Detection of dicofol and related pesticides in human breast milk from China, Korea and Japan

Previously, we demonstrated that the concentrations of DDTs were greater in breast milk collected from Chinese mothers than from Japanese and Korean mothers. To investigate dicofol as a possible source of the DDTs in human breast milk, we collected breast milk samples from 2007 to 2009 in China (Beijing), Korea (Seoul, Busan) and Japan (Sendai, Takarazuka and Takayama). Using these breast milk samples, we quantified the concentrations of dichlorobenzophenone, a pyrolysis product of dicofol (simply referred to as dicofol hereafter), dichlorodiphenyltrichloroethane and its metabolites (DDTs) using GC-MS. Overall, 12 of 14 pooled breast milk samples from 210 mothers contained detectable levels of dicofol (>0.1 ng g⁻¹ lipid). The geometric mean concentration of dicofol in the Japanese breast milk samples was 0.3 ng g⁻¹ lipid and significantly lower than that in Chinese (9.6 ng g⁻¹ lipid) or Korean breast milk samples (1.9 ng g⁻¹ lipid) (p < 0.05 for each). Furthermore, the ΣDDT levels in breast milk from China were 10-fold higher than those from Korea and Japan. The present results strongly suggest the presence of extensive emission sources of both dicofol and DDTs in China. However, exposure to dicofol cannot explain the large exposure of Chinese mothers to DDTs because of the trace levels of dicofol in the ΣDDTs. In the present study, dicofol was confirmed to be detectable in human breast milk. This is the first report to identify dicofol in human samples.     

Applicability of microwave-assisted extraction combined with LC-MS/MS in the evaluation of booster biocide levels in harbour sediments

A new sample treatment method for the determination of four common booster biocides (Diuron, TCMTB, Irgarol 1051 and Dichlofluanid) in harbour sediment samples has been developed that uses liquid chromatography-tandem mass spectrometry (LC-MS/MS) after microwave-assisted extraction, followed by clean-up and a solid phase extraction preconcentration step (MAE-SPE). The effects of different variables on MAE-SPE were studied. The recoveries obtained were greater than 75%, and the relative standard deviation was less than 7%. The detection limits ranged between 0.1 and 0.3 ng g⁻¹. The developed methodology was successfully applied to the evaluation of the presence of booster biocides in sediment samples from different harbours and marinas of Gran Canaria Island (Canary Islands, Spain).     

Photoinduced reduction of divalent mercury in ice by organic matter

Reduction of divalent mercury and subsequent emission to the atmosphere has been identified as loss process from surface snow, but its mechanism and importance are still unclear. The amount of mercury that stays in the snow pack until spring is of significance, because during snow melt it may be released to the aquatic environment and enter the food web. Better knowledge of its fate in snow might further assist the interpretation of ice core data as paleo-archive. Experiments were performed under well-controlled laboratory conditions in a coated wall flow tube at atmospheric pressure and irradiated with light between 300 nm and 420 nm. Our results show that the presence of benzophenone and of oxalic acid significantly enhances the release of mercury from the ice film during irradiation, whereas humic acid is less potent to promote the reduction. Further it was found that oxygen or chloride, and acidic conditions lowered the photolytically induced mercury release in the presence of benzophenone, while the release got larger with increasing temperatures.     

Transcriptome analysis provides insights for understanding the adverse effects of endosulfan in Drosophila melanogaster

Indiscriminate use of agrochemicals worldwide, particularly, persistent organic pollutants (POPs), is of concern. Endosulfan, a POP, is used by various developing/developed nations and is known to adversely affect the development and the hormonal profiles of humans and animals. However, little is known about the molecular players/pathways underlying the adverse effects of endosulfan. We therefore analyzed the global gene expression changes and subsequent adverse effects of endosulfan using Drosophila. We used Drosophila melanogaster keeping in view of its well annotated genome and the wealth of genetic/molecular reagents available for this model organism. We exposed third instar larvae of D. melanogaster to endosulfan (2.0 μg mL⁻¹) for 24 h and using microarray, we identified differential expression of 256 genes in exposed organisms compared to controls. These genes are associated with cellular processes such as development, stress and immune response and metabolism. Microarray results were validated through quantitative PCR and biochemical assay on a subset of genes/proteins. Taking cues from microarray data, we analyzed the effect of endosulfan on development, emergence and survival of the organism. In exposed organisms, we observed deformities in hind-legs, reminiscent of those observed in higher organisms exposed to endosulfan. In addition, we observed delayed and/or reduced emergence in exposed organisms when compared to their respective controls. Together, our studies not only highlight the adverse effects of endosulfan on the organism but also provide an insight into the possible genetic perturbations underlying these effects, which might have potential implications to higher organisms.     

