Kinetic assessment of persistent halogenated xenobiotics in cell culture models: comparison of mono- and poly-halogenated compounds

We evaluated the suitability of single and multiple cell type cultures as model systems to characterise cellular kinetics of highly lipophilic compounds with potential ecotoxicological impact. Confluent mono-layers of human skin fibroblasts, rat astrocytoma C6 cells, non-differentiated and differentiated mouse 3T3 cells were kept in culture medium supplemented with 10% foetal calf serum. For competitive uptake experiments up to four different cell types, grown on glass sectors, were exposed for 3 h to ¹⁴C-labelled model compounds, dissolved either in organic solvents or incorporated into unilamellar lecithin liposomes. Bromo-, or chloro-benzenes, decabromodiphenylether (DBP), and dichlorodiphenyl ethylene (DDE) were tested in rather high concentration of 20 μM. Cellular toxicity was low. Compound levels were related to protein, DNA, and triglyceride contents. Cellular uptake was fast and dependent on physico-chemical properties of the compounds (lipophilicity, molecular size), formulation, and cell type. Mono-halogenated benzenes showed low and similar uptake levels (= low accumulation compounds). DBP and DDE showed much higher cellular accumulations (= high accumulation compounds) except for DBP in 3T3 cells. Uptake from liposomal formulations was mostly higher than if compounds were dissolved in organic solvents. The extent of uptake correlated with the cellular content of triglycerides, except for DBP. Uptake competition between different cell types was studied in a sectorial multi-cell culture model. For low accumulation compounds negligible differences were found among C6 cells and fibroblasts. Uptake of DDE was slightly and that of DBP highly increased in fibroblasts. Well-defined cell culture systems, especially the sectorial model, are appropriate to screen for bioaccumulation and cytotoxicity of (unknown) chemical entities in vitro.     

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.     

Dietary habits associated with the presence of organochlorine pesticides in human milk

Abstract

This study aims to establish the relationship between the consumption of certain foods and the presence of organochlorine pesticides in human milk. A total of 167 samples of breastmilk were collected. Sample analysis was carried out by gas chromatography with electron capture detector. Pesticide concentrations (op’DDT, pp’DDT, pp’DDE, Σ-DDT, HCB, β-HCH) were grouped by consumption level of fish, dairy products, meat, eggs, and seafood and then were compared to each other. The odds ratio (OR) was calculated between the concentration of pesticides (higher and/or lower than median) and the exposure variable (high consumption). The results indicated low median concentrations of HCB, β???HCH, op’DDT and pp’DDT, whose fluctuations and trends between different frequencies of food consumption were not significant. pp’DDE and Σ???DDT values according to the increase in consumption of fish were significantly increased. Women with high fish consumption have a higher risk of high concentrations of pp’DDE and Σ-DDT (OR: high consumption: 5.6 (1.3–23.6). A protective effect was observed in the consumption of dairy products (β-HCH and op’DDT), meat (HCB), and seafood (pp’DDT). These results suggest that it is possible that the consumption of fish, dairy products, meat, and seafood influences the presence of organochlorine pesticides in the studied population.     

有色金属工业中持久性有机污染物的来源及其控制对策

介绍了四类非故意排放的持久性有机污染物及其形成条件,深入研究了有色金属冶炼、再生生产过程及有色金属深加工过程中持久性有机污染物的来源,并提出了在有色金属工业中控制持久性有机污染物排放的对策和措施。     

Effects of amendments on the uptake and distribution of DDT in Cucurbita pepo ssp pepo plants

The effects of soil amendments on the phytoextraction of ∑DDT (DDT + DDD + DDE) from soil ([∑DDT] ∼ 1500 ng/g) by a pumpkin variety of Cucurbita pepo ssp pepo were tested and the patterns of ∑DDT storage throughout the plant shoot were examined. The soil amendments did not increase the total amount of ∑DDT extracted into plant shoots, but new information about ∑DDT distribution in the plants was obtained. As observed previously, the ∑DDT concentration in plant leaves (mean 290 ng/g) was significantly lower than in plant stems (mean 2600 ng/g). Further analysis revealed that ∑DDT composition was consistent throughout the plant shoot and that ∑DDT concentration in leaves and stems decreased exponentially as distance from the root increased, which was previously unknown. This new information about the patterns of ∑DDT uptake and translocation within pumpkin plants highlights the need for appropriate plant sampling strategies in future POPs phytoextraction research.     

Partitioning of organochlorine pesticides from water to polyethylene passive samplers

The mass transfer rates and equilibrium partitioning behaviour of 14 diverse organochlorine pesticides (OCP) between water and polyethylene (PE) passive samplers, cut from custom made PE sheets and commercial polyethylene plastic bags, were quantified. Overall mass transfer coefficients, k_O, estimated PE membrane diffusion coefficients, D_PE, and PE-water partitioning coefficients, K_PE-water, are reported. In addition, the partitioning of three polycyclic aromatic hydrocarbons (PAHs) from water to PE is quantified and compared with literature values. K_PE-water values agreed mostly within a factor of two for both passive samplers and also with literature values for the reference PAHs. As PE is expected to exhibit similar sorption behaviour to long-chain alkanes, PE-water partitioning coefficients were compared to hexadecane-water partitioning coefficients estimated with the SPARC online calculator, COSMOtherm and a polyparameter linear free energy relationship based on the Abraham approach. The best correlation for all compounds tested was with COSMOtherm estimated hexadecane-water partitioning coefficients.     

