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.     

Extraction and clean-up methods for organochlorine pesticides determination in milk

Organochlorine pesticides (OCPs) can cause environmental damage and human health risks since they are lipophilic compounds with high resistance to degradation and long half-lives in humans. As most persistent OCPs have been banned years ago, it is expected to find these compounds at trace levels in environment. Therefore, increasingly sensitive and reliable analytical techniques are required to ensure effective monitoring of these compounds. The aim of this review is to discuss extraction and clean-up methods used to monitor OCP residues in milk, reported in the last 20 years. To carry out this review, an exhaustive bibliographic review was conducted. Despite the disadvantages of conventional extraction and clean-up methods, such as liquid–liquid, solid-phase or Soxhlet extractions, these procedures are still used due to their reliability. New extraction methods, like solid-phase microextraction, matrix solid-phase dispersion or QuEChERS, have not been thoroughly evaluated for OCP determination in milk. Almost all the methodologies analyzed in this review presented good performance characteristics according to the performance acceptability criteria set in SANCO’s procedure. Comparison between limits of quantification (LOQ) and detection (LOD), for the reported methodologies, is not always possible due to the heterogeneity of the units. Thus, researchers should take into account an homogenization of LOD and LOQ units, according to the international regulations and MRLs established. Finally, more research is necessary to obtain the ideal methodology for OCPs determination in milk, which comprises the environmentally friendly characteristics of the new techniques and the reliability of the traditional methodologies.     

Sequestration of organochlorine pesticides in soils of distinct organic carbon content

In the present study, five soil samples with organic carbon contents ranging from 0.23% to 7.1% and aged with technical dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH) for 15 months were incubated in a sealed chamber to investigate the dynamic changes of the OCP residues. The residues in the soils decreased over the incubation period and finally reached a plateau. Regression analysis showed that degradable fractions of OCPs were negatively correlated with soil organic carbon (SOC) except for α-HCH, while no correlation was found between degradation rate and SOC, which demonstrated that SOC content determines the OCP sequestration fraction in soil. Analysis of the ratio of DDT and its primary metabolites showed that, since it depends on differential sequestration among them, magnitude of (p,p′-DDE + p,p′-DDD)/p,p′-DDT is not a reliable criterion for the identification of new DDT sources.     

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.     

Concentrations of organochlorine pesticides and 2,4,6-trichloroanisole in cork bark

Organochlorine pesticides are persistent lipophilic organic pollutants and tend to accumulate in growing plants. During growth, cork is in contact with the open air for long periods (9-12 years). Owing to the previous widespread use of organochlorine pesticides and their high persistence in the environment, there is a risk that residues of such pesticides may be present in cork.In this study, the concentrations of 14 organochlorine pesticides—all of which are indicators of environmental pollution—were analyzed in cork bark samples from three regions in Spain and one in Portugal. In addition, the concentrations of 2,4,6-trichlorophenol (TCP) and 2,4,6-trichloroanisole (TCA) were also analyzed.Our results show only very low concentrations of lindane, γ-HCH (<2.6 ng g⁻¹) and its byproducts α-HCH (<3.5 ng g⁻¹) and β-HCH (<0.6 ng g⁻¹).Among the DDT and its metabolites, only two were found: p,p′-DDT was found in a cork sample from Extremadura (0.1 ng g⁻¹) and p,p′-DDE was present at a maximum concentration of 2.9 ng g⁻¹ in a cork sample from Castile-La Mancha. However, all concentrations were well below the legal limit established by Regulation (EC) No. 396/2005 (10 ng g⁻¹ in foodstuffs). We can conclude, therefore, that the cork samples we studied complied with food safety standards.     

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.     

Thirty year monitoring of PCBs, organochlorine pesticides and tetrabromodiphenylether in eel from The Netherlands

Because of their excellent properties as a biomonitor, yellow eels (Anguilla anguilla) have been used for time-trend monitoring of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and tetrabrominated diphenylether (tetra-BDE). The program has now lasted for thirty years and has delivered valuable information on trends and spatial differences of these compounds in the delta of the rivers Rhine and Meuse and other Dutch canals, rivers and lakes. Specific local PCB, HCH and dieldrin contaminations were identified. Temporal trends show a slow decrease of PCB concentrations since 1977. Eels from the rivers Rhine and Meuse still exceed present European maximum residue limits for dioxin-like PCBs. Apart from some exceptions, OCP and tetra-BDE concentrations have also decreased, and more than those of PCBs. Fat contents of eel have decreased from an average of 21 to ca. 13%. This decrease in fat contents, coincides with the strong reduction of the European eel stock.     

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.     

