深圳河典型内分泌干扰物分布和季节变化规律研究

2011年6月至2012年5月在深圳河沿程采集水样,采用固相萃取一氮吹一衍生化的预处理方法和气相色谱/质谱联用法,对壬基酚(NP)、辛基酚(OP)、双酚A(BPA)、雌酮(E1)、雌二醇(E2)、17α-雌二醇(17α-E2)、雌三醇(E3)、雌炔醇(EE2)等8种内分泌干扰物(EDCs)在深圳河的浓度分布和时空变化规律进行了研究.同时通过主成分分析考察了EDCs与常规水质污染物的关系.结果表明,NP、BPA、E1、E3、EE2在深圳河各河段均有检出,而OP、17α-E2、E2的检出率均低于20％,EDCs主要来源是NP和BPA;深圳河旱季和雨季EDCs的浓度变化大,其中NP浓度表现出旱季高雨季低的规律,旱季浓度是雨季的1.74～5.63倍,但BPA和3种甾醇类雌激素的浓度呈现出了雨季高旱季低的相反变化规律,这应该与污水处理厂雨季污水溢流有关;通过主成分分析发现,BPA与DO存在明显的负相关关系,生物作用可能在BPA去除和甾醇类雌激素转化中起到了重要作用,具体机制还有待进一步研究.     

Assessment of risk to humans of bisphenol A in marine and freshwater fish from Pearl River Delta, China

Bisphenol A (BPA) is a high production-volume chemical used in the manufacture of a wide variety of consumer products. However it is also a ubiquitous contaminant that can interfere with endocrine systems of wildlife and humans. China is the “world factory” and the Pearl River Delta is the major manufacturing center and is consequently polluted. Concentrations of BPA in meats of marketable fish had not been previously reported for this region. In the study upon which we report here concentrations of BPA were determined in 20 common species of freshwater and marine fish, collected from markets in Hong Kong, SAR, China. A comprehensive analytical method based on SPE extraction and liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) was developed, validated and applied. The method limit of detection (LOD) and limit of quantification (LOQ) were 0.5 and 1.25 ng g⁻¹ dw, respectively. BPA was detected in 19 species of fish at concentrations, ranging from 0.5 to 2.0 ng g⁻¹ ww. Average daily BPA intake per person ranged from 1.1 × 10² ng d⁻¹ for marine fish and 2.2 × 10² ng d⁻¹ for freshwater fish. Concentrations of BPA in fish from Hong Kong markets unlikely would be causing adverse population-level effects in humans.     

Determination of 4-tert-octylphenol, 4-nonylphenol and bisphenol A in surface waters from the Haihe River in Tianjin by gas chromatography-mass spectrometry with selected ion monitoring

The estrogenic pollutants 4-tert-octylphenol (OP), 4-nonylphenol (NP) and bisphenol A (BPA) were determined in surface water samples from the Haihe River, Tianjin, China. The analytes were extracted and concentrated from 300 ml acidified water samples by liquid–liquid extractions using dichloromethane, derivatized with trifluoroacetic anhydride, and quantified by gas chromatography–mass spectrometry (GC–MS) with selected ion monitoring (SIM). Among the samples collected from 14 sampling sites, only one sample was found to have a relatively high concentration of BPA (8.30 μg l⁻¹) and NP (0.55 μg l⁻¹). The concentrations of OP, NP and BPA in the other samples were in the range of 18.0–20.2, 106–296 and 19.1–106 ng l⁻¹, respectively. Recoveries for OP, NP and BPA in the spiked water samples were all over 80%.     

Parental phenols exposure and spontaneous abortion in Chinese population residing in the middle and lower reaches of the Yangtze River

Widespread use of phenols has led to ubiquitous exposure to phenols. In experimental animals, phenols increased resorptions, reduced live litter size and fetal body weights. However, there are limited epidemiological evidences of the relationships between exposure to phenols and pregnancy outcomes. We evaluated the associations between parental urinary levels of various phenols and spontaneous abortion in a Chinese population residing in the middle and lower reaches of the Yangtze River. A case-control study was conducted that included 70 case couples with medically unexplained spontaneous abortion and 180 control couples who did not have a history of spontaneous abortion and had at least one living child. Both parental urinary phenols were measured by ultra-high performance liquid chromatography-tandem mass spectrometry including bisphenol A (BPA), benzophenone-3 (BP-3), 2,3,4-trichlorophenol (2,3,4-TCP), pentachlorophenol (PCP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP). Compared with the low exposure group, there was an increased risk of spontaneous abortion with high paternal urinary PCP concentration [odds ratio (OR) = 2.09, 95% Confidence Interval (CI), 1.05–4.14], and maternal exposure to 4-n-OP and alkylphenol(s) also significantly increased the risk of spontaneous abortion (OR = 2.21, 95% CI, 1.02–4.80; OR = 2.81, 95% CI, 1.39–5.65, respectively). Our study firstly provides the evidence that paternal PCP exposure, maternal 4-n-OP and alkylphenol(s) exposure are associated with spontaneous abortion in humans.     

