Zulin Zhang

Fate and assessment of persistent organic pollutants in water and sediment from Minjiang River Estuary, southeast China

Persistent organochlorine compounds were analyzed in surface water, porewater and surficial sediment samples from Minjiang River Estuary, which is the first large river in Fujian Province, Southeast of China. The total concentrations of 18 organochlorine pesticides were 214.4-1819, 4541-13,699 ng/l, 28.79-52.07 ng/g in surface water, porewater and sediments (dry weight) respectively, and those of 21 polychlorinated biphenyls (PCBs) in the three phases were: 203.9-2473, 3192-10,855 ng/l, 15.14-57.93 ng/g respectively. The results showed that the concentrations of these selected organochlorine pesticides and PCBs in porewater were higher than those in surface water. It may be due to the fact that these organic hydrophobic pollutants tend to stay in the sediments, and then re-suspend from the sedimentary phase to the upper water. We have analyzed the distribution characteristics of individual organochlorine pesticide components and PCBs, and found that alpha-HCH, DDE, Heptachlor, Endosulfan II, Methoxychlor were the most common organochlorine pesticides contaminants. Considering the groups of HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH) and DDTs (DDTs=DDT+DDD+DDE), the predominance of beta-HCH, DDE in all water, porewater and sediment samples was clearly observed. This observation suggested that beta-HCH was resistant to biodegradation and the DDTs had been transformed to its metabolites, DDE and DDD, of which DDE that was more un-degradable. The PCB congeners containing 3-6 chlorines had the great preponderance in the three phase. These results were compared with those present in other estuaries and harbors. A risk assessment was evaluated for the persistent organic pollutants in the Minjiang River Estuary.

Contamination by polycyclic aromatic hydrocarbons in the Jiulong River Estuary and Western Xiamen Sea, China

The distribution of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in water, sediment and pore water of the Jiulong River Estuary and Western Xiamen Sea, China. Total PAH concentrations varied from 6.96 to 26.9 microg/l in water, 59-1177 ng/ g dry weight in surficial sediments, and 158-949 microg/l in pore water. The PAHs were present in higher levels in pore water than in surface water, due possibly to higher concentrations of dissolved organic carbon or colloids with which the hydrophobic pollutants were strongly associated. Such a concentration gradient implies a potential flux of pollutants from sediment pore water to overlying water. The levels of PAHs in water and pore water were significantly higher than those found in 1998, suggesting recent inputs of these compounds into the area and re-working of sediment phase. The composition pattern of PAHs in the three phases was dominated by high molecular weight PAHs, in particular 5-ring PAHs. The salinity profile of dissolved PAHs suggested that they all behaved non-conservatively due to deviation from the theoretical dilution line. No correlation was found between PAH concentrations in sediment and those in pore water, and the correlation between the partition coefficients of PAHs and sediment organic carbon content was not significant, suggesting the complexity of the partition behaviour of PAHs. As a result of high PAH concentrations in water and pore water, it is likely that they may have caused mortality to certain exposed organisms.

Multi-phase distribution of organic micropollutants in Xiamen Harbour, China

Abstract Xiamen Harbour, in the Xiamen Special Economic Zone of the People’s Republic of China, was studied for its water and sediment quality, by determining the levels of 16 polycyclic aromatic hydrocarbons (PAHs), 12 polychlorinated biphenyls (PCBs) and 18 organochlorine insecticides in water, suspended particulate matter (SPM), pore water and sediment samples from nine stations in the Harbour. Total PAH concentrations varied from 106 to 945 ng/l in water,

Simultaneous extraction and clean-up of polybrominated diphenyl ethers and polychlorinated biphenyls from sheep liver tissue by selective pressurized liquid extraction and analysis by gas chromatography-mass spectrometry.