Determination of lipid peroxidation and cytotoxicity in calcium, magnesium, titanium and hectorite (SHCa-1) suspensions

This paper reports data on the relative ability of CaO, CaCl₂, MgO, MgCl₂, TiO₂, and hectorite (SHCa-1) to induce oxidative stress (as determined by lipid peroxidation, LP) in biological matrices. The effectiveness of structural (oxide form) versus soluble Ca and Mg to induce LP is compared. An assessment on cytotoxicity as affected by soluble and structural Ca, Mg, TiO₂ and SHCa-1 is also addressed. LP was screened and monitored using the Thiobarbituric Acid Reactive Substances (TBARS). The extent of TBARS production was found to vary with the type and initial concentration of the soluble or structural cation, Ca or Mg respectively. Obtained results showed higher magnitude values for the latter set of experiments. In the presence of TiO₂ no significant TBARS production was detected pointing out a negligible effect of TiO₂ on LP. At solid concentrations ca. 100 ppm, CaO appears to be more effective than SHCa-1 to induce LP. By contrast at ca. 25 ppm, MgO appears to be more effective than the clay mineral. The SHCa-1 LP-inducing activity has been proven to closely relate to structural Ca. The prevalence of mechanisms that may induce LP but not cytotoxicity (as determined by cell growth inhibition) was also addressed. Results on cell growth inhibition as affected by soluble and structural Ca, Mg, TiO₂ and hectorite provide evidence to support that structural Ca or Mg brings about significantly higher variations than soluble Ca.     

Spatial distribution of polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs) in an e-waste dismantling region in Southeast China: Use of apple snail (Ampullariidae) as a bioindicator

Fengjiang is a large e-waste dismantling site located in southeast China. In this paper, apple snail and soil samples were collected from this e-waste dismantling site and 25 vicinal towns to investigate the contamination status, spatial distributions and congener patterns of polychlorinated biphenyls (PCBs) and polybrominated biphenyl ethers (PBDEs). Total PCB concentrations in apple snails (3.78-1812 ng g⁻¹ dry weight (dw)) were significant higher than that in soil samples (0.48-90.1 ng g⁻¹ dw). PBDE (excluding BDE 209) concentrations in apple snail and soil samples ranged from 0.09 to 27.7 ng g⁻¹ dw and 0.06 to 31.2 ng g⁻¹ dw, respectively. Concentrations of PCBs and PBDEs in snails and soils correlated negatively with the distance from Fengjiang. Both the concentrations and profiles of the pollutants were significantly correlated (p < 0.05) between the snail and soil samples, indicating the suitability of apple snail as a reliable bioindicator for PCBs and PBDEs contamination in this region. Relatively high concentrations of PCBs and PBDEs at locations far from e-waste dismantling sites implied that these pollutants have been transported to surrounding regions.     

Dietary patterns and blood levels of PCDDs, PCDFs, and dioxin-like PCBs in 1656 Japanese individuals

The association between dietary patterns and blood dioxin levels has not been fully investigated. The present study population consisted of 755 men and 901 women (aged 15-73 years) living in 90 different areas of 30 prefectures of Japan. Dietary habits were assessed by inquiring about the consumption frequency of 28 foods, food groups and beverages. In addition, the blood levels of 29 polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzo-furans (PCDFs), and dioxin-like polychlorinated biphenyl (DL-PCBs) congeners were determined by high-resolution gas chromatography/mass spectrometry. The median total toxicity equivalent (TEQ) in the blood, which was calculated on the basis of the toxicity equivalency factors of WHO (2005), was 16 pg TEQ g⁻¹ lipid. Principal component analysis identified five dietary patterns: Healthy diet (high intake of vegetables and fruits); Meat/High fat intake (high intake of meat, meat products, and eggs); Seafood and Alcohol (high intake of fish, shellfish, and alcoholic beverages); Miscellaneous; and Milk products and Alcohol intake (high intake of milk, Milk products, and alcoholic beverages). After adjusting for sex, age, body mass index, and smoking habits, the Seafood and Alcohol pattern scores were significantly related to higher blood levels of total TEQ and PCDDs/PCDFs/DL-PCBs, and the Milk products and Alcohol pattern scores were correlated with higher blood levels of DL-PCBs. More detailed analysis showed that the intake frequencies for alcoholic beverages and seafood were independently and positively associated with total TEQ and the TEQ of PCDFs and DL-PCBs. The association between alcoholic beverage intake and PCDDs was also significant. Analysis of dietary patterns may be useful for identifying the dietary characteristics of individuals with a high dioxin body burden.     