Changes in persistent contaminant concentration and CYP1A1 protein expression in biopsy samples from northern bottlenose whales, Hyperoodon ampullatus, following the onset of nearby oil and gas development

A small population of endangered northern bottlenose whales (Hyperoodon ampullatus) inhabits "The Gully" a Marine Protected Area on the Scotian Shelf, eastern Canada. Amid concerns regarding nearby oil and gas development, we took 36 skin and blubber biopsy samples in 1996-1997 (prior to major development) and 2002-2003 (five years after development began), and three samples from a population in the Davis Strait, Labrador in 2003. These were analysed for cytochrome P4501A1 (CYP1A1) protein expression (n=36), and for persistent contaminants (n=23). CYP1A1 showed generally low expression in whales from The Gully, but higher levels during 2003, potentially coincident with recorded oil spills, and higher levels in Davis Strait whales. A range of PCB congeners and organochlorine compounds were detected, with concentrations similar to other North Atlantic odontocetes. Concentrations were higher in whales from The Gully than from the Davis Strait, with significant increases in 4,4'-DDE and trans-nonachlor in 2002-2003 relative to 1996-1997.     

Occurrence, source diagnosis, and biological effect assessment of DDT and its metabolites in various environmental compartments of the Pearl River Delta, South China: A review

This review summarizes and analyzes available data in the literature (mostly after 2000) on the occurrence of dichlorodiphenyltrichloroethane (DDT) and its main metabolites, dichlorodiphenyldichloroethane (DDD) and chlorodiphenyldichloroethylene (DDE), in the environment of the Pearl River Delta (PRD), South China. Generally, the concentration levels of the sum of DDT, DDD, and DDE, designated as DDTs thereafter, have not significantly declined since 1983. However, the composition of DDTs residues has changed with time. DDTs in soil, freshwater sediment and freshwater fish species were mainly residues from chronological use. There is evidence that new point sources, such as dicofol and anti-fouling paint, may have contributed DDTs to various environmental compartments. Risk assessment against existing criteria indicated that the levels of DDTs in water and some fish species may pose adverse effects to humans or wildlife, and those in sediment/soil may also cause negative impacts to the eco-environment of the PRD.     

Ecotoxicological Assessment of Sediment, Suspended Matter and Water Samples in the Upper Danube River. A pilot study in search for the causes for the decline of fish catches (12 pp)

Goals, Scope and Background Fish populations, especially those of the grayling (Thymallus thymallus), have declined over the last two decades in the upper Danube River between Sigmaringen and Ulm, despite intensive and continuous stocking and improvement of water quality since the 1970s. Similar problems have been reported for other rivers, e.g. in Switzerland, Great Britain, the United States and Canada. In order to assess if ecotoxicological effects might be related to the decline in fish catch at the upper Danube River, sediment, suspended matter and waste water samples from sewage treatment plants were collected at selected locations and analyzed in a bioanalytical approach using a battery of bioassays. The results of this pilot study will be used to decide if a comprehensive weight-of-evidence study is needed. Methods Freeze-dried sediments and suspended particulate matters were extracted with acetone in a Soxhlet apparatus. Organic pollutants from sewage water were concentrated using XAD-resins. In order to investigate the ecotoxicological burden, the following bioassays were used: (1) neutral red assay with RTL-W1 cells (cytotoxicity), (2) comet assay with RTLW1 cells (genotoxicity), (3) Arthrobacter globiformis dehydrogenase assay (toxicity to bacteria), (4) yeast estrogen screen assay (endocrine disruption), (5) fish egg assay with the zebrafish (Danio rerio; embryo toxicity) and (6) Ames test with TA98 (mutagenicity). Results and Discussion The results of the in vitro tests elucidated a considerable genotoxic, cytotoxic, mutagenic, bacteriotoxic, embryotoxic and estrogenic burden in the upper Danube River, although with a very inhomogeneous distribution of effects. The samples taken from Riedlingen, for example, induced low embryo toxicity, but the second highest 17β-estradiol equivalent concentration (1.8 ng/L). Using the fish egg assay with native sediments, a broad range of embryotoxic effects could be elucidated, with clear-cut dose-response relationships for the embryotoxic effects of contaminated sediments. With native sediments, embryotoxicity was clearly higher than with corresponding pore waters, thus corroborating the view that – at least for fish eggs – the bioavailability of particle-bound lipophilic substances in native sediments is higher than generally assumed. The effect observed most frequently in the fish egg assay was a developmental delay. A comparison of our own results with locations along the rivers Rhine and Neckar demonstrated similar or even higher ranges of ecotoxicological burdens in the Danube River. Conclusions The complex pattern of ecotoxicological effects caused by environmental samples from the Danube River, when assessed in an in vitro biotest battery using both acute and more specific endpoints, showed that integration of different endpoints is essential for appropriate hazard assessment. Overall, the ecotoxicological hazard potential shown has indeed to be considered as one potential reason for the decline in fish catches at the upper Danube River. However, based on the results of this pilot study, it is not possible to elucidate that chemically induced alterations are responsible for the fish decline. Recommendations and Perspective . In order to confirm the ecological relevance of the in vitro results for the situation in the field and especially for the decline of the grayling and other fishes, further integrated investigations are required. For linking the weight of evidence obtained by in vitro assays and fish population investigations, the application of additional, more specific biomarkers (e.g. vitellogenin induction, EROD and micronucleus assay) has been initiated in fish taken from the field as well as in situ investigations.     

