Environmental estrogens in an urban aquatic ecosystem: I. Spatial and temporal occurrence of estrogenic activity in effluent-dominated systems

The present study investigated occurrence of environmental estrogens (EEs) in waterways managed by the Metropolitan Water Reclamation District of Greater Chicago (‘District’) — one of the largest and most complex water districts in the United States. The objectives of the study were: (i) to document spatial and temporal occurrence of EEs in the Chicago Area Waterways (CAWs); (ii) to determine whether water reclamation plant (WRP) effluents contribute to estrogenic pollution of the receiving streams; (iii) to determine whether the mandated water quality monitoring data could be used to predict estrogenic pollution in the receiving streams; and (iv) to determine whether snow melt, storm runoff and combined sewer overflows may also be contributors of estrogenic activity to these systems. The estrogenic potency of the waterways was assessed using a cell-based reporter gene assay. The water quality data was readily available as part of the District's regular monitoring program. Our findings indicate that EEs are commonly found in the CAWs, and that WRP effluents are one of, but not the only important contributor to estrogenic activity. Mean estrogenic activities in CAWs (11 ng estradiol equivalents (EEQs/L)) are well within the values reported for other urban areas and WRP effluents. The estrogenic activity exhibited significant seasonal variation with highest values noted during the spring and summer months. When comparing the mean estrogenic activity of general use waters, secondary contact waters and WRP effluents, we found that general use waters had significantly lower estrogenic activity (ca 5 ng EEQ/L) than the other two matrices (ca 15 and 17 ng EEQ/L respectively). Our analyses indicate that estrogenic activity of the waterways was not reliably associated with mandated water quality parameters, and that such measurements may not be useful for predicting estrogenic activity, especially so in the complex urban systems. One of the prominent findings of this study is that EEs do not follow predictable spatial patterns — many of the upstream sites in the heavily urbanized areas had levels of estrogenic activity comparable to those found in the effluents and downstream locations. Our data suggest that surface runoff and snow melt are estrogenic (0–9 ng EEQ/L), and given that their estrogenic activities are similar to those of their receiving waterways (0–7 ng EEQ/L), we conclude that these non-WRP sources are important contributors to estrogenic activity of the CAWs.     

Environmental fate of alkylphenols and alkylphenol ethoxylates--a review

Alkylphenol ethoxylates (APEs) are widely used surfactants in domestic and industrial products, which are commonly found in wastewater discharges and in sewage treatment plant (STP) effluents. Degradation of APEs in wastewater treatment plants or in the environment generates more persistent shorter-chain APEs and alkylphenols (APs) such as nonylphenol (NP), octylphenol (OP) and AP mono- to triethoxylates (NPE1, NPE2 and NPE3). There is concern that APE metabolites (NP, OP, NPE1-3) can mimic natural hormones and that the levels present in the environment may be sufficient to disrupt endocrine function in wildlife and humans. The physicochemical properties of the APE metabolites (NP, NPE1-4, OP, OPE1-4), in particular the high K(ow) values, indicate that they will partition effectively into sediments following discharge from STPs. The aqueous solubility data for the APE metabolites indicate that the concentration in water combined with the high partition coefficients will provide a significant reservoir (load) in various environmental compartments. Data from studies conducted in many regions across the world have shown significant levels in samples of every environmental compartment examined. In the US, levels of NP in air ranged from 0.01 to 81 ng/m3, with seasonal trends observed. Concentrations of APE metabolites in treated wastewater effluents in the US ranged from < 0.1 to 369 microg/l, in Spain they were between 6 and 343 microg/l and concentrations up to 330 microg/l were found in the UK. Levels in sediments reflected the high partition coefficients with concentrations reported ranging from < 0.1 to 13,700 microg/kg for sediments in the US. Fish in the UK were found to contain up to 0.8 microg/kg NP in muscle tissue. APEs degraded faster in the water column than in sediment. Aerobic conditions facilitate easier further biotransformation of APE metabolites than anaerobic conditions.     

