appear to provide satisfactory preservation when lipid based results are given or when the fat content has to be determined (wet or whole weight). Further research with a larger number of samples, inclusion also of other groups of persistent organic pollutants such as organochlorine pesticides or brominated flame retardants, a longer duration of storage time, and at temperatures greater than US or German room temperature is indicated in order to recommend the routine use of potassium dichromate as preservative for whole blood intended for dioxin, dibenzofuran, and PCB analysis.     

Method for the determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum based on a gel permeation chromatographic clean-up

A gel permeation chromatographic (GPC) clean-up based method was developed for determination of selected organochlorine pesticides and polychlorinated biphenyls in human serum. The method permits automation of the sample extract clean-up stage and is designed to work with small amounts of sample. Different working variables were studied in its development, including injection volume, flow rate, and fat amount as the most representative coextract. The method provides solvent and time savings. Initial extraction was performed using 96-well solid-phase disk extraction plates, and quantification was performed by gas chromatography with electron capture detection and mass spectrometry. Recoveries of PCB congeners 28, 52, 101, 118, 138, 153, and 180 and organochlorine pesticides HCB, β-HCH, γ-HCH, heptachlor epoxide, p,p′-DDE, and p,p′-DDT at two spiking levels ranged from 55% to 115% with relative standard deviations ranging from 2.0% to 14.6%. Limits of quantification ranged from 0.06 to 0.16 ng mL⁻¹ for PCBs and from 0.12 to 0.36 ng mL⁻¹ for organochlorine pesticides. Finally, the method was applied to the analysis of 38 serum samples and the results were compared with those of another procedure validated at the laboratory.     

Development,validation and application of a method to analyze phenols in water samples by solid phase micro extraction-gas chromatography-flame ionization detector

In this work the development, validation and application of method using Solid Phase Microexctration (SPME) for the analyses of five pollutants (phenol, 2-nitrophenol, 2,4-dimethylphenol, 2,4-dichlorophenol and 4-chloro, 3-methyl phenol) in supplying water, using gas chromatography (GC) with flame ionization detector (FID) is described. The optimal conditions obtained for SPME were: fiber type: Poliacrylate (PA); extraction time: 40 minutes; extraction temperature: 70°C; amount of salt added to sample (NaCl): 15%; desorption temperature: 8 minutes. The parameters studied in the method validation were: limit of detection (0.3 and 3.5 μ g.L^{? 1}); precision, measured by the variation coefficient (between 2.1 and 8.8%); calibration curve and linearity, by using the external standardization method (between 1 and 50 50 μ g.L^{? 1}). After the methodology development, samples of water collected in Atibaia River (São Paulo - Brazil) were analyzed, using the optimized methodology. Three water samples collected in the rain season showed a peak with retention time close to 4-chloro, 3 methyl phenol further analyzed by Gas Chromatography-Mass Spectrometry for the identity confirmation. In spite of the fact that none target compounds were found in the river water samples analyzed, the presence of two phenols different from those investigated (p-terc butyl phenol; butylated hydroxytoluene) were detected. These results together with the results of the limit of detection (that showed to be lower than the maximum concentration of phenols demanded by different environment control agencies), and the results of the validation, indicate the applicability of this method for the analysis of selected phenols in river water samples.     

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.     

Development, validation and application of a method to analyze phenols in water samples by solid phase micro extraction-gas chromatography-flame ionization detector

In this work the development, validation and application of method using Solid Phase Microexctration (SPME) for the analyses of five pollutants (phenol, 2-nitrophenol, 2,4-dimethylphenol, 2,4-dichlorophenol and 4-chloro, 3-methyl phenol) in supplying water, using gas chromatography (GC) with flame ionization detector (FID) is described. The optimal conditions obtained for SPME were: fiber type: Poliacrylate (PA); extraction time: 40 minutes; extraction temperature: 70 degrees C; amount of salt added to sample (NaCl): 15%; desorption temperature: 8 minutes. The parameters studied in the method validation were: limit of detection (0.3 and 3.5 microg.L(- 1)); precision, measured by the variation coefficient (between 2.1 and 8.8%); calibration curve and linearity, by using the external standardization method (between 1 and 50 50 microg.L(- 1)). After the methodology development, samples of water collected in Atibaia River (S?o Paulo - Brazil) were analyzed, using the optimized methodology. Three water samples collected in the rain season showed a peak with retention time close to 4-chloro, 3 methyl phenol further analyzed by Gas Chromatography-Mass Spectrometry for the identity confirmation. In spite of the fact that none target compounds were found in the river water samples analyzed, the presence of two phenols different from those investigated (p-terc butyl phenol; butylated hydroxytoluene) were detected. These results together with the results of the limit of detection (that showed to be lower than the maximum concentration of phenols demanded by different environment control agencies), and the results of the validation, indicate the applicability of this method for the analysis of selected phenols in river water samples.     