Persistent organic pollutants (PCB, DDT, HCH, HCB & BDE) in eels (Anguilla anguilla) in Scotland: Current levels and temporal trends

Eels are an ideal biomonitor for persistent organic pollutants (POPs) because of their high lipid content, longevity and tendency to remain within a defined range during their freshwater life phase. This study investigated concentrations of POPs in eels (Anguilla anguilla) from 30 sites across Scotland, including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (BDEs), DDT (and metabolites), hexachlorocyclohexanes (α, β, γ-HCH), hexachlorobenzene (HCB), hexachlorobutadiene (HCBD) and pentachlorobenzene. Despite its EU-wide ban ∼30 years ago, DDT and its derivatives were detected in almost all samples. PCB 153 and 138 were the most widely detected PCB congeners, while BDE 47 was the dominant BDE. Pentachlorobenzene was not detected, while HCBD was detected once only. α-HCH, β-HCH and HCB concentrations were very low (generally <3 μg/kg or below detection). When compared with 1986 and 1995 data, the results revealed considerable decreases in p,p′-DDE concentrations. More drastic reductions were evident for γ-HCH, reflecting the tightening restrictions on pesticide use imposed over the previous decades.     

Validation of a GC-MS/MS method for simultaneous determination of 86 persistent organic pollutants in marine sediments by pressurized liquid extraction followed by stir bar sorptive extraction

A multiresidue method for the analysis of 86 persistent pollutants in marine sediments at ultra-trace level has been developed and validated using pressurized liquid extraction (PLE) and stir-bar sorptive extraction (SBSE) coupled with thermal desorption and gas chromatography-triple quadrupole mass spectrometry (TD-GC-MS/MS QqQ). The compounds analyzed belong to various families such as polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenylethers, organophosphorus and organochlorine pesticides and other pesticides such as urons, and triazines. The analytes have very different polarities and log K_ow values, which is an important parameter in the optimization of a SBSE method. Due to PLE high efficiency and throughput rates, along with the proven ability for multiresidue analysis and excellent sensitivity of SBSE, we present an efficient method. The limits of quantification obtained ranged from 0.014 to 1.0 ng g⁻¹, with detection limits below pg g⁻¹ levels. In order to validate the proposed methodology, quality parameters such as recovery, linearity and reproducibility were studied. Recoveries ranged from 63% to 119%, reproducibility (in terms of Relative Standard Deviation for ten determinations) was lower than 35% in all cases, and determination coefficients higher than 0.990 for all analytes. The main factors that affect PLE, SBSE and GC-MS/MS procedures were optimized. The method was applied to the analysis of nine marine sediments obtained from the nine main submarine wastewater discharge points (emissaries) presents along the coast of Tenerife Island (Canary Islands, Spain).     

Persistent organochlorine pollutants and menstrual cycle characteristics

An evolving body of evidence suggests an adverse relation between persistent organochlorine pollutants (POPs) and menstruation, though prospective longitudinal measurement of menses is limited and served as the impetus for study. We prospectively assessed the relation between a mixture of persistent organochlorine compounds and menstrual cycle length and duration of bleeding in a cohort of women attempting to become pregnant. Eighty-three (83%) women contributing 447 cycles for analysis provided a blood specimen for the quantification of 76 polychlorinated biphenyls and seven organochlorine pesticides, and completed daily diaries on menstruation until a human chorionic gonadotropin confirmed pregnancy or 12 menstrual cycles without conception. Gas chromatography with electron capture detection was used to quantify concentrations (ng g⁻¹ serum); enzymatic methods were used to quantify serum lipids (mg dL⁻¹). A linear regression model with a mixture distribution was used to identify chemicals grouped by purported biologic activity that significantly affected menstrual cycle length and duration of bleeding adjusting for age at menarche and enrollment, body mass index, and cigarette smoking.A significant 3-d increase in cycle length was observed for women in the highest tertile of estrogenic PCB congeners relative to the lowest tertile (β = 3.20; 95% CI 0.36, 6.04). A significant reduction in bleeding (<1 d) was observed among women in the highest versus lowest tertile of aromatic fungicide exposure (γ = −0.15; 95% CI −0.29, −0.00). Select POPs were associated with changes in menstruation underscoring the importance of assessing chemical mixtures for female fecundity.     

Persistent organic pollutant in a fish community of a sub-alpine lake

This study investigated the presence of organochlorine pollutants in abiotic and biotic samples from Lake Como (Italy). DDTs and PCBs were found to be the major contaminants, ranging from 0.04 to 4.25 and from 0.25 to 40.8 μg/g lipid respectively. Evidence of biomagnification according to the trophic role of the investigated organisms was highlighted by means of Stable Isotope Analysis. A Trophic Magnification Factor (TMF) was calculated for the chemicals of interest and the applicability of the method for global use was confirmed. Statistically significant correlation has been found between the calculated trophic level and the concentrations of more lipophilic compounds, while for the less lipophilic (e.g., HCH, 3CBs) the relationship is no statistically significant and the TMF is close to 1.The role of the foraging area in affecting PCB and DDT concentrations within aquatic ecosystems has been highlighted by a Principal Component Analysis (PCA).