Effects of 17alpha-ethinylestradiol on the reproduction of the cladoceran species Ceriodaphnia reticulata and Sida crystallina

Single-species tests allow the assessment of chronical effects of endocrine disruptors on organisms under laboratory conditions. In the current study, three-generation tests with Ceriodaphnia reticulata and Sida crystallina were carried out to examine the influence of the synthetic hormone 17alpha-ethinylestradiol (EE) on the reproduction of these cladoceran species. For each species, six different concentrations (10-500 microg/l EE) and two controls were tested with eight replicates for a duration of 4 weeks. The test was initiated by transferring one neonate individual into a test vessel which was incubated under standardized conditions. Every 2 days, the medium was renewed and life history parameters such as survivorship of the adults and juveniles, clutch size, first appearance and number of produced offspring were investigated. Acute toxicity tests showed that C. reticulata (EC50 (24 h) 1814 microg/l) was more sensitive towards the substance compared to S. crystallina (EC50 (24 h) >4100 microg/l). The juvenile phase of S. crystallina was significantly shorter at concentrations above 100 microg/l EE. For C. reticulata, 17alpha-ethinylestradiol caused a higher mortality of the newly hatched juveniles at EE concentrations above 200 microg/l. No effects were found for mortality of adult animals, birth rate, number of juveniles per female and net reproduction rate of S. crystallina and C. reticulata. Thus, sublethal effects on parental generation exposed to EE lead to disturbances in reproduction and to affection of their offspring. Negative consequences for the population dynamic cannot be excluded, e.g. the decrease of a population.     

Estrogenic and androgenic activities in total plasma measured with reporter-gene bioassays: relevant exposure measures for endocrine disruptors in epidemiologic studies?

Measurements of estrogenic and androgenic activities in total plasma with Chemically Activated LUciferase gene eXpression (CALUX?) bioassays could provide biologically relevant measures for exposure to endocrine disruptors in epidemiologic studies. The objective of this study was to explore the effects of a variety of sources of potential endocrine disruptors on estrogenic and androgenic activities in total plasma measured by CALUX?. Plasma samples and interview data on sources of potential endocrine disruptors were collected from 108 men with different exposures profiles. CALUX? measurements (BioDetection Services) involved human U2-OS cell lines controlled by the estrogen receptor alpha and the androgen receptor. Mean differences (beta) in 17β-estradiol equivalents (EEQs) and dihydrotestosterone equivalents (AEQs) between exposure groups were estimated using general linear models. Mean plasma AEQs and EEQs were 9.1×10(-1)ng/ml and 12.0pg/ml, respectively. Elevated AEQs were found in smokers (beta 1.9 (95%CI 0.1-3.6)×10(-1)ng/ml) and heavy drinkers (1.4 (0.2-3.1)×10(-1)ng/ml), and in men occupationally exposed to disinfectants (1.6 (0.3-3.5)×10(-1)ng/ml) or welding/soldering fumes (1.4 (-0.2-2.9)×10(-1)ng/ml). Occupational exposure to pesticides, disinfectants, and exhaust fumes seemed to be associated with increased plasma EEQs: 1.5 (-0.2-3.2)pg/ml, 2.1 (0.2-3.9)pg/ml, and 2.9 (0.6-5.2)pg/ml, respectively. Moderate to high plasma dioxin levels, measured in a subgroup by the dioxin-responsive CALUX?, were accompanied by a 20% increase in AEQs. This is the first study in which CALUX? was used to assess hormone activities in total plasma. Although the results are not yet readily interpretable, they indicate that these measurements can be valuable for epidemiologic studies on endocrine disruptors and give direction for further research.     

