Brominated flame retardants and other organobromines in Norwegian predatory bird eggs

A set of 62 unhatched eggs was collected from six different predatory bird species throughout Norway after incubation period was completed. They were analysed for PBDE, PBB, TBBP A and naturally occurring halogenated compounds. BDE 47, 99 and 153 were the dominating congeners, with species dependent PBDE patterns. BDE 153 was observed as the most abundant congener in eggs of peregrine falcon, golden eagle and merlin. The highest PBDE level (sum of nine congeners) was found in eggs of white-tailed sea eagle with up to 800ng/gww (median sumPBDE: 184ng/gww), followed by eggs of peregrine falcon and osprey (median sumPBDE: 155 and 105ng/gww, respectively). Golden eagle eggs showed the lowest concentration of all species (median sumPBDE: 3ng/gww). The levels in the peregrine falcon are similar to those found earlier in the Baltic region [Lindberg, P., Sellstrom, U., Haggberg, L., de Wit, C.A., 2004. Higher brominated diphenyl ethers and hexabromocyclododecane found in eggs of peregrine falcons (Falco peregrinus) breeding in Sweden. Environmental Science & Technology. 38 (1), 93-96]. The differences between species are not fully explainable, due to lack of data from the major food species. BB 101 and 153 were found in eggs of all investigated bird species. Especially in samples of white-tailed sea eagle, peregrine falcon and goshawk additional unknown penta- and hexabrominated biphenyls were detected. TBBP A was detected in all of eight eggs analysed sampled from four different bird of prey species. The naturally occurring halogenated compounds Q1, the dibromotrichloro monoterpene MHC-1, and 2,4,6-tribromoanisole (TBA) were detected in all of seven analysed samples except for one peregrine falcon egg.     

Environmental contaminants in prey and tissues of the peregrine falcon in the Big Bend Region, Texas, USA.

Peregrine falcons (Falco peregrinus) have been recorded nesting in Big Bend National Park, Texas, USA and other areas of the Chihuahuan Desert since the early 1900s. From 1993 to 1996, peregrine falcon productivity rates were very low and coincided with periods of low rainfall. However, low productivity also was suspected to be caused by environmental contaminants. To evaluate potential impacts of contaminants on peregrine falcon populations, likely avian and bat prey species were collected during 1994 and 1997 breeding seasons in selected regions of western Texas, primarily in Big Bend National Park. Tissues of three peregrine falcons found injured or dead and feathers of one live fledgling also were analyzed. Overall, mean concentrations of DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene], a metabolite of DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane], were low in all prey species except for northern rough-winged swallows (Stelgidopteryx serripennis, mean = 5.1 microg/g ww). Concentrations of mercury and selenium were elevated in some species, up to 2.5 microg/g dw, and 15 microg/g dw, respectively, which upon consumption could seriously affect reproduction of top predators. DDE levels near 5 microg/g ww were detected in carcass of one peregrine falcon found dead but the cause of death was unknown. Mercury, selenium, and DDE to some extent, may be contributing to low reproductive rates of peregrine falcons in the Big Bend region.     

Biological response of high-back crucian carp (Carassius auratus) during different life stages to wastewater treatment plant effluent

This study presents the adverse effects of endocrine disrupting chemicals (EDCs) in effluent of wastewater treatment plants (WwTPs) on fish health. A study of chronic exposure to WwTPs effluent for 10 months was undertaken in high-back crucian carp (Carassius auratus) during different life stages, covering early-life-stage (ELS), prespawning period, and postspawning period. Condition factor (CF), gonadosomatic index (GSI), hepatosomatic index (HSI), and plasma vitellogenin (VTG) levels were employed as indicators to assess biological effects of effluent on this gynogenesis species. Meanwhile, some high-back crucian carp were caged in Demonstration Base of Biological Purification for Filter-feeding Fish (hereinafter, Demonstration Base), as WwTPs effluent exposure controls. In the meantime, a depuration study was carried out to determine whether or not the estrogenic effects caused by effluent exposure could be reduced after moving fish into EDCs-free water. CF, HSI, GSI, and plasma Vtg levels of high-back crucian carp caged in Demonstration Base were generally in accordance with seasonal change. Effluent exposure inhibited gonadal growth, reducing GSI in ELS while increasing it around spawning, sharpened liver burdens, increasing HSI, and induced abnormal Vtg expression in juvenile high-back crucian carp, augmenting Vtg concentrations in plasma. Around spawning period, Vtg in high-back crucian carp were mainly induced by endogenous estrogens, and EDCs in effluent had less influence on them. Staying in EDCs-free water for 30 days made high-back crucian carp recover from effects of previous effluent exposure, relieving inhibition of gonadal development and hypertrophy of liver as well as reducing Vtg induced by EDCs in effluent. The results revealed that high-back crucian carp in ELS are more sensitive to WwTPs effluent exposure. Additionally, the depuration study showed a clearance of the estrogenic effects caused by effluent.     

Endocrine Disruptors in Mediterranean top marine predators

- DOI: http://dx.doi.org/10.1065/espr2006.01.018 Background, Aims and Scope Man-made Endocrine Disruptors (EDs) range across all continents and oceans. Some geographic areas are potentially more threatened than others: one of these is the Mediterranean Sea. Levels of some xenobiotics are much higher here than in other seas and oceans. In this paper we review the final results of a project in which the hypothesis that Mediterranean top predator species (such as large pelagic fish and marine mammals) are potentially at risk due to EDs was investigated. Methods In a four-year survey on the Mediterranean population of swordfish (Xiphias gladius), the potential toxicological effects of organochