Rapid determination of dichlorodiphenyltrichloroethane and its main metabolites in aqueous samples by one-step microwave-assisted headspace controlled-temperature liquid-phase microextraction and gas chromatography with electron capture detection

A rapid and sensitive analytical method for the determination of dichlorodiphenyltrichloroethane (DDT) and its main metabolites in environmental aqueous samples has been developed using one-step microwave-assisted headspace controlled-temperature liquid-phase micro-extraction (MA-HS-CT-LPME) technique coupled with gas chromatography-electron-capture detection (GC-ECD). In this study, the one-step extraction of DDT and its main metabolites was achieved by using microwave heating to accelerate the evaporation of analytes into the controlled-temperature headspace to form a cloudy mist vapor zone for LPME sampling. Parameters influencing extraction efficiency were thoroughly optimized, and the best extraction for DDT and its main metabolites from 10-mL aqueous sample at pH 6.0 was achieved by using 1-octanol (4-μL) as the LPME solvent, sampling at 34 °C for 6.5 min under 249 W of microwave irradiation. Under optimum conditions, excellent linear relationship was obtained in the range of 0.05-1.0 μg/L for 1-dichloro-2,2-bis-(p′-chlorophenyl)ethylene (p,p′-DDE), 0.1-2.0 μg/L for o,p′-DDT, 0.15-3.0 μg/L for 1,1-dichloro-2,2-bis-(p′-chlorophenyl)ethane (p,p′-DDD) and p,p′-DDT, with detection limits of 20 ng/L for p,p′-DDE, and 30 ng/L for o,p′-DDT, p,p′-DDD and p,p′-DDT. Precision was in the range of 3.2-11.3% RSD. The proposed method was validated with environmental water samples. The spiked recovery was between 95.5% and 101.3% for agricultural-field water, between 94% and 99.7% for sea water and between 93.5% and 98% for river water. Thus the established method has been proved to be a simple, rapid, sensitive, inexpensive and eco-friendly procedure for the determination of DDT and its main metabolites in environmental water samples.     

Cytogenetic status of human lymphocytes after exposure to low concentrations of p,p'-DDT, and its metabolites (p,p'-DDE, and p,p'-DDD) in vitro

Despite that the use of DDT has been restricted for more than 40 years to malaria affected areas, low doses of this pesticide and its metabolites DDE and DDD can be found in the environment around the world. Although it has been shown that these pollutants induce cell and DNA damage, the mechanisms of their cytogenotoxic activity remains largely unknown. This study looks into their possible genotoxic effects, at doses that can be found in body fluids, on human lymphocytes using the cytokinesis-block micronucleus assay and the comet assay. After exposure for 1, 6, and 24 h compounds p,p′-DDT (0.1 μg mL⁻¹), p,p′-DDE (4.1 μg mL⁻¹), and p,p′-DDD (3.9 μg mL⁻¹) showed increase in DNA damage. The most significant results were observed at exposure period of 24 h where number of micronucleated cells increased from control 2.5 ± 0.71 to 23.5 ± 3.54, 13.5 ± 0.71, and 16.5 ± 6.36 for DDT, DDE, and DDD, respectively. Similar effect was observed using comet test where the percentage of DNA in comets tail increased from control 1.81 ± 0.16 to 17.24 ± 0.55, 11.21 ± 0.56 and 9.28 ± 0.50 for each compound, respectively. At the same time Fpg-comet assay failed to report induction of oxidative DNA damage of these pollutants. Additionally, the type of cell death was determined using diffusion assay and necrosis dominated. Our findings suggest that even at low concentrations, these pesticides could induce cytogenetic damage to human peripheral blood lymphocytes and in that manner have the impact on human health as well.     

New DDT inputs after 30 years of prohibition in Spain. A case study in agricultural soils from south-western Spain

This study provides information on the current status of contamination by DDT in agricultural soils in south-western Spain. A recent use of technical DDT in at least 17% of the soils was found based on the values (<1) of the ratio Rp,p^′/p,p^′=[p,p^′-DDE+p,p^′-DDD]/[p,p^′-DDT]. According to the ratio Ro,p^′/p,p^′=[o,p^′-DDT]/[p,p^′-DDT], a dicofol type contamination was detected in about 27% of the soils. A wide range of concentrations was observed (0.08-11.1 ng/g d.w.) regardless of the type of crop soil. Enantiomeric fractions (EFs), based on the chiral analysis of o,p′-DDT residues differed from the racemic value (0.500) in most soils but they were not correlated with the study variables [DDTs], SOM, Rp,p^′/p,p^′ and Ro,p^′/p,p^′. Given the health risks posed by DDT, our findings support how the environmental control of legacy pollutants such as DDT cannot be neglected.     

Placental transfer of DDT in mother-infant pairs from Northern Thailand

The present study objective was to investigate ratios and correlation coefficients between dichlorodiphenyltrichloroethane (DDT) compounds in cord and maternal sera of mother-infant pairs from northern Thailand. The study site was located in Chiang Dao District of Chiang Mai Province which was an agricultural and former malaria endemic area. DDT compounds were analyzed in 88 cord and maternal serum samples using gas chromatography-electron capture detection (GC-ECD). p,p′-DDE (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene) was the major component and detected in every cord and maternal serum samples with geometric means of 1,255 and 1,793 n g^?1 lipids, respectively. p,p′-DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane) was detected at 89.8 and 100% of cord and maternal serum samples, respectively. The second and third highest levels detected were p,p′-DDD (1,1-dichloro-2,2-bis(p-chlorophenyl)ethane) and p,p′-DDT, respectively. The ratios between cord and maternal sera for p,p′-DDE, p,p′-DDT, and p,p′-DDD that were less than 1 had high correlation coefficients (ratio = 0.70, r = 0.82 for p,p′-DDE, ratio = 0.62, r = 0.66 for p,p′-DDT, and ratio = 0.79, r = 0.78 for p,p′-DDD). The high correlation coefficients indicate that cord serum levels of DDT compounds could be accurately estimated from maternal serum levels. It can be concluded that cord serum levels of p,p′-DDE, p,p′-DDT, and p,p′-DDD were approximately 70%, 62%, and 79% of maternal serum levels, respectively. Furthermore, our findings can be applied in public health to monitor and evaluate risk among infants from high DDT exposure area.     

Biodegradation of 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) by using Serratia marcescens NCIM 2919

A solvent tolerant bacterium Serratia marcescens NCIM 2919 has been evaluated for degradation of DDT (1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane). The bacterium was able to degrade up to 42% of initial 50 mg L^?1 of DDT within 10 days of incubation. The highlight of the work was the elucidation of DDT degradation pathway in S. marcescens. A total of four intermediates metabolites viz. 2,2-bis (chlorophenyl)-1,1-dichloroethane (DDD), 2,2-bis (chlorophenyl)-1,1-dichloroethylene (DDE), 2,2-bis (chlorophenyl)-1-chloroethylene (DDMU), and 4-chlorobenzoic acid (4-CBA) were identified by GC-Mass and FTIR. 4-CBA was found to be the stable product of DDT degradation. Metabolites preceding 4-CBA were not toxic to strain as reveled through luxuriant growth in presence of varying concentrations of exogenous DDD and DDE. However, 4-CBA was observed to inhibit the growth of bacterium. The DDT degrading efficiency of S. marcescens NCIM 2919 hence could be used in combination with 4-CBA utilizing strains either as binary culture or consortia for mineralization of DDT. Application of S. marcescens NCIM 2919 to DDT contaminated soil, showed 74.7% reduction of initial 12.0 mg kg^?1 of DDT after 18-days of treatment.     

Metabolism of DDT in Different Tissues of Young Rats

The bioconcentration and distribution pattern of p,p′-DDT 1,1,1-1trichloro-2,2-bis(2-chlorophenyl-4-chlorophenyl)-ethane] and its main metabolites (p,p′-DDD [1,1-dichloro-2,2-bis (4-chlorophenyl) ethane] and p,p′-DDE [1,1-dichloro-2,2-bis (4-chlorophenyl) in adipose tissue, liver, brain, kidney, thymus, and testis were examined in young rats after 10 days of intraperitoneal injection of 50 and 100 mg of p,p′-DDT/kg of body weight. Analyses were performed by high-resolution gas chromatography. p,p′-DDT was found to be accumulated in a dose-dependent manner with the highest concentration in adipose tissue. However, in brain, the accumulation of pesticide was low and remained unchanged at the higher dose. This difference may relate to the protective role of the blood-brain barrier, which limits the access of the xenobiotic in the cerebral compartment, and to the differential tissue lipid composition. Although tissues concentration of p,p′-DDE and p,p′-DDD correlated positively to total p,p′-DDT levels, the active role in detoxification of pollutants may explain why p,p′-DDD is more abundant in liver than in the rest of organs. On the contrary, in brain, the concentration of p,p′-DDE is higher than that of p,p′-DDD, suggesting that the metabolism of the parent insecticide proceeds via more than one pathway.     