Estrogenic activity in extracts and exudates of cyanobacteria and green algae

Here is presented some of the first information on interactions of compounds produced by cyanobacteria and green algae with estrogen receptor signaling. Estrogenic potency of aqueous extracts and exudates (culture spent media with extracellular products) of seven species of cyanobacteria (10 different laboratory strains) and two algal species were assessed by use of in vitro trans-activation assays. Compounds produced by cyanobacteria and algae, and in particular those excreted from the cells, were estrogenic. Most exudates were estrogenic with potencies expressed at 50% of the maximum response under control of the estrogen receptor ranging from 0.2 to 7.2 ng 17β-estradiol (E₂) equivalents (EEQ)/L. The greatest estrogenic potency was observed for exudates of Microcystis aerigunosa, a common species that forms water blooms. Aqueous extracts of both green algae, but only one species of cyanobacteria (Aphanizomenon gracile) elicited significant estrogenicity with EEQ ranging from 15 to 280 ng 17β-estradiol (E₂)/g dry weight. Scenedesmus quadricauda exudates and extracts of Aphanizomenon flos-aquae were antagonistic to the ER when coexposed to E₂. The EEQ potency was not correlated with concentrations of cyanotoxins, such as microcystin and cylindrospermopsin, which suggests that the EEQ was comprised of other compounds. The study demonstrates some differences between the estrogenic potency of aqueous extracts prepared from the same species, but of different origin, while the effects of exudates were comparable within species. The observed estrogenic potencies are important namely in relation to the possible mass expansion of cyanobacteria and release of the active compounds into surrounding water.     

Derivation of a screening methodology for evaluating radiation dose to aquatic and terrestrial biota

The United States Department of Energy (DOE) currently has in place a radiation dose standard for the protection of aquatic animals, and is considering additional dose standards for terrestrial biota. These standards are: 10 mGy/d for aquatic animals, 10 mGy/d for terrestrial plants, and, 1 mGy/d for terrestrial animals. Guidance on suitable approaches to the implementation of these standards is needed. A screening methodology, developed through DOE's Biota Dose Assessment Committee (BDAC), serves as the principal element of DOE's graded approach for evaluating radiation doses to aquatic and terrestrial biota. Limiting concentrations of radionuclides in water, soil, and sediment were derived for 23 radionuclides. Four organism types (aquatic animals; riparian animals; terrestrial animals; and terrestrial plants) were selected as the basis for development of the screening method. Internal doses for each organism type were calculated as the product of contaminant concentration, bioaccumulation factor(s) and dose conversion factors. External doses were calculated based on the assumption of immersion of the organism in soil, sediment, or water. The assumptions and default parameters used provide for conservative screening values. The screening methodology within DOE's graded approach should prove useful in demonstrating compliance with biota dose limits and for conducting screening assessments of radioecological impact. It provides a needed evaluation tool that can be employed within a framework for protection of the environment.     

Measurement of estrogenic activity in sediments from Haihe and Dagu River, China

Sediments from two rivers in China, the Haihe and Dagu Rivers, were examined for estrogenic activity using an estrogen receptor (ER)-mediated in vitro bioassay system. ER-active compounds were isolated from sediments by Soxhlet extraction, and the crude extracts were fractionated using a florisil column into three fractions. The estrogenic activity of each extract was detected by measuring luciferase activity in the human breast cancer cell line MCF-7 transfected with a luciferase receptor gene. Significant estrogenic activity was observed in each total extract. The 17beta-estradiol equivalents (E2-EQs) ranged from 8.24 to 95.28 ng E2 g(-1) dw. As a result, the relative estrogenic potencies of three fractions in this study descended in the order of Fraction 3>Fraction 2>Fraction 1. The results of the bioassay analysis indicated the heavy pollution status of these sites with estrogenic contaminants. In this study, five selected chemicals, the natural estrogens 17beta-estradiol (E2) and estrone (E1), and the xeno-estrogens 4-octylphenol (OP), 4-nonylphenol (NP), and Bisphenol A (BPA) were also analyzed using the in vitro bioassay. The estrogenic activity of these chemicals were E2>E1>NP>OP>BPA.     