Nonparametric functional data estimation applied to ozone data: prediction and extreme value analysis

The study of extreme values and prediction of ozone data is an important topic of research when dealing with environmental problems. Classical extreme value theory is usually used in air-pollution studies. It consists in fitting a parametric generalised extreme value (GEV) distribution to a data set of extreme values, and using the estimated distribution to compute return levels and other quantities of interest. Here, we propose to estimate these values using nonparametric functional data methods. Functional data analysis is a relatively new statistical methodology that generally deals with data consisting of curves or multi-dimensional variables. In this paper, we use this technique, jointly with nonparametric curve estimation, to provide alternatives to the usual parametric statistical tools. The nonparametric estimators are applied to real samples of maximum ozone values obtained from several monitoring stations belonging to the Automatic Urban and Rural Network (AURN) in the UK. The results show that nonparametric estimators work satisfactorily, outperforming the behaviour of classical parametric estimators. Functional data analysis is also used to predict stratospheric ozone concentrations. We show an application, using the data set of mean monthly ozone concentrations in Arosa, Switzerland, and the results are compared with those obtained by classical time series (ARIMA) analysis.     

Carry-over of dietary organochlorine pesticides, PCDD/Fs, PCBs, and brominated flame retardants to Atlantic salmon (Salmo salar L.) fillets

Information on carry-over of contaminants from feed to animal food products is essential for appropriate human risk assessment of feed contaminants. The carry-over of potentially hazardous persistent organic pollutants (POPs) from feed to fillet was assessed in consumption sized Atlantic salmon (Salmo salar). Relative carry-over (defined as the fraction of a certain dietary POP retained in the fillet) was assessed in a controlled feeding trial, which provided fillet retention of dietary organochlorine pesticides (OCPs), dioxins (PCDD/Fs), polychlorinated biphenyls (PCBs), and brominated flame retardants (BFRs). Highest retention was found for OCPs, BFRs and PCBs (31-58%), and the lowest retentions were observed for PCDD/Fs congeners (10-34%). National monitoring data on commercial fish feed and farmed Atlantic salmon on the Norwegian market were used to provide commercially relevant feed-to-fillet transfer factors (calculated as fillet POP level divided by feed POP level), which ranged from 0.4 to 0.5, which is a factor 5-10 times higher than reported for terrestrial meat products. For the OCP with one of the highest relative carry-over, toxaphene, uptake and elimination kinetics were established. Model simulations that are based on the uptake and elimination kinetics gave predicted levels that were in agreement with the measured values. Application of the model to the current EU upper limit for toxaphene in feed (50 μg kg⁻¹) gave maximum fillet levels of 22 μg kg⁻¹, which exceeds the estimated permissible level (21 μg kg⁻¹) for toxaphene in fish food samples in Norway.     

Development of a combined isotopic and mass-balance approach to determine dissolved organic carbon sources in eutrophic reservoirs

A combined mass-balance and stable isotope approach was set up to identify and quantify dissolved organic carbon (DOC) sources in a DOC-rich (9 mg L⁻¹) eutrophic reservoir located in Western France and used for drinking water supply (so-called Rophemel reservoir). The mass-balance approach consisted in measuring the flux of allochthonous DOC on a daily basis, and in comparing it with the effective (measured) DOC concentration of the reservoir. The isotopic approach consisted, for its part, in measuring the carbon isotope ratios (δ¹³C values) of both allochthonous and autochthonous DOC sources, and comparing these values with the δ¹³C values of the reservoir DOC. Results from both approaches were consistent pointing out for a DOC of 100% allochthonous origin. In particular, the δ¹³C values of the DOC recovered in the reservoir (−28.5 ± 0.2‰; n = 22) during the algal bloom season (May-September) showed no trace of an autochthonous contribution (δ¹³C in algae = −30.1 ± 0.3‰; n = 2) being indistinguishable from the δ¹³C values of allochthonous DOC from inflowing rivers (−28.6 ± 0.1‰; n = 8). These results demonstrate that eutrophication is not responsible for the high DOC concentrations observed in the Rophemel reservoir and that limiting eutrophication of this reservoir will not reduce the potential formation of disinfection by-products during water treatment. The methodology developed in this study based on a complementary isotopic and mass-balance approach provides a powerful tool, suitable to identify and quantify DOC sources in eutrophic, DOC-contaminated reservoirs.