Methodological aspects of a national population-based study of persistent organochlorine compounds in serum

Key methodological aspects are presented for a study of concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and organochlorine pesticides in the serum of a sample of the New Zealand population aged 15 years and older. The study took advantage of the sampling frame and sample collection and interview processes of the National Nutrition Study (NNS). An additional blood sample for this organochlorines study was collected by the NNS and questions added to the NNS questionnaire. Serum was obtained from the blood and, based on responses to questions in the questionnaire, samples with possible occupational exposure to organochlorines were excluded. Remaining samples providing at least 2 ml of serum were pooled within 80 strata defined according to geographic area, age group, sex and ethnicity. A minimum number of five individual serum samples was required for pooling within a stratum. Within strata with sufficient samples, two or three pooled samples were created for variance calculation. Eligible for inclusion in the study were 2497 individual serum samples. Sixty strata had sufficient serum samples for pooling and chemical analysis. This was the first study of organochlorine compounds with a national population-based sample. Two factors that made the study feasible deserve emphasis. First, being able to "piggy-back" on another study. Second, pooling of samples to reduce analytic expenses. It is hoped that the methods used in this study will form the basis for other studies investigating organochlorine concentrations in national populations.     

Gas chromatographic analysis of organic marker compounds in fine particulate matter using solid-phase microextraction

A gas chromatographic method that uses solid-phase microextraction for analysis of organic marker compounds in fine particulate matter (PM2.5) is reported. The target marker compounds were selected for specificity toward emission from wood smoke, diesel or gasoline combustion, or meat cooking. Temperature-programmed volatilization analysis was used to characterize the thermal stabilities and volatile properties of the compounds of interest. The compounds were thermally evaporated from a quartz filter, sorbed to a solid phase microextraction (SPME) fiber, and thermally desorbed at 280 degrees C in a gas chromatograph injection port connected via a DB 1701 capillary separating column. Various experimental parameters (fiber type, time, and temperature of sorption) were optimized. It was found that high extraction yield could be achieved using a polyacrylate fiber for polar substances, such as levoglucosan, and a 7-microm polydimethylsiloxane (PDMS)-coated fiber for nonpolar compounds, such as hopanes and polyaromatic hydrocarbon. A compromise was made by selecting a carboxen/PDMS fiber, which can simultaneously extract all of the analytes of interest with moderate-to-high efficiency at 180 degrees C within a 30-min accumulation period. The optimized method was applied to the determination of levoglucosan in pine wood combustion emissions. The simplicity, rapidity, and selectivity of sample collection with a polymer-coated SPME coupled to capillary gas chromatography (GC) made this method potentially useful for atmospheric chemistry studies.     

Analysis of Organophosphorus Pesticides in Whole Milk by Solid Phase Microextraction Gas Chromatography Method

Solid phase microextraction (SPME) was used for the extraction of residual coumaphos and dichlorvos in whole milk. The residues were analyzed by capillary gas chromatography equipped with nitrogen phosphorus detector (GC-NPD). A manual SPME holder with a 100-μm polyacrylate fiber was used. The optimized conditions for extraction by SPME method were: sample agitation, absorption temperature of 30°C, absorption time of 40 min, desorption time of 10 min, and sample volume was 16.0 mL in the vial. Under these conditions, the calibration graphs were linear in the range of 0.17 μgL^?1 to 1.75 μgL^?1 for coumaphos and 0.69 μgL^?1 to 6.90 μgL^?1 for dichlorvos. Precision was good with RSD values of 13% for coumaphos and 14% for dichlorvos. The detection limits (LOD) were 0.060 μgL^?1 for dichlorvos and 0.052 for coumaphos. The quantification limits (LOQ) were 0.086 μgL^?1 for dichlorvos and 0.066 μgL^?1 for coumaphos. The results obtained in this study suggest that SPME is a suitable technique for residual pesticide analysis of milk. The data demonstrate that particular OP pesticides used in dairy farming in the region of Minas Gerais were found to contaminate cow whole milk, and the residues are not removed by treating the milk by boiling.     