Persistence of organochlorine chemical residues in fish from the Tombigbee River (Alabama, USA): Continuing risk to wildlife from a former DDT manufacturing facility

Organochlorine pesticide and total polychlorinated biphenyl (PCB) concentrations were measured in largemouth bass from the Tombigbee River near a former DDT manufacturing facility at McIntosh, Alabama. Evaluation of mean p,p′- and o,p′-DDT isomer concentrations and o,p′- versus p,p′-isomer proportions in McIntosh bass indicated that DDT is moving off site from the facility and into the Tombigbee River. Concentrations of p,p′-DDT isomers in McIntosh bass remained unchanged from 1974 to 2004 and were four times greater than contemporary concentrations from a national program. Total DDT in McIntosh bass exceeded dietary effect concentrations developed for bald eagle and osprey. Hexachlorobenzene, PCBs, and toxaphene concentrations in bass from McIntosh also exceeded thresholds to protect fish and piscivorous wildlife. Whereas concentrations of DDT and most other organochlorine chemicals in fish have generally declined in the U.S. since their ban, concentrations of DDT in fish from McIntosh remain elevated and represent a threat to wildlife.     

Occurrence and levels of organochlorine compounds in human breast milk in Bangladesh

In low-income countries, the use of some organochlorine pesticides is still common in order to increase food production. Monitoring the chemical exposure is an important step in risk-reducing strategies. This is the first study to report concentrations of organochlorines in breast milk of women from Bangladesh where farming is the main income source.Organochlorines such as p,p′-DDT, o,p′-DDT, p,p′-DDE, p,p′-DDD (i.e., ∑DDT), HCB, α-, β- and γ-HCH, trans-chlordane, cis-chlordane, oxy-chlordane, trans-nonachlor, cis-nonachlor, mirex and polychlorinated biphenyls (CB 28, 52, 99, 101, 105, 114, 118, 123, 128, 138, 141, 149, 153, 156, 157, 163, 167, 170, 180, 183, 187, 189, 194) were analyzed in breast milk collected in 2002 from 72 first-time mothers (median age 20 years) living in the rural area Matlab, Bangladesh.While the concentrations of PCBs and many of the pesticides were low, the concentrations of p,p′-DDT and its metabolite p,p′-DDE were high (median 349 and 1645 ng g⁻¹ lipid, respectively) in comparison to other countries. The median value of ∑DDT was 2123 ng g⁻¹ lipid. The estimated daily exposure to p,p′-DDT, p,p′-DDE and ∑DDTs was 10, 30 and 42 μg kg⁻¹ body weight, respectively, in 3 months old infants. The p,p′-DDE/p,p′-DDT ratio ranged from 1 to 23, where 58% of the mothers had a ratio below 5 indicating recent or ongoing DDT exposure.This study reports infant exposure and maternal body burden of organochlorines through breast milk. Although the findings give no reason to limit breast-feeding, it is essential to identify the main exposure sources and find means to decrease the exposure.     

Sterilization affects soil organic matter chemistry and bioaccumulation of spiked p,p′-DDE and anthracene by earthworms

Laboratory experiments were conducted to assess the effects of soil sterilization on the bioavailability of spiked p,p′-DDE and anthracene to the earthworms Eisenia fetida and Lumbricus terrestris. Physical and chemical changes to soil organic matter (SOM) induced by sterilization were also studied. Uptake of both compounds added after soil was autoclaved or gamma irradiated increased for E. fetida. Sterilization had no effect on bioaccumulation of p,p′-DDE by L. terrestris, and anthracene uptake increased only in gamma-irradiated soils. Analyses by FT-IR and DSC indicate sterilization alters SOM chemistry and may reduce pollutant sorption. Chemical changes to SOM were tentatively linked to changes in bioaccumulation, although the effects were compound and species specific. Artifacts produced by sterilization could lead to inaccurate risk assessments of contaminated sites if assumptions derived from studies carried out in sterilized soil are used. Ultimately, knowledge of SOM chemistry could aid predictions of bioaccumulation of organic pollutants.     

