Estrogenic activity profiles and risks in surface waters and sediments of the Pearl River system in South China assessed by chemical analysis and in vitro bioassay

Estrogenic activity risks in the Pearl River system (Liuxi River, Zhujiang River and Shijing River) in South China were assessed by combined chemical analysis and recombinant yeast estrogen screen (YES) bioassay for surface waters and sediments collected in both dry and wet seasons. The xenoestrogens 4-tert-octylphenol, 4-nonylphenol and bisphenol A were detected at almost every sampling site at concentrations of several ng L(-1) (ng g(-1)) to tens of μg L(-1) (μg g(-1)) in surface waters (and sediments). The estrogens estrone and 17β-estradiol were also detected in most of the samples with concentrations from several ng L(-1) (ng g(-1)) to tens of ng L(-1) (ng g(-1)) in surface waters (and sediments). However, synthetic estrogens diethylstilbestrol and 17α-ethinylestradiol were only detected at a few sites. The 17β-estradiol equivalents (EEQ) screened by the YES bioassay were in the range of 0.23-324 ng L(-1) in surface waters and from not detected to 101 ng g(-1) in sediments. Shijing River displayed one to two orders of magnitude higher levels for both measured chemical concentrations and estrogenic activities than the Zhujiang River and the Liuxi River. A risk assessment for the surface waters showed high risks for the downstream reaches of the Liuxi River and the upstream to midstream reaches of the Zhujiang River and the Shijing River. Higher estrogenic risks were observed in the wet season than in the dry season for surface waters, probably due to the input of runoff and direct overflow of small urban streams during heavy rain events. Only small variations in estrogenic risk were found for the sediments between the two seasons, suggesting that sediments are a sink for these estrogenic compounds in the rivers.     

Bioluminescent yeast estrogen assay (BLYES) as a sensitive tool to monitor surface and drinking water for estrogenicity

Estrogenic Endocrine Disrupting Chemicals (EDCs) are a concern due to their ubiquity and recognized adverse effects to humans and wildlife. Methods to assess exposure to and associated risks of their presence in aquatic environment are still under development. The aim of this work is to assess estrogenicity of raw and treated waters with different degrees of pollution. Chemical analyses of selected EDCs were performed by liquid chromatography-tandem mass spectrometry, and estrogenic activity was evaluated using in vitro bioluminescent yeast estrogen assay (BLYES). Most raw water samples (18/20) presented at least one EDC and 16 rendered positive in BLYES. When EDCs were detected, the bioassay usually provided a positive response, except when only bisphenol A was detected at low concentrations. The highest values of estrogenic activity were detected in the most polluted sites. The maximum estrogenic activity observed was 8.7 ng equiv. of E2 L(-1). We compared potencies observed in the bioassay to the relative potency of target compounds and their concentrations failed to fully explain the biological response. This indicates that bioassay is more sensitive than the chemical approach either detecting estrogenic target compounds at lower concentrations, other non-target compounds or even synergistic effects, which should be considered on further investigations. We have not detected either estrogenic activity or estrogenic compounds in drinking water. BLYES showed good sensitivity with a detection limit of 0.1 ng equiv. E2 L(-1) and it seems to be a suitable tool for water monitoring.     

Ground level nitrogen dioxide concentrations in the rural Waikato Valley,New Zealand

Ground level nitrogen dioxide (NO₂) concentrations have been measured for one year over an area of 400 square kilometres in rural New Zealand using an array of 21 sites. Three passive samplers were exposed at each site for intervals of two weeks from August 1989 to August 1990. The exposure sites were centred around the Waikato Valley township of Huntly (population 6900). Important features of the survey area include a 1000 MW thermal power station situated on the outskirts of the town, the Waikato River and State Highway 1, a major north-south traffic route along the valley. The NO₂ concentrations in the survey area ranged from below 0.1 to 10.1 ppb, with an annual average of 1.2 ppb. Seasonal variations indicate summer values about three times lower than those found in the winter. The spatial distribution of NO₂ appears to be related to contributions from State Highway 1.     