Long-term air monitoring of organochlorine pesticides using Semi Permeable Membrane Devices (SPMDs) in the Alps

Atmospheric sampling of organochlorine pesticides (OCPs) was conducted using Semi Permeable Membrane Devices (SPMDs) deployed in the Alps at different altitudinal transects for two consecutive exposure periods of half a year and a third simultaneous year-long period. Along all the altitude profiles, the sequestered amounts of OCPs increased in general with altitude. SPMDs were still working as kinetic samplers after half a year for the majority of the OCPs. However, compounds with the lowest octanol-air partition coefficient (K_oa), reached equilibrium within six months. This change in the SPMD uptake was determined for the temperature gradient along the altitude profile influencing K_oa, OCPs availability in the gaseous phase, and SPMD performance. In sum, it seems two effects are working in parallel along the altitude profiles: the change in SPMD performance and the different availability of OCPs along the altitudinal transects determined by their compound properties and concentrations in air.     

Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean

The purpose of this study was to develop an analytical method for the determination of organophosphorus and pyrethroid pesticides in soybean by pressurized liquid extraction (PLE). Two organic solvents, acetone and acetonitrile, were evaluated as extraction solvents. In both cases, the amount of extract was enhanced with increasing extraction temperature. The extracts obtained using acetonitrile were measured by gas chromatography/mass spectrometry after a cleanup process based on the analytical method for the Japanese Positive List System for Agricultural Chemicals Remaining in Foods. The effect of extraction temperature (range: 40– 130°C) on extraction efficiency was evaluated by a recovery study using 21 organophosphorus pesticides and 10 pyrethroid pesticides as target analytes and acetonitrile as the solvent. The results indicated that at 130°C, some organophosphorus pesticides might be degraded, whereas extraction temperatures between 70°C and 100°C were optimal. Next, a prepared sample containing fenitrothion and permethrin was analyzed. Although the sample was not soaked in water prior to analysis, PLE provided analytical results comparable to those obtained by solvent extraction with homogenization. Therefore, PLE is considered a simple and alternative technique for the extraction of organophosphorus and pyrethroid pesticides in soybean.     

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.     

Simultaneous determination of organochlorine pesticides and bisphenol A in edible marine biota by GC-MS

A study to assess the level of organochlorine pesticides (OCPs) and bisphenol A (BPA) in edible marine biota collected from coastal waters of Malaysia was conducted using GC-MS and SPE extraction. An analytical method was developed and validated to measure the level of 15 OCPs and BPA simultaneously from five selected marine species. It was observed that some samples had low levels of p,p′-DDE, p,p′-DDT and p,p′- DDD ranging from 0.50 ng g⁻¹ to 22.49 ng g⁻¹ dry weight (d.w) but significantly elevated level of endosulfan I was detected in a stingray sample at 2880 ng g⁻¹ d.w. BPA was detected in 31 out of 57 samples with concentration ranging from below quantification level (LOQ: 3 ng g⁻¹) to 729 ng g⁻¹ d.w. The presence of OCPs is most likely from past use although there is also indication of illegal use in recent times. The study also reveals that BPA is more widely distributed in coastal species caught off the coast of the most developed state. The potential health risk from dietary intakes of OCPs and BPA from the analysed fish species was negligible.     

Assessment of daily intake of organochlorine pesticides from milk in different regions of Poland

The common occurrence of organochlorine compounds in the environment, food and human tissues may constitute a serious threat to human health. The method of gas chromatography-mass spectroscopy was used to determine the content of pesticides in 15 samples of raw cow's milk from different regions of Poland. The results revealed high levels of p,p′-DDE, p,p′-DDT, heptachlor and aldrin. The studied milk contained lindane in average concentrations within the maximum limits. Although in 20% of all samples tested, the concentration of lindane exceeded permissible limits, while in 15% of samples the content of Σ DDT was too high. But the average daily consumption of milk containing organochlorine pesticides poses no direct threat to human health, because daily intake (DI) for all compounds were below the acceptable daily intake (ADI). Attention should be paid to the exposure of consumers to pesticide residues from other dairy foods.     

National survey of the levels of persistent organochlorine pesticides in the breast milk of mothers in China

The occurrence of persistent organochlorine pesticides (OCPs) in breast milk samples collected from mothers from twelve provinces in mainland China was investigated. Dichlorodiphenyltrichloroethanes (DDTs) were the most prevalent agent, followed by HCHs and HCB, whereas levels of chlordane compounds, drins and mirex were lower. The relatively lower DDE/DDT ratio in the Fujian rural area suggested more recent exposure to DDT than in other areas. The mean level of DDTs in breast milk from the southern China was higher than those from northern China (p < 0.05). A positive correlation was observed between concentration of DDTs in human milk and consumption of animal-origin food, suggesting that this parameter could play an important part in influencing OCPs burdens in lactating women. The mean estimated daily intakes of different OCPs for breastfed infants were lower than the tolerable daily intake.     