长江口九段沙水域有机氯农药分布

对九段沙（HCHs）水域采集滩涂水样以及沉积物，进行GC-ECD检测，研究有机氯农药的分布。结果表明，九段沙水域水体中六六六含量为6．6～17．1ng／L，平均值9．93ng／L，滩涂沉积物中的六六六含量为2．32～6．30ng／g；九段沙水域水体中滴滴涕（DDTs）含量4．99～46．6ng／L，平均值为18．53ng／L，滩涂泥样中的滴滴涕（DDTs）含量5．9～70．83ng／g。从异构体成分分析，九段沙水域受到了陆上林丹使用的影响，但是东海海水的冲刷能降低林丹所占六六六含量的比例；另外滴滴涕则显示较早期的污染，表现为代谢物（DDD和DDE）含量较高的现象，同时调查发现该水域在近期可能有滴滴涕输入。     

Distribution of pesticides, PAHs and heavy metals in prawn ponds near Kolleru lake wetland, India

This paper discussed the distribution of pesticides, polycyclic aromatic hydrocarbons (PAHs) and heavy metals in water, sediment and prawn from intensive prawn ponds (n=8) near the Kolleru lake wetland, India and assessed the quality of prawn for human consumption and also discussed the possible effects of these pollutants on pond environment and aquatic environment. The chemicals and other products used in prawn ponds near the Kolleru lake wetland were documented. The sediment, prawn and water samples were collected six times from selected prawn ponds during the production period of 3 months. Water samples were analyzed for selected physico-chemical parameters. The levels of pesticides, PAHs and heavy metals were found to decrease in the order sediment followed by prawn and water. The maximum concentrations of pesticides in sediment, prawn and water were alpha-BHC (174.2 microg g(-)(1)), gamma-BHC (234 microg g(-)(1)), malathion (256 microg g(-)(1)), chloripyrifos (198.5 microg g(-)(1)), endosulfan (238 microg g(-)(1)), dieldrin (19.6 microg g(-)(1)) and p,p'-DDT (128.6 microg g(-)(1)). Isodrin was found below detectable limit. The maximum concentrations of PAHs in sediment, prawn and water are anthracene (0.901 microg kg(-)(1)), fluranthene (0.601 microg kg(-)(1)), pyrene (0.786 microg kg(-)(1)), chrysene (0.192 microg kg(-)(1)), benzo(a)pyrene (0.181 microg kg(-)(1)) and benzo(ghi)perylene (227 microg kg(-)(1)). Benzo(e)pyrene, perylene, isomers of dibenzoanthracene and coronene were found below detectable limits. The maximum concentrations of heavy metals in sediment, prawn and water and also in prawn feed are Cu (791 microg g(-)(1)), Pb (270 microg g(-)(1)), Cd (1.07 microg g(-)(1)), Mn (4417 microg g(-)(1)), Ni (8.1 microg g(-)(1)), Co (5.8 microg g(-)(1)), Zn (1076 microg g(-)(1)), Cr (36.4 microg g(-)(1)), As (2.9 microg g(-)(1)), Se (6.3 microg g(-)(1)), Th (2.1 microg g(-)(1)) and Mo (0.762 microg g(-)(1)).     

Daily intake of 4-nonylphenol in Taiwanese

Alkylphenol polyethoxylates (APEO), alkylphenols combined with ethylene oxide, are a class of nonionic surfactants. APEO have been widely used for industrial, agricultural and household applications, and are biodegraded to more persistent and estrogen-active products, namely, nonylphenol (NP), octylphenol (OP), butylphenol (BP), nonylphenol monoethoxylate (NP(1)EO) and nonylphenol diethoxylate (NP(2)EO). This study determined NP levels in commonly consumed foodstuffs to assess daily intake of NP in a Taiwanese population. This study analyzes 318 of samples from 25 types of commonly consumed foodstuffs in northern, central, southern and eastern regions of Taiwan and estimates daily intake of NP in 466 subjects. Moreover, daily NP intake for 3915 additional subjects was estimated by analyzing data from the Nutrition and health survey in Taiwan (NAHSIT). The foodstuff samples were analyzed for five alkylphenol compounds simultaneously by HPLC with fluorescence detection. Additionally, the average compositions of typical foods consumed in Taiwan were investigated. In combination with alkylphenol levels in these foodstuffs, daily intake of NP in Taiwanese was calculated. The average daily intake of NP for the 466 subjects was 28.04+/-25.32 microg/day. Estimated daily intake of NP, based on NP levels in this study as well as the NAHSIT data, was 31.40 microg/day. Rice was the most commonly consumed source of NP, the proportion was 21.46% among daily intake of NP and the following were aquatic products and livestock, which percentage were 17.97% and 17.38%, respectively. Additionally, oysters had the highest NP levels (235.8+/-90.7 ng/g) in four regions of Taiwan, followed by salmon (123.8+/-116.2 ng/g). This study suggested that the average daily NP intake in Taiwan is 4-fold and 8.5-fold higher than daily intake in Germany and New Zealand, respectively and rice was the major source of NP intake.     