Occurrence of estrogenic chemicals in South Korean surface waters and municipal wastewaters

Broad scale monitoring of estrogenic compounds was performed at 19 sampling points throughout the Yeongsan and Seomjin river basins and 5 wastewater treatment plants (WWTPs) adjacent to the Gwangju area, Korea, from December 2005 to August 2007. The concentrations of estrogenic compounds, including estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), bisphenol-A, nonylphenol (NP) and 4-octylphenol (OP), in the samples was measured with gas chromatography/mass spectrometry (GC-MS). In addition, the estrogenic activities throughout the river were investigated using the E-screen assay. Of the six estrogenic chemicals, NP (114.6-336.1 ng L(-1)) and EE2 (0.23-1.90 ng L(-1)) were detected at the highest and lowest levels, respectively in both the river waters and the WWTP effluents. Bisphenol-A showed the largest concentration range, from 7.5 to 335 ng L(-1). The concentrations of E1, E2 and octylphenol ranges were 3.6-69.1, 1.2-10.7, and 2.2-16.9 ng L(-1), respectively. According to the calculated estradiol equivalent concentration (EEQ); however, no estrogenic contribution was observed due to the phenolic compounds in the river waters and effluents. E1 and E2 dominated in both the river water and effluent samples, with contributions to the calculated EEQ of over 79 and 77%, respectively. Conversely, EE2 was rarely detected in the river waters (21%) and effluents (0%). The largest contribution of EE2 to the calculated EEQ was 21% in the river water at S-7. The levels of E1, E2, and EE2 were remarkably decreased in the effluents, indicating that the 5 WWTPs did not contribute to the estrogenic effect of the receiving streams. Overall, the WWTPs did not contributed to the estrogenic activity of the receiving waters, but the livestock industry or wildlife may play an important role in the estrogenic contribution to river water.     

Improved application of recombinant yeast assays on environmental samples by size exclusion chromatography

The utility of HPLC with a size exclusion chromatography (SEC) column for the fractionation of environmental samples was examined to expand the applicability of recombinant yeast assays (RYAs) for the measurement of estrogenic activity in environmental samples. The elution of steroidal hormone standards through SEC was tested, and river water and sediment samples were subjected to SEC fractionation. The retention times of all estrogen standards were longer than those of the major components with absorbance at 230 nm of the environmental sample matrix. The estrogenic activity of SEC fractions of environmental samples from highly polluted sites was measured using RYA and revealed the existence of estrogenic compounds that could not be detected or quantified in extracted samples before fractionation. The fractions from environmental samples that corresponded to the retention time of estrone, 17[small beta]-estradiol, and estriol were analyzed with LC/MS/MS. These three estrogens were separated into three different fractions, and the concentration of estrone coincided with the estrogenic activity of the fraction in which it was detected. The profile of estrogenic activity of SEC fractions indicated the molecular size of the estrogenic compounds and the yeast growth inhibitors in samples.     

Dynamics of steroid estrogen daily concentrations in hospital effluent and connected waste water treatment plant

Hospital effluent and connected waste water treatment plant (WWTP) influent and effluent were sampled daily to determine the levels and inter-day variations of three naturally occurring steroid estrogens: estrone, 17β-estradiol, estriol, and synthetic 17α-ethinylestradiol. After solid phase extraction, interferences were removed with a silica gel clean-up step and the samples analysed using gas chromatography with mass selective detection (GC-MSD). The determined inter-day concentrations in hospital effluent were between 8.6 to 31.3 ng L(-1) for estrone, 相似文献   

Possible biological significance of contaminated sediments in Port Jackson,Sydney, Australia