Influence of plant-earthworm interactions on SOM chemistry and p,p'-DDE bioaccumulation

Laboratory experiments assessed how bioaccumulation of weathered p,p′-DDE from soil and humic acid (HA) chemistry are affected by interactions between the plants Cucurbita pepo ssp. pepo and ssp. ovifera and the earthworms Eisenia fetida, Lumbricus terrestris, and Apporectodea caliginosa. Total organochlorine phytoextraction by ssp. pepo increased at least 25% in the presence of any of the earthworm species (relative to plants grown in isolation). Uptake of the compound by ssp. ovifera was unaffected by earthworms. Plants influenced earthworm bioaccumulation as well. When combined with pepo, p,p′-DDE levels in E. fetida decreased by 50%, whereas, in the presence of ovifera, bioconcentration by L. terrestris increased by more than 2-fold. Spectral analysis indicated a decrease in hydrophobicity of HA in each of the soils in which both pepo and earthworms were present. However, HA chemistry from ovifera treatments was largely unaffected by earthworms. Risk assessments of contaminated soils should account for species interactions, and SOM chemistry may be a useful indictor of pollutant bioaccumulation.     

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.     

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.     

Development of enzyme immunoassay for detection of DDT

Dichlorodiphenyltrichloroethane (DDT) is one of the persistent organic pollutants (POPs) widely found in the environment and in the general population. In this study, a direct competitive enzyme immunoassay (EIA) has been developed for the quantitative analysis of DDT. To generate a specific polyclonal antibody for EIA, p, p′-DDT was conjugated to porcine thyroglobulin for rabbit immunization. At optimized EIA conditions, the standard curves ranged from 0.137 to 100 ng/mL with the quantification limit of 0.41 ng/mL. The coefficients of variation (CV%) were 5.42–10.53% for intra-assay and 6.04–7.26% for inter-assay. Cross-reactivities with DDT metabolites (DDTs, including o, p′-DDT, p, p′-DDD, o, p′-DDD, p, p′-DDE, o, p′-DDE, p, p′-dichlorobenzophenone (DCBP), o, p′-DCBP) were investigated. The polyclonal antibody showed relatively low and/or no cross-reactivity with these compounds, and the assay was seen to be highly selective for p, p′-DDT. Moreover, the DDTs could be ranked by their reactivity: DDT > DDD > DDE > DCBP. In addition, the characterization of the polyclonal antibody indicated that the antiserum possesses a high specificity for p, p′-isomers. The results indicated that the developed EIA using this antibody could be a convenient and supplemental analytical tool for monitoring DDT.     

Fenton (H2O2/Fe) reaction involved in Penicillium sp. culture for DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane)] degradation

The purpose of this work was to demonstrate that a Fenton (H₂O₂/Fe) reaction was involved in DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane)] degradation in a culture of Penicillium sp. spiked with FeSO₄. A commercial DDT mixture (10% DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene], 30% o,p-DDT and 60% of p,p′ -DDT) of 10 mg L^{? 1} was used. Hydrogen peroxide (H₂O₂), tartaric acid and oxalic acid were identified at 18 h in culture media, with and without added DDT; this correlated positively with lowering of pH from 5.8 to 2.7. Lower concentrations of oxalic acid and H₂O₂ (7.9 and 52.6 mg L^{? 1}, respectively) occurred in media with DDT at 30 h, in comparison to that one without DDT mixture (27.9 and 65.3 mg L^{? 1}, respectively), at this time there was maximum degradation (87.7, 91.7 and 94.2%) for DDE, o,p-DDT and p,p′-DDT, respectively. We propose that the degradation of the DDT mixture by Penicillium sp. was through a Fenton reaction (H₂O₂/Fe) under acidic conditions produced in situ during the fungal culture amended with FeSO₄.     

DDT residues in water, sediment, domestic and indigenous biota from a currently DDT-sprayed area

DDT is used for indoor residual spraying (IRS) in Limpopo Province, northern South Africa to control malaria. Through IRS, DDT may reach the outdoor environment via dust and air and from possible spillages during application. In this area the local people consume domestic chickens, wild fish or birds. Fish from the river catchment and impoundments seem to be the major source of protein intake. Water, sediment and tissue samples from two such fish species, domestic chickens and wild birds (terrestrial and aquatic) from this DDT-sprayed area were analysed for DDT and metabolite residues. The samples contained p,p′-DDT, p,p′-DDD and p,p′-DDE residues, with the latter the most ubiquitous and in the highest concentrations. These findings raise concern that both water and food may be major routes of human exposure to DDT and metabolites, thereby posing possible adverse human health implications to the local communities.     