Development and validation of an enzyme-linked immunosorbent assay for vitellogenin in Chinese loach (Misgurnus angaillicaudatus)

A competitive enzyme-linked immunosorbent assay (ELISA) was developed for the quantification of vitellogenin (Vtg) in the plasma of Chinese loach (Misgurnus angaillicaudatus). Vtg was isolated by anion exchange membrane chromatography from the plasma of 17beta-estradiol (E(2))-treated loach. Polyclonal antibody against Vtg was raised in rabbits, and the specificity of the antibody was assessed by Western blotting analysis. No cross-reactivity was observed with plasma from male loach. Plasma samples from vitellogenic females and E(2)-treated males were diluted parallel with the purified Vtg standard curve in the ELISA. The detection limit of the assay was 5.7 ng ml(-) (1) and a working range of the standard curve was between 15.6 and 1000 ng ml(-) (1). The intra- and inter-assay coefficients of variations were 6.9% and 10.4%, respectively. The recovery was 104.4%. The assay was applied for measuring vitellogenin concentration in the plasma from 24 wild Chinese loach from Lianyungang, Jiangsu Province, in October 2003. It was found that, in addition to females (plasma Vtg concentration ranging from 518.4 microg ml(-) (1) to 1922.3 microg ml(-) (1)), male loach showed low plasma Vtg--from undetectable (two fish) to 2.9+/-0.7 microg ml(-) (1) (mean+/-S.D.). The results indicate that this method provides a valuable tool for the study of estrogenic effect in Chinese loach.     

Derivation of ecotoxicity thresholds for uranium

Assessment of the risk of impact from most radionuclides is based on the total radiological dose rate to the organism of concern. However, for uranium (U) there can be greater risk from chemical toxicity than radiological toxicity (depending on the isotopic composition). Chemical ecotoxicity of U is dependent on several environmental parameters. The most important are carbonate content, because of the formation of soluble carbonate complexes, and divalent cation content (Ca++ and Mg++), because of their competitive interaction with the uranyl ion (UO2++). This study summarizes the literature available to set PNECs (predicted no-effect concentrations) for chemical toxicity of U to non-human biota. The corresponding radiological doses were estimated, and as expected chemical toxicity proved to be the greater concern. There were limited data from some types of biota; however, PNECs for the types of biota of interest were as follows: terrestrial plants--250 mg U kg(-1) dry soil; other soil biota--100 mg U kg(-1) dry soil; freshwater plants--0.005 mg U L(-1) water; freshwater invertebrates--0.005 mg U L(-1) water; freshwater benthos--100 mg U kg(-1) dry sediment; freshwater fish at water hardnesses of: <10 mg CaCO3 L(-1) (very soft water)--0.4 mg U L(-1) water; 10-100 mg CaCO3 L(-1) (soft water)--2.8 mg U L(-1) water; and >100 mg CaCO3 L(-1) (hard water)--23 mg U L(-1) water; or as a function of hardness--0.26 (hardness as mg CaCO3 L(-1); mammals--0.1 mg U kg(-1) body weight d(-1).     

Comparative study of estrogenic potencies of estradiol, tamoxifen, bisphenol-A and resveratrol with two in vitro bioassays