Concentrations and distributions of 18 organochlorine pesticides listed in the Stockholm Convention in surface sediments from the Liaohe River basin,China

Organochlorine pesticides (OCPs) were analyzed in 26 surface sediment samples from the Liaohe River basin, and the distributions of and potential environmental risks posed by OCPs in the basin were evaluated. Eighteen OCPs listed in the Stockholm Convention were determined using isotope-dilution gas chromatography–high resolution mass spectrometry. This is the first study of hexachlorobenzene (HCB) in the Liaohe River basin sediments. The total OCP concentrations were 0.39–68.06 ng g^?1 dry weight. The total α-, β-, γ-, and δ-hexachlorocyclohexane (HCH), the total dichlorodiphenyltrichloroethane (DDT – p,p′-dichlorodiphenyldichloroethane (DDD), p,p′-dichlorodiphenyldichloroethylene (DDE), o,p^'-DDT, and p,p′-DDT), and the HCB concentrations in the sediment samples were 0.1–28.48 ng g^?1 (mean 4.01 ng g^?1), 0.08–6.52 ng g^?1 (mean 3.07 ng g^?1), and 0.18–24.8 ng g^?1 (mean 4.38 ng g^?1), respectively. The HCB concentrations were higher than the concentrations of the other OCPs, and the HCHs and HCB together were the dominant OCPs. β-HCH was the most abundant HCH isomer. The concentrations of DDTs and other OCPs were relatively low, and the (DDE+DDD)/DDT ratios (>0.5) and DDD/DDE ratios (<1) indicated that no recent DDT inputs had occurred in the Liaohe River system. The main sources of HCHs were probably the historical production and agricultural use of HCH in the study area. The DDT and HCH concentrations were generally below or similar to the concentrations that have been found in other parts of the world. An ecotoxicological evaluation indicated that HCHs in surface sediments pose slight risks to human and ecological health in the Liaohe River basin.     

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).     

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.     

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.     

Organochlorine pesticides in the ambient air of Chiapas, Mexico

Organochlorine (OC) pesticides were measured in the ambient air of Chiapas, Mexico during 2000-2001. Concentrations of some OC pesticides (DDTs, chlordanes, toxaphene) were elevated compared with levels in the Great Lakes region, while those of other pesticides were not (hexachlorocyclohexanes, dieldrin). While this suggests southern Mexico as a source region for the former group of chemicals, comparably high levels have also been reported in parts of the southern United States, where their suspected sources are soil emissions (DDTs, toxaphene) and termiticide usage (chlordane). Ratios of p,p'-DDT/p,p'-DDE and trans-chlordane/cis-chlordane/trans-nonachlor (TC/CC/TN) in Chiapas suggest a mixture of fresh and weathered sources, while congener profiles of toxaphene suggest emission of old residues from soils. This is supported by air parcel back trajectory analysis, which indicated that air masses over Chiapas at the time of sampling had previously passed over areas of continuing or recent use of some OC pesticides as well as areas of past use.     

Residue levels of organochlorine pesticides in cattle meat and organs slaughtered in selected towns in West Shoa Zone,Ethiopia

Residue levels of organochlorine pesticides (OCP) in a total of 90 cattle samples comprising meat, liver and kidney collected from carcasses slaughtered in six towns in West Shoa Zone, Ethiopia, (Ambo, Guder, Ginchi, Gedo, Holeta and Tikur Inchini), have been determined. The pesticides were extracted by solid phase extraction (SPE) and quantification was carried out using gas chromatography-mass spectrometry (GC-MS). A good linearity (r² > 0.998) was found in the range 0.001–7.00 mg/kg for the samples studied. Most of the pesticides had recoveries in the range 81–99% and values of relative standard deviation (RSD) <7.2% for repeatability and reproducibility, showing good accuracy and precision of the method. The concentration level of the studied organochlorines followed the order: p, p’ dichloro-diphenyl-trichloroethane (DDT) > endosulfan>o,p′-DDT >lindane>dieldrin>endrin>aldrin>chlorothanolin while the order of contamination in the analyzed organs was liver > kidney > meat. Heat treatment of the meat, kidney and liver samples (boiling for 90 min.) produced an overall reduction of 62.2%, 44.5%, 37.7%, 29%, 31%, 34.3% and 30.8% in lindane, o, p′-DDT, endosulfan, p, p′-DDT, chlorothanolin, aldrin, dieldrin, and endrin, respectively. Although the residual contents of the organochlorines detected in all the contaminated samples analyzed from the six cities were below the respective maximal permissible levels set by international organizations, samples from Holeta town were more contaminated and may necessitate effective monitoring as bioaccumulation of these residues may pose health problems in human beings.