Comprehensive investigations of estuaries incentral New South Wales has identified Port Jackson as themost contaminated waterway on the eastern seaboard ofAustralia. Extensive areas of the estuary are mantled insediment containing high concentrations of a large range ofmetallic and organic contaminants. Although extensive, thisdatabase does not provide an effective basis for determiningthe potential adverse effects of chemicals on livingresources. In the absence of any ecotoxicologicalinformation, the recently published (1999) draft Australianand New Zealand Environmental and Conservation Council(ANZECC) sediment quality guidelines have been used toassess possible adverse biological effects of thesetoxicants. The ANZECC guidelines use the lower effects range of thewidely used U. S. National Oceanic and AtmosphericAdministration (NOAA) scheme to identify potentiallycontaminated sediment and as a threshold to trigger foradditional investigative work. This guideline level has beenused in the current study to assess possible toxicity ofcontaminated sediments in Port Jackson. It is estimated thatsediments in approximately 26% of the estuary, mainly theupper parts of the harbour and much of the central harbour,have a 67% probability of being toxic. Sediments in thecentral harbour and a major tributary, the Middle Harbour,comprising about 40% of the estuary, have a 13 to 25%probability of toxicity. All sediments in the harbour,except at the mouth of the estuary, would require additionalenvironmental assessment based on the proposed draft ANZECCsediment quality guidelines.     

A passive sampler for hydrogen sulfide

The silver nitrate/fluorescein mercuric acetate fluorimetric method for the measurement of atmospheric hydrogen sulfide has been adapted to passive sampling. Standard samplers have been tested and used in both indoor and outdoor environments. Sampler performance was not dependent on construction materials or sunlight intensity and gave similar results to active sampling. Two case studies were carried out, one in the Horniman Museum and its associated storage and study building, London, UK, and the other in the vicinity of a pulp and paper mill and geothermal area North Island, New Zealand. The detection limit of the samplers (50 ppt average for a one-week exposure) provides the opportunity to make measurements in a variety of locations provided exposure times are sufficiently long, i.e., up to one month in areas of low hydrogen sulfide concentration.     

Environmental estrogenic effects and gonadal development in wild goldfish (Carassius auratus)

Serum vitellogenin (VTG) contents of wild goldfish (Carassius auratus) were investigated as a sensitive biomarker for artificial estrogenic compounds in aquatic environments. Goldfish was sampled from a pristine area, a river situated 5 km downstream from a sewage treatment works (STW), and also from the Young-San River in Korea. The female yolk precursor protein VTG was not detected when gonadosomatic index (GSI) was less than 0.85%, while VTG levels of >10 microg/ml were found in males whose GSI was less than 1.53%. In male goldfish sampled from STW and the Young-San River, the higher VTG corresponded to lower GSI. This study suggested a trend that gonad development was connected to VTG levels in both sexes, and the application of GSI and histological analysis provide an attractive possibility that it could be included in the panel of markers used for estrogenic activity investigation of aquatic environments.     

Estrogenicity of pyrethroid insecticide metabolites

There is concern that insecticides are able to mimic the action of 17beta-estradiol by interaction with the human estrogen receptor. Pyrethroids are commonly used insecticides and several have been assessed for potential endocrine disrupting activity by various methods. It has been noted that some metabolites of pyrethroids, in particular, permethrin and cypermethrin, have chemical structures that are more likely to interact with the cellular estrogen receptor than the parent pyrethroid. For this study permethrin and cypermethrin metabolites 3-(4-hydroxy-3-phenoxy)benzyl alcohol, 3-(4-hydroxy-3-phenoxy)benzoic acid, and N-3-(phenoxybenzoyl)glycine were synthesised, and together with the commercially available 3-phenoxybenzyl alcohol, 3-phenoxybenzaldehyde, and 3-phenoxybenzoic acid, were studied in a recombinant yeast assay expressing human estrogen receptors (YES). Three metabolites, 3-phenoxybenzyl alcohol, 3-(4-hydroxy-3-phenoxy)benzyl alcohol, and 3-phenoxybenzaldehyde, showed estrogenic activity of approximately 10(5) less than that of 17beta-estradiol. No activity was observed in the yeast assay for 3-phenoxybenzoic acid, 3-(4-hydroxy-3-phenoxy)benzoic acid, and N-3-(phenoxybenzoyl)glycine. The results from this study show that pyrethroid metabolites are capable of interacting with the human estrogen receptor, and so might present a risk to human health and environmental well being. The impact would be expected to be small, but still add to the overall environmental xenoestrogen load.     