Occurrence and temporal variations of the xenoestrogens bisphenol A, 4-<Emphasis Type="Italic">tert</Emphasis>-octylphenol,and tech. 4-nonylphenol in two German wastewater treatment plants

GOAL, SCOPE, AND BACKGROUND: The xenoestrogens bisphenol A, 4-tert-octylphenol, and the technical isomer mixture of 4-nonylphenol (tech. 4-nonylphenol) belong to the group of chemicals which are called endocrine disrupters due to their property of causing hormonal dysfunctions in the endocrine system of organisms at very low concentrations. Bisphenol A, 4-tert-octylphenol, and the tech. 4-nonylphenol (mixture of isomers) were determined in water samples collected from the influent and effluent of two German wastewater treatment plants (WWTP) during a long-time sampling period from February 2003 till August 2005 to assess their occurrence and temporal variations in WWTPs. METHODS: The compounds were extracted and concentrated from water by solid-phase extraction (SPE) using Bond Elut PPL cartridges and quantified by use of gas chromatography-mass spectrometry (GC-MS). RESULTS: The influent concentrations were as follows: Bisphenol A < limit of detection of the method (< ldm)--12,205 ng L(-1), tech. 4-nonylphenol < ldm--10,186 ng L(-1), and 4-tert-octylphenol 39-1,495 ng L(-1). The measured effluent concentrations were lower with values in the range of < ldm--7,625 ng L(-1) for bisphenol A, < ldm--14,444 ng L(-1) for tech. 4-nonylphenol, and < ldm--392 ng L(-1) for 4-tert-octylphenol. All target compounds were largely eliminated during the wastewater treatment process. The elimination efficiency varied between 73% and 93%. DISCUSSION: All analytes show highly fluctuating influent concentrations with very high peak concentrations at particular sampling times. The variation of effluent concentrations is by far lower than the variation of influent concentrations. For tech. 4-nonylphenol, a significant temporal concentration variation has been detected with very high concentrations up to the microgram-per-liter level in the time from February 2003 till July 2003 and clearly decreasing concentrations in the time from June 2004 till August 2005. This corresponds well with the implementation of Directive 2003/53/EC (nonylphenol and nonylphenol ethoxylates in the European Union "may not be placed on the marked or used as a substance or constituent of preparations in concentrations equal or higher than 0.1% by mass") from January 2005 on. Bisphenol A is present in the effluent samples in a wide range of concentrations from below the detection limit to high concentrations up to the microgram-per-liter level. For 4-tert-octylphenol, no particular trend of concentration development has been observed. CONCLUSIONS: Combined SPE and GC-MS proved to be an efficient method to identify and quantify polar organic compounds in environmental samples. With respect to the concentrations measured in the present study, bisphenol A sometimes is the prominent compound in influent samples. Neither bisphenol A nor 4-tert-octylphenol or tech. 4-nonylphenol show seasonal variations. However, there was a significant general trend of decreasing concentrations of tech. 4-nonylphenol in influent and effluent samples from both WWTPs which probably reflects the implementing Directive 2003/53/EC. RECOMMENDATIONS AND PERSPECTIVES: Further research is needed to investigate whether the observed decrease of tech. 4-nonylphenol concentrations in German WWTPs since June 2004 will continue further on. The reason for the high effluent concentrations of bisphenol A in only a few samples has to be clarified in further research. The results from this study provide insight into the concentration development of the xenoestrogens bisphenol A, tech. 4-nonylphenol, and 4-tert-octylphenol in WWTPs in the time span between 2003 and 2005.