We describe a selective pressurized liquid extraction (SPLE) method, followed by gas chromatography-mass spectrometry (GC-MS), for the simultaneous extraction and clean-up of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in sheep liver tissue samples. The on-line clean-up of liver tissue by SPLE was tested using differing amount of acid-modified silica (sulphuric acid:silica gel, 1:2, w/w), the most effective amount being 20 g. Different extraction solvents (iso-hexane and dichloromethane), either alone or in various combinations, were used to extract these target compounds from spiked liver samples. Variables affecting the SPLE extraction efficiency, including temperature, pressure, number of extraction cycles and static extraction time were studied; the optimum parameters were 80 °C, 10.3 MPa, 2 cycles and 5 min, respectively. The SPLE based method was compared with more traditional Soxhlet, off-line PLE, ultrasonic and heating extraction methods. Overall the mean percentage recoveries for all target chemicals using SPLE were 86-103% (n=3, SD < 9%), and compared favourably with the Soxhlet (63-109%, n=3, SD < 8%), off-line PLE (82-104%, n=3, SD < 18%), ultrasonic (86-99%, n=3, SD < 11%) and heating (72-102%, n=3, SD < 21%) extraction methods. The limits of detection of the proposed method were 5-96 pg g⁻¹ and 2-29 pg g⁻¹ for the different PBDE and PCB chemicals studied, respectively. The outputs of the proposed method were linear over the range from 0.02 to 30 ng g⁻¹, for all PCB and PBDE congeners except for PBDE 100 and 153 (0.05-30 ng g⁻¹) and PBDE 183 (0.1-30 ng g⁻¹). The method was successfully applied to sheep liver samples for the determination of the target PBDE and PCB compounds.

Dissolved insecticides and polychlorinated biphenyls in the Pearl River Estuary and South China Sea

Persistent organic pollutants (POPs) such as organochlorine (OCl) insecticides and polychlorinated biphenyls (PCB), together with the new generation of organophosphorus (OP) insecticides, are of global concern, due to their widespread occurrence, persistence, bioaccumulation and hormone disruption potential. This paper represents an attempt to study the source and transportation of such pollutants in estuarine and coastal environments as an integrated ecosystem, by determining the levels of 18 OCl insecticides, 21 PCB congeners, and 17 OP insecticides in the Pearl River Estuary and South China Sea. The total concentrations varied from 126-1198 ng l(-1) for OCl insecticides, 33.38-1064 ng l(-1) for PCB congeners, and 4.44-6356 ng l(-1) for OP insecticides in the Pearl River Estuary. In comparison, their levels in the South China Sea were significantly lower, varying from 57.09-202 ng l(-1) for OCl insecticides, 21.72-144 ng l(-1) for PCBs, and 1.27-122 ng l(-1) for OP insecticides, respectively. The predominance of beta-HCH in HCHs, and DDE in DDTs in all water samples was clearly observed, suggesting beta-HCH and DDEs resistance to further degradation. The PCBs were dominated by those with 3-6 chlorines. The distribution characteristic of OP insecticides shows that five compounds (methamidophos, dimethoate, malathion, dichlorvos and omethoate) accounted for 56% and 72% of the total OP insecticide concentration. The relationship between pollutant concentrations and salinity in the estuary showed that they were all removed during the mixing process, therefore behaving non-conservatively.

Selective pressurized liquid extraction of estrogenic compounds in soil and analysis by gas chromatography-mass spectrometry.

A selective pressurized liquid extraction (SPLE) method, followed by gas chromatography-mass spectrometry (GC-MS), for the simultaneous extraction and clean-up of estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), estriol (E3) and bisphenol A (BPA) from soil samples is described. The on-line clean-up of soil by SPLE was achieved using different organic matter retainers, including silica, alumina and Florisil, the most effective being silica. Thus, different amounts of silica, in conjunction with different extraction solvents (acetone, ethyl acetate, isohexane and dichloromethane), either alone or in combination, were used to extract the target chemicals from spiked soil samples. It was shown that 3g silica resulted in satisfactory rates of recovery of target compounds and acetone:dichloromethane (1:3, v/v) was efficient in extracting and eluting estrogenic compounds for SPLE. Variables affecting the SPLE efficiency, including temperature and pressure were studied; the optimum parameters were 60°C and 1500 psi, respectively. The limits of detection (LODs) of the proposed method were 0.02-0.37 ng g(-1) for the different estrogenic chemicals studied. The outputs using the proposed method were linear over the range from 0.1 to 120 ng g(-1) for E1, E2, EE2, 0.2-120 ng g(-1) for E3, and 0.5-120 ng g(-1) for BPA. The optimized method was further verified by performing spiking experiments in natural soil matrices; good rates of recovery and reproducibility were achieved for all selected compounds and the method was successfully applied to soil samples from Northeast Scotland, for the determination of the target compounds.