This study was undertaken to compare the sensitivity of two in vitro screening test methods and to determine the accuracy of predicted response to spiked laboratory water samples. A newly developed enzyme-linked receptor assay (ELRA) and a widely used yeast estrogen screen (YES) assay were selected to evaluate the estrogenic responses. Four natural, pharmaceutical, xenobiotic or phytobiotic chemicals: 17beta-estradiol (E2), tamoxifen, bisphenol-A and resveratrol were examined, and 17beta-E2 was used as a positive control. 17beta-E2 can strongly induce estrogenic response in both test systems, however, ELRA was found to be more sensitive to 17beta-E2 with a detection limit of 0.07 microg/l compared to 0.88 microg/l in YES assay. Similar results were obtained for bisphenol-A and resveratrol, and their estrogen potencies relative to E2 (100%) determined by ELRA were at least 5.6 times greater than produced by YES assay. ELRA was unable to distinguish the anti-estrogen tamoxifen and YES assay is also poor at distinguishing. Comparison of response to spiked laboratory water samples show that ELRA can give accurate determination to all four chemicals with recoveries among 70-120%, while YES can only give accurate determination to 17beta-E2 and bisphenol-A with recoveries among 69-112%. The comparative results provide evidence that ELRA is more suitable for rapid screening estrogenic potency of the environmental samples. Combination of ELRA and mammalian cellular assay will constitute an advantageous test to specify agonistic or antagonistic effects.     

Distribution and dissipation pathways of nonylphenol polyethoxylates in the Yellow River: Site investigation and lab-scale studies

Spatial distribution of nonylphenol polyethoxylates (NPEOs) and nonylphenol (NP) was investigated in a field study in Lanzhou Reach of the Yellow River. NPEOs and their metabolites were found in the river, with the maximum dissolved concentrations of 6.38 nmol/L for NPEOs, 0.19 nmol/L for nonylphenol ethoxy acetic acids (NPECs) and 0.79 nmol/L for NP, respectively. The maximum concentrations in the sediment and suspended particle samples were 1.50 and 5.09 nmol/g for NPEOs and NP, respectively. The effects of particles, light and microorganism on the dissipation of NPEOs in the river water were investigated based on lab-scale experiments. When natural particles were removed, 72% and 22% degradation of NPEOs were achieved at 120 h in non-sterile and sterile conditions with light, respectively. Different concentrations of NPECs were also observed in these experiments. When suspended particle matters (SPMs) were present, about 38-50% of NPEOs were sorbed to the particulate phase in only 1 h. As a result, the degradation of NPEOs and production of NPECs were inhibited. However, the combined sorption and degradation in the presence of SPMs resulted in lower dissolved NPEO concentrations than those in the absence of SPMs. Biodegradation was the most important pathway for NPEOs degradation in the river water, while NPECs seemed to be produced through both biological and abiological pathways.     

Organochlorine compounds and heavy metals in the soft tissue of the mussel Mytilus galloprovincialis collected from Lake Faro (Sicily, Italy)

Three hundred samples of Mytilus galloprovincialis were collected from five stations (north, south, east, west and centre) of Lake Faro to evaluate the concentrations of organochlorine compounds and heavy metals. Quantitative determinations of organochlorine pesticides and PCBs were made by GC-ECD and confirmed with GC-MS. Concentrations of "essential" (Cu, Se and Zn) and "toxic" (As, Cd, Hg and Pb) metals were determined by an atomic absorption spectrophotometer. The results obtained show the low residue levels of p,p'-DDE in six samples of M. galloprovincialis from southern (7.00-11.00 ng/g w.w. and 148.3-275 ng/g l.w.) and western (7.60-15.37 ng/g w.w. and 126.7-256.2 ng/g l.w.) areas of Lake Faro. No appreciable residues of PCBs were found in any of the samples examined. Zn concentrations (range 11.0-18.5 microg/g w.w.) were higher than Cu (range 188.3-396.0 ng/g w.w.) and Se (range 93.5-288.9 ng/g w.w.) in all areas of origin. Cd (range 41.9-63.8 ng/g w.w.), Pb (range 64.8-93.0 ng/g w.w.) and Hg levels (range 5.7-13.1 ng/g w.w.) showed lower concentrations than permitted MRLs. The As levels were below detection limits for the all mussel samples. In conclusion, the absence of PCBs, the low levels of p,p'-DDE, the concentrations of Cd, Hg and Pb below permitted MRLs in M. galloprovincialis, used as a "biological indicator", show that Lake Faro is not at contamination risk from these contaminants and moreover is free from health problems for the consumer of mussel products.     