Vitellogenin induction in Cyprinus carpio treated with 17beta-estradiol and 4-nonylphenol

The aim of the present study was to demonstrate induction ofvitellogenin in the common carp (Cyprinus carpio) as abiomarker for monitoring freshwater ecosystems. Sexually undifferentiated specimens of common carp were treated experimentally with 17-estradiol and increasing doses of 4-nonylphenol and levels of plasma Vtg were measured in orderto: 1) validate an ELISA assay for plasma Vtg in the common carpusing the polyclonal rabbit anti-salmon Vtg antibody AA1 (Biosense, Norway); 2) check the sensitivity of carp juvenilesin producing Vtg in response to estrogen stimulation. The grouptreated with 17-estradiol showed high induction (156%)with respect to controls, also groups treated with 4-nonylphenolshowed induction of Vtg. The group treated with 100 mg kg^-1b.wt showed an induction of 61%. A statistically significantcorrelation was found between dose and response. This preliminary study demonstrate a response to the ELISA assay for Vtg in the common carp using rabbit anti-salmon antibody AA1. With further evidence the tested biomarker might be proposed for large scale monitoring of estrogenic effects caused by pollution in urban and industrial effluents.     

Human plasma levels of POPs,and diet among native people from Uelen,Chukotka

Some of the people living in the Chukotka Peninsula of Russia depend heavily on marine mammals, but little is known of the exact dietary patterns and plasma levels of POPs among these populations. In this study, POPs levels in plasma from 50 participants from the isolated community of Uelen (Bering Strait) were determined and related to dietary information obtained through a food frequency questionnaire. The intake of marine mammals was high and the combined intake of blubber from walrus, seal and whale was a significant predictor (p < 0.01) of plasma concentrations of sum PCBs and borderline for sum CDs (p = 0.02) and sum DDTs (p = 0.04). There was a significant gender difference in the levels of POPs, and among women there was a significant increase with age. Extensive breastfeeding and lower blubber intake among women could be possible explanations for this gender difference. Despite the high intake of blubber the plasma levels of PCBs and DDTs were lower than some of those reported for the East Coast of Greenland. The geometric mean values for sum PCBs (17 congeners) and sum DDTs were 1316 ng g(-1) lipids and 563 ng g(-1) lipids, respectively. PCB 163, which partly co-eluted with PCB 138, was found in high concentrations (40% of PCB 138). This raises questions regarding the validity of using PCB 138 and PCB 153 to calculate the level of Arochlor 1260. The geometric mean of sum CDs was 518 ng g(-1) lipids. Concentrations of beta-HCH (geometric mean; 410 ng g(-1) lipids) were higher than observed for other native populations depending on marine mammals. Transportation of beta-HCH by ocean currents through the Bering Strait into the Arctic Ocean or regional point sources might explain these elevated levels.     

Reproductive health indicators of fishes from Pennsylvania watersheds: association with chemicals of emerging concern

Fishes were collected at 16 sites within the three major river drainages (Delaware, Susquehanna, and Ohio) of Pennsylvania. Three species were evaluated for biomarkers of estrogenic/antiandrogenic exposure, including plasma vitellogenin and testicular oocytes in male fishes. Smallmouth bass Micropterus dolomieu, white sucker Catostomus commersonii, and redhorse sucker Moxostoma species were collected in the summer, a period of low flow and low reproductive activity. Smallmouth bass were the only species in which testicular oocytes were observed; however, measurable concentrations of plasma vitellogenin were found in male bass and white sucker. The percentage of male bass with testicular oocytes ranged from 10 to 100 %, with the highest prevalence and severity in bass collected in the Susquehanna drainage. The percentage of males with plasma vitellogenin ranged from 0 to 100 % in both bass and sucker. Biological findings were compared with chemical analyses of discrete water samples collected at the time of fish collections. Estrone concentrations correlated with testicular oocytes prevalence and severity and with the percentage of male bass with vitellogenin. No correlations were noted with the percentage of male sucker with vitellogenin and water chemical concentrations. The prevalence and severity of testicular oocytes in bass also correlated with the percent of agricultural land use in the watershed above a site. Two sites within the Susquehanna drainage and one in the Delaware were immediately downstream of wastewater treatment plants to compare results with upstream fish. The percentage of male bass with testicular oocytes was not consistently higher downstream; however, severity did tend to increase downstream.     