Comparison of organochlorine compound concentrations in colostrum and mature milk

Human breast milk represents the best choice for the nutrition of infants. It is often used for monitoring human exposures to environmental chemicals. Uniquely suited to meet human biological needs, breast milk composition, especially fat content, changes significantly with time from delivery. With the aim to compare the concentration of organochlorine compounds (OCs) in colostrum versus mature milk, we obtained samples of fourth-fifth day postpartum milk (colostrum) and day-14 postpartum milk (mature milk) from 12 women enrolled in the project "Early Childhood Development and PCB Exposure in Slovakia". The concentrations of selected organochlorine pesticides and congeners of polychlorinated biphenyls (PCBs) were measured using gas chromatography with electron capture detection and reported on lipid adjusted basis. No significant differences were found between organochlorine levels in colostrum and those in mature milk samples. A very close correlation was found between the concentrations of organochlorine compounds in colostrum and mature milk (Spearman correlation coefficient r=0.94-0.98 for PCBs, and r=0.85-0.99 for organochlorine pesticides, p<0.001 for all compounds). The present study concludes that the use of colostrum samples provides a close estimate of the child's exposure to OCs in the early neonatal period and demonstrates that, despite the lower fat content, colostrum specimens are adequate to conduct OC analyses.     

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.     

Concentration of organochlorine pesticides in wine corks

Wine corks were extracted and analyzed for 23 organochlorine pesticides, including alpha-, beta-, and gamma-hexachlorocyclohexanes (HCH), hexachlorobenzene, DDT, DDE and DDD, chlordane, endosulfan, dieldrin, aldrin, and endrin. This was done to investigate the occurrence, concentrations, composition profiles, and possible sources of organochlorine contamination. All groups of compounds were detected in every sample investigated, with the exception of aldrin and endrin. The total concentrations of organochlorine compounds in all samples ranged from 75-120 ng/g lipid, and for most compounds, the concentrations of organochlorines in cork were consistent with published data for other plant tissues. Differences in the relative abundances of the various classes of organochlorine pesticides were substantial and were probably due to differences in the pesticide usage practices of the various regions in which the cork producing trees were grown.     

Calibration of the Chemcatcher passive sampler for the monitoring of priority organic pollutants in water

An integrative passive sampler consisting of a C18 Empore disk receiving phase saturated with n-octanol and fitted with low-density polyethylene diffusion membrane was calibrated for the measurement of time-weighted average concentrations of hydrophobic micropollutants, including polyaromatic hydrocarbons and organochlorine pesticides, in water. The effect of temperature and water turbulence on kinetic and thermodynamic parameters characterising the exchange of analytes between the sampler and water was studied in a flow-through system under controlled conditions. It was found that the absorption of test analytes from water to the sampler is related to their desorption to water. This allows for the in situ calibration of the uptake of pollutants using offload kinetics of performance reference compounds. The sampling kinetics are dependent on temperature, and for most of the tested analytes also on the flow velocity. Sampler-water partition coefficients did not significantly change with temperature.     

Simultaneous determination of organochlorine and pyrethriod pesticide residues in the Chinese patent medicines by gas chromatography-tandem mass spectrometry

A simple, sensitive, reliable method was developed for the simultaneous determination of organochlorine and pyrethriod pesticide residues in Chinese patent medicines Six ingredient rehmannia pills and Xiaoyao pills. These pesticides were extracted by ethyl acetate. The extraction time and volume of ethyl acetate were optimized. Cleanup of extracts was performed with dispersive-solid phase extraction using graphitized carbon black as the sorbent. The determination of pesticides in the final extracts was carried out by gas chromatography–tandem mass spectrometry in multiple reaction monitoring mode (GC-MS/MS, MRM). The linearity of the calibration curves is good in matrix-matched standard and yields the coefficients of determination (R²) ≥0.99 for all of the target analytes. Under optimized conditions, the average recoveries (five replicates) for most pesticides range from 75.5% to 114.6%, and RSDs are less than 10.0%. The LODs of 18 pesticides in Six ingredient rehmannia pill and Xiaoyao pills are in the range of 0.01–8.82 μg kg^?1. The developed method meets the requirements of pesticide residue analysis and could be effectively used for routine analysis of the organochlorine and pyrethriod pesticide residues in Six ingredient rehmannia pills and Xiaoyao pills.     

A High Volume Stack Sampler

This paper deals with the development design, and trial application of a sampling train to gather a relatively large amount of particulate sample in a short period of time. With air pollution sources installing control equipment to reduce emissions to the required low levels, it becomes necessary to use a sampling device which can collect a representative sample in a reasonable period of time. Some of the sampling trains currently being specified are expensive, awkward, and nearly impossible to use under field conditions. The high-volume train overcomes ail of these shortcomings and has some additional advantages. It uses the same glass fiber filter that is specified for ambient air particulate sampling so the emission test results are directly comparable to ambient air sampling data. The laboratories currently weighing and analyzing the glass filters need no additional equipment for the emission sampling analysis. The sample collected by the high-volume probe may be analyzed microscopically for size and characteristics of the particles. This is very important if control equipment is to be specified for the process or source. The high-volume sampler was evaluated on field tests of wood fired boilers, incinerators, wigwam burners, asphalt batching plants, seed cleaning plants, and wood fiber filtration systems. The results of several typical tests using the sampler on these sources are included in the paper.