Persistent organic pollutants in the Scheldt estuary: Environmental distribution and bioaccumulation

Levels of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs) were determined in the sediment and several species (European flounder, Platichthys flesus; common sole, Solea solea; Chinese mitten crab, Eriocheir sinensis; shore crab, Carcinus maenas; brown shrimp, Crangon crangon; blue mussel, Mytilus edulis and bristle worms, Polychaeta) from 7 locations in the Scheldt estuary (SE, the Netherlands–Belgium). Overall POP levels in the sediment were low. The average PCB and PBDE concentrations were respectively 31.5 and 115 ng/g dry weight (dw). Highest sediment loads were measured in the vicinity of Antwerp (368 ng PCBs/g dw), a location with intense harbor and industrial activities. Pollution concentrations in the tissues of biota were species-specific. Blue mussels contained the highest lipid concentrations (2.74 ± 0.55%) and reached the highest contamination levels (from 287 to 1688 ng PCBs/g ww, from 2.09 to 12.4 ng PBDEs/g ww). Lowest tissue loads were measured in brown shrimp (from 3.27 to 39.9 ng PCBs/g ww, from 0.05 to 0.47 ng PBDEs/g ww). The PCB congener profile in most of the species was similar with the pattern found in the sediment. PCB 153 was the most abundant congener (16.5–25.7% in biota, 10.4% in sediment). In the sediment, the total amount of PBDEs consisted for more than 99% of BDE 209. Congener BDE 47 had the highest concentrations in all sampled species (38.5–70.1%). Sediment POP loadings and tissue concentrations were poorly correlated, indicating that a simple linear or non-linear relationship is insufficient to describe this relationship, possible caused by the complexity of the bioaccumulation processes and the variability in exposure. Because of the high PCB levels, regular consumption of fish and seafood, especially mussels, from the Scheldt estuary should be avoided.     

Occurrence of phthalate esters in water and sediment of urban lakes in a subtropical city, Guangzhou, South China

Extensive use of phthalate esters (PAEs) in both industrial processes and consumer products has resulted in the ubiquitous presence of these chemicals in the environment. This study reports the first data on the concentrations of 16 phthalate esters (PAEs) in water and sediments of the urban lakes in Guangzhou City. PAEs were detected in all samples analyzed, mainly originating from urban stormwater runoff, atmospheric deposition, as well as untreated discharge of industrial wastewater and municipal sewage. The Sigma(16)PAEs concentrations in water and sediments ranged from 1.69 to 4.72 microg L(-1) and 2.27 to 74.94 microg g(-1)-dry weight (dw), with the mean concentrations of 2.91 microg L(-1) and 20.85 microg g(-1)-dw, respectively, which indicates that sediment is a significant sink for PAEs. Variability of the Sigma 16PAEs concentrations in water and sediment in the urban lakes was almost consistent. The spatial distribution of PAEs was site-specific. Of the 16 PAEs, DMP, DEP, DnBP, DiBP, DMPP, and DEHP were present in all water and sediment samples. DnBP was abundant in water (53.0-81.2%), while no single dominant congener was found in sediments. The abundances of DiBP were similar to those of DEHP, and DiBP and DEHP collectively accounted for 77.2-97.6% of the Sigma 16PAEs concentrations. Congener specific analysis confirmed that DnBP was a predictive indicator for the dissolved summation operator16 PAEs concentration (correlation coefficient r=0.968, p<0.01), and that DiBP was a predictive indicator for the sediment summation operator16 PAEs concentration (r=0.975, p<0.01). As compared to the results for other studies, the urban lakes of Guangzhou were moderately polluted by PAEs.     

Estuarine and coastal zone marine pollution by the nonionic alkylphenol ethoxylates endocrine disrupters: is there a potential ecotoxicological problem?