Effects of Polychlorinated Biphenyls in CD-1 Mice: Reproductive Toxicity and Intergenerational Transmission

Several studies indicate that in utero and perinatal exposure to polychlorinated biphenyls (PCBs) induces adverse reproductive effects, but it remains unclear whether such effects may be transmitted to subsequent generations. We therefore investigated the association between maternal exposure to PCBs and reproductive health in male and female offspring over three generations. Mouse dams were fed 0, 1, 10, and 100 μg/kg/day of a PCB mixture (101 + 118) during pregnancy and lactation. PCB levels were measured in the tissues of both dams and offspring. PCB concentrations at all doses investigated were greater in the offspring than in the dams (p ≤ 0.0001) confirming that the progeny were exposed as a result of maternal exposure. In F1 offspring, exposure to PCBs resulted in reductions in (1) testis weight (p ≤ 0.05) and seminiferous tubule diameter (p ≤ 0.05), (2) sperm viability (p ≤ 0.0001) and developmental capacity (p ≤ 0.05), (3) ovary weight (p ≤ 0.05), (4) oocyte developmental capacity (p ≤ 0.05), and (5) increased follicular atresia (p ≤ 0.0001). In females, adverse effects were observed only in the F1 animals. In contrast, male offspring exhibited reduced sperm viability and altered seminiferous tubule distribution up to the third generation, showing intergenerational transmission. In summary, our data indicate that exposure to PCBs at the time of gonadal sex determination perturbed, significantly, the reproductive physiology of male and female offspring in adulthood. Furthermore, male reproductive deficiencies may be observed in at least two further generations. These findings have significant implications for reproductive health and fertility of animals and humans.

Bioaccumulation of persistent organic pollutants in the deepest ocean fauna

The legacy and reach of anthropogenic influence is most clearly evidenced by its impact on the most remote and inaccessible habitats on Earth. Here we identify extraordinary levels of persistent organic pollutants in the endemic amphipod fauna from two of the deepest ocean trenches (>10,000 metres). Contaminant levels were considerably higher than documented for nearby regions of heavy industrialization, indicating bioaccumulation of anthropogenic contamination and inferring that these pollutants are pervasive across the world’s oceans and to full ocean depth.

Foetal and post-natal exposure of sheep to sewage sludge chemicals disrupts sperm production in adulthood in a subset of animals

Exposure to ubiquitous, environmental chemicals (ECs) has been hypothesized as a cause for declining male reproductive health. Understanding the long-term effects of EC exposure on reproductive health in humans requires animal models and exposure to ‘real life’, environmentally relevant, mixtures during development, a life stage of particular sensitivity to ECs. The aim of this study was to evaluate the effects of in utero and post-natal exposure to environmentally relevant levels of ECs, via sewage sludge application to pasture, on the adult male sheep testis. Hormones, liver concentrations of candidate ECs and Sertoli and germ cell numbers in testes of adult rams that were exposed to ECs in sewage sludge in utero, and until weaning via maternal exposure, and post-weaning via grazing pastures fertilized with sewage sludge, were quantified. Evaluated as a single group, exposure to sludge ECs was without significant effect on most parameters. However, a more detailed study revealed that 5 of 12 sludge-exposed rams exhibited major spermatogenic abnormalities. These consisted of major reductions in germ cell numbers per testis or per Sertoli cell and more Sertoli cell-only tubules, when compared with controls, which did not show any such changes. The sludge-related spermatogenic changes in the five affected animals were significantly different from controls (p < 0.001); Sertoli cell number was unaffected. Hormone profiles and liver candidate EC concentrations were not measurably affected by exposure. We conclude that developmental exposure of male sheep to real-world mixtures of ECs can result in major reduction in germ cell numbers, indicative of impaired sperm production, in a proportion of exposed males. The individual-specific effects are presumed to reflect EC effects on a heterogeneous population in which some individuals may be more susceptible to adverse EC effects. Such effects of EC exposure in humans could have adverse consequences for sperm counts and fertility in some exposed males.

Maternal and fetal tissue accumulation of selected endocrine disrupting compounds (EDCs) following exposure to sewage sludge-treated pastures before or after conception

This paper reports patterns of accumulation of selected EDCs in adult and fetal livers of sheep exposed to sewage sludge-treated pastures, at different times and at two stages of development.