In situ polar organic chemical integrative sampling (POCIS) of steroidal estrogens in sewage treatment works discharge and river water

A passive sampler (the polar organic chemical integrative sampler; POCIS) was assessed for its ability to sample natural estrogens (17β-estradiol, E2; estrone, E1 and estriol, E3) and the synthetic estrogen (17α-ethynylestradiol, EE2) in the outlet of a sewage treatment works over several weeks. The performance of the POCIS was investigated and optimised in the laboratory before field deployment with high recoveries (66-99%) were achieved for all estrogens. Moreover, it was shown that POCIS does not exhibit any preferential selectivity towards any of the target compounds. The sampling rates of E1, E2 and E3 were 0.018 ± 0.009, 0.025 ± 0.014 and 0.033 ± 0.019 L d(-1), respectively. Following field deployments of 28 days in the discharge of a sewage works, POCIS was shown to enhance the sensitivity of estrogen detection, especially for E3, and provide time-weighted average (TWA) concentrations of E1, E2 and E3, ranging from undetectable to 12 ng L(-1) upstream of the outflow of a sewage treatment works, 13 to 91 ng L(-1) at the outflow and 8 to 39 ng L(-1) downstream of the outflow. This revealed that E1, E2 and E3 are not completely removed during sewage treatment, with concentrations most likely being maintained by contributions from conjugated estrogen analogues. Grab water samples showed considerable variation in the concentrations of estrogens over a longer period (6 months). The results confirm that POCIS is an effective and non-discriminatory method for the detection of low concentrations of estrogens in the aquatic environment.     

Daily dietary intakes of zinc,copper, lead,and cadmium as determined by duplicate portion sampling combined with either instrumental analysis or the use of food composition tables,Shiraz, Iran

Estimation of essential and toxic element intakes is crucial to evaluate the risks of deficiency or toxicity. The purpose of this study was to investigate and also to compare the dietary intakes of zinc (Zn) and copper (Cu) by adults living in Shiraz, Iran, determined by two procedures: duplicate portion sampling of 21 hospital meals combined with either instrumental analysis (voltammetric measurement) or the use of food composition tables (FCTs). The level of exposure to lead (Pb) and cadmium (Cd) was evaluated as well. The daily Zn intakes of both methods were not significantly different and were higher than the RDA values except the value measured by the instrumental analysis which was lower than the RDA established for a male adult. Daily intake of Cu determined by instrumental analysis was significantly lower and closer to RDA for adults compared with the value estimated by FCTs. The dietary intakes of Pb and Cd were 313 and 61 % of the respective provisional tolerable weekly intakes (PTWIs), respectively. The accuracy of two methods used for estimation of Zn intake was similar. In the case of Cu, the use of FCTs, in which the influence of environmental conditions and dietary habits of meal preparation is not taken into account, overestimated dietary intake. The risk of zinc deficiency was found in adult males. Moreover, the estimated intake of Pb, but not Cd, could be a cause of concern for Shiraz population. Thus, conducting regular periodic studies to assess the dietary intake of mentioned elements are recommended.     

Dietary exposure estimates of 16 polycyclic aromatic hydrocarbons (PAHs) in Xuanwei and Fuyuan, counties in a high lung cancer incidence area in China

Xuanwei and Fuyuan are located in the southwest of China and have the highest lung cancer incidence in China, possibly even highest in the world. Dietary samples were collected from these two counties and the contamination status of sixteen polycyclic aromatic hydrocarbons (PAHs) were determined. PAH components, food constituents, dietary exposure level, as well as spatial difference, were studied in the different groups. The percentage of dietary intake to total intake of PAHs was calculated and the relationship between the dietary intake of PAHs and the abnormal lung cancer incidence was primarily discussed. The results showed that rice and potatoes were the main foods of the local residents in Xuanwei and Fuyuan. The daily exposure doses of Bap (benzo[a]pyrene), total PAHs, and TEQs (toxic equivalents) based on Bap toxicity in two counties were estimated to be 458 ng d(-1), 14,532 ng d(-1), and 896 ng d(-1), respectively, which were much less than those in other cities reported previously. The lower ingestion amount of food with a relatively higher content of PAHs, such as meat and fish, could account for the lower exposure doses. PAHs with less than 4 rings occupied a high percentage of the total PAHs in food samples. The exposure doses varied significantly among different sites and even different families at the same site. Dietary exposure was not the main exposure route of PAHs at most sites. It appears that there was not a direct relationship between dietary exposure and the lung cancer incidence. However, high ratios of dietary intake to total PAHs intake (1.33%-70.61%) were found in several areas and rational diet suggestions should be given in these areas in the future.     

不同地域人发中重金属污染特征与来源解析

以某高校新生发样为研究样本,将生源地分为东北、西北、西南、华北、华南、华中、华东7个地域,采用电感耦合等离子发射光谱法对发样中所含铬、铜、镍、铅、锌进行测定,通过非参数检验及偏相关性检验分析不同地区发样中重金属含量与性别、身体质量指数(BMI)的关系。结果显示,所采集发样中铬、铜、镍、铅、锌的含量变化范围依次为0.22~101.84、0.36~112.24、0.70~128.75、1.39~136.13、1.12~719.50μg/g;发样中重金属浓度的地区排序为东北>华东>华北>西北>华中>西南>华南。聚类分析和主成分分析结果显示,不同地区发样中重金属的来源有所差异:东北、西北、华北地区发样中重金属可能主要来源于燃煤、工业生产过程、机动车排放,方差贡献率分别为39.47%、25.78%、22.89%;华中、华东、西南、华南地区发样中重金属可能主要来源于工业生产过程、机动车排放、冶金化工过程,贡献率分别为47.76%、27.51%、18.24%。相关性检验显示,男性发样内铬、铜、镍、铅含量高于女性。其中,偏胖或偏瘦女性存在较高的铅暴露风险;40.2%的男性发锌含量低于正常值下限,24.4%的女性发锌含量低于正常值下限,且偏瘦女性发内缺锌现象显著;男、女发铜含量高于正常值上限的比例分别为91.8%、85.6%,存在不同程度的铜暴露风险。     

Assessment of public exposure to naturally occurring radioactive materials from mining and mineral processing activities of Tarkwa Goldmine in Ghana

Studies have been carried out in a Goldmine in Ghana to determine the exposure of the public to naturally occurring radioactive materials from processing of gold ore. Direct gamma spectrometry and neutron activation analysis techniques were used to analyse soil, rock, water and dust samples from the mining environment. The mean activity concentrations measured for (238)U, (232)Th and (40)K in the soil/rock samples were 15.2, 26.9 and 157.1 Bq kg(?-?1), respectively. For the water samples, the mean activity concentrations were 0.54 and 0.41 Bq l(?-?1)) and 7.76 Bq l(?-?1) for (226)Ra, (232)Th and (40)K, respectively. The mean activity concentrations measured in the dust samples were 4.90 and 2.75 μBq m(?-?3) for (238)U and (232)Th, respectively. The total annual effective dose to the public was estimated to be 0.69 mSv. The results in this study compared well with typical world average values. The results indicate an insignificant exposure of the public from the activities of the Goldmine.     

Determination of naphthalene by competitive fluorescence immunoassay

A reliable and sensitive competitive fluorescence immunoassay for the quantitative determination of naphthalene (NA) was developed. 2-naphthoxy acetic acid (NAA) was selected as the hapten of naphthalene. Active ester method (AEM) was used to couple the NAA to carrier proteins (bovine serum albumin) to form artificial immune antigen. Male New Zealand white rabbits were immunized with this antigen to obtain polyclonal antibodies, with which, a novel fluorescence immunoassay for detection of NA was described. Under best conditions, NA can be determined in the concentration range of 0.1-100 microg/L with a detection limit of 0.05 microg/L. The cross-reactivities of the anti-NA antibody to seven structurally related compounds were below 15%. Some environmental samples were analyzed with satisfactory results. It shows a good accuracy and suitability to analyze NA in environmental water.