The nonionic biodegradation-resistant ("hard") alkylphenol ethoxylate (APEO) surfactants and their degradation products are known endocrine disrupting chemicals (EDCs). We report here the findings concerning the APEOs concentrations and homologic distribution profiles in Israel's estuarine and coastal zone seawater to serve as a case study. The concentrations in sewage-containing rivers, estuaries and 50-60-m offshore sea (Mediterranean) water were found to be 12.5-75.1, 4.2-25.0 and 0.9-2.6 microg/L, respectively. The corresponding homologic distribution profiles were found to be within the range of 1-10% each, somewhat skewing, as expected, towards the more toxic shorter-chain ethoxylates. Egg production by zebrafish, exposed to 75, 25 and 10 microg/L of a typical industrial APEOs was reduced up to 89.6%, 84.7% and 76.9%, respectively, between the 8th and 28th days of exposure. Apparently, there is a potential APEOs-related ecotoxicological health risk problem.     

Pollution historical trends as recorded by sediments at selected sites of the Venice Lagoon

Polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and hexaclorobenzene (HCB) were determined in three sediment cores of the Venice Lagoon: I1, from the San Giuliano Canal that is likely the main source of pollutants for the study area; E, representing the lagoon sediment of the zone of Campalto; and M3, typical of a salt marsh environment and mostly subject to atmospheric inputs. Maximum concentrations were found in core I1: 25-1858 ngI-TE kg(-1) (PCDD/Fs), 1.7-13 microg kg(-1) (HCB), and 107-717 microg kg(-1) (PCBs) are surficial and peak values, respectively. The lagoon sediment (E), is much less contaminated: 24-47 ngI-TE kg(-1) for PCDD/Fs, 2.3-3.6 microg kg(-1) for HCB, and 56-203 microg kg(-1) for PCBs, whereas M3 shows the lowest values: 1.6-6.0 ngI-TE kg(-1) for PCDD/Fs, 0.3-0.6 microg kg(-1) for HCB, and 7.1-39 microg kg(-1) for PCBs. In any case, the recent trend is toward a decrease of pollutant concentration. The chronology of cores E and M3 is based on both 210Pb and 137Cs activity-depth profiles. The maximum concentrations of PCDD/Fs, HCB, and PCBs correspond to the years 1949, 1980, and 1968, respectively. The homologue profiles of PCDD/Fs confirm that I1 has been subject to an industrial source while the other sites also recorded significant contributions, changing over time, of octachlorinated dioxin from combustion. A comparison of the pollutant inventories, all normalised to 210Pb inventories, suggests that the atmospheric contribution to the contamination of the area of Campalto is low: the upper limits range from 6% (PCDD/Fs) to 17% (HCB).     

Distribution of PBDEs in air particles from an electronic waste recycling site compared with Guangzhou and Hong Kong, South China

Air samples of total suspended particles (TSP, particles less than 30-60 microm), and particles with aerodynamic diameter smaller than 2.5 microm (PM(2.5)) were collected simultaneously at Guiyu (an electronic waste recycling site), three urban sites in Hong Kong and two urban sites in Guangzhou, South China from 16 August to 17 September 2004. Twenty-two PBDE congeners (BDE-3, -7, -15, -17, -28, -49, -71, -47, -66, -77, -100, -119, -99, -85, -126, -154, -153, -138, -156, -184, -183, -191) in TSP and PM(2.5) were measured. The results showed that the overall average concentrations of TSP and PM(2.5) collected at Guiyu were 124 and 62.1 microg m(-3), respectively. The monthly concentrations of the sum of 22 BDE congeners contained in TSP and PM(2.5) at Guiyu were 21.5 and 16.6 ng m(-3), with 74.5 and 84.3%, contributed by nine congeners (BDE-28, -47, -66, -100, -99, -154, -153, -183 and -191 respectively). This pattern was similar to Tsuen Wan site of Hong Kong. Two urban sites of Guangzhou had the same congener pattern, but were different from Yuen Long and Hok Tsui sites of Hong Kong. The results also showed that the amount of mono to penta brominated congeners, which are more toxic, accounted for 79.4-95.6% of Sigma(22)PBDEs from all sites. All congeners tested in Guiyu were up to 58-691 times higher than the other urban sites and more than 100 times higher than other studies reported elsewhere. The higher concentration in the air was due to heating or opening burning of electronic waste since PBDEs are formed when plastics containing brominated flame retardants are heated.