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.     

Levels of persistent organic pollutants in air in China and over the Yellow Sea

The occurrence of persistent toxic substances (PTS) in China and possibly their regional transport in the Yellow and East China Seas region was studied. Organochlorines in atmospheric gas-phase and particulate matter were collected by high-volume sampling (filters and polyurethane foams) during 2 weeks in June 2003 (dry season) simultaneously at a Yellow Sea coastal site in an urban area, Qingdao, China, and a rural island site, Gosan, Jeju Island, Korea. Using GC methods, the samples were analysed for 9 persistent organic pollutants (POPs) regulated under the global POP convention, namely aldrin, chlordane (cis- and trans-isomers CC and TC), DDT and metabolites (o,p′-DDT, p,p′-DDD, and p,p′-DDE), dieldrin, endrin, heptachlor, hexachlorobenzene (HCB), mirex and PCB (congeners number 28, 52, 101, 153 and 180), and for hexachlorocyclohexane (α-, β- and γ-isomers), a PTS and now considered for regulation under the convention, too. At the coastal site additionally o,p′-DDE and -DDD, β-endosulfan, isodrin, heptachlorepoxide and δ-HCH, and at the island site additionally p,p′-DDT and 12 additional PCB congeners were analysed. 9 samples were collected at the coastal and 15 (for PCBs 5) at the island site. Long-range advection pathways were determined based on analysed back-trajectory calculations.The mean concentrations of DDT and its metabolites, HCB, HCH, and PCB at the coast were in the 100–1000 pg m⁻³ range. Higher concentrations prevailed during nighttime. The levels were in general lower at the island site, but not for DDT. Local sources are likely. PCBs were even 2 orders of magnitude lower, suggesting that PCBs are not subject to regional transport but elevated concentrations in air are limited to the source areas. Organochlorine pesticide levels on the other hand were seemingly determined by regional transport over Mainland China rather than by emissions in the coastal area. The currently used pesticides mirex and chlordane were found at elevated levels, i.e. 79 (6.6–255) and 36 (<6–71) pg m⁻³, respectively, at the coast but not over the island. The POPs pesticides aldrin, dieldrin and endrin, never registered in China, were mostly found at <10 pg m⁻³ except for endrin at the coastal site (up to 400 pg m⁻³) and aldrin at the island site (up to 50 pg m⁻³).     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 15 organochlorine pesticides (OCPs) in completely different matrices of traditional Chinese medicine (TCM). The method employed a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.1, 0.5 and 2.0 mg kg⁻¹. Mean recoveries mostly ranged between 76.0% and 114.0% (96.0% on average), and relative standard deviations (RSD) were generally below 10% (4.72% on average). Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity. The contamination status of 15 OCPs on 80 different TCMs marketed in China, and a total of 400 samples were also performed using a previously validated method. 15 OCPs were benzene hexachloride (BHC, including α-BHC, β-BHC, γ-BHC, δ-BHC), hexachlorobenzene, heptachlor, heptachlor epoxide, aldrin, p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT, mirex, endrin, dieldrin. This study indicates that the proposed method is useful for analyzing OCPs in TCM.     

Accumulation levels and characteristics of some pesticides in human adipose tissue samples from Southeast China

This paper presents a comprehensive study of pesticide levels and bio-accumulation characteristics in human adipose tissues among residents of Southeast China. A large number of adipose samples (n = 633) were selected for 58 pesticides and were analyzed by high sensitive Gas Chromatography-Tandem Mass Spectrometry (GC-MS/MS). The results showed that POPs pesticides were frequently detected, including 2,4′-DDD, 2,4′-DDE, 2,4′-DDT, 4,4′-DDD, 4,4′-DDE, 4,4′-DDT, α-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), and mirex. Other detected pesticide species were dicofol, methamidophos and chlordimeform, which have rarely been reported. Comparing to different countries, the concentrations of total DDT and HCH in these three Chinese southeastern sites were in the middle range, whereas the HCB and mirex were in the lower end. A significant correlation was observed between region as well as age and POPs pesticide levels. Some pesticide residue levels were also found significantly correlated to occupation. However, there was no significant correlation between gender and pesticides. Meanwhile, it is interesting to find that mortality of malignant tumors tends to associate with the pesticides levels in human adipose tissue. More importantly, the measured data presented in this study provide realistic information which is useful for assessing human exposure to pesticides in the general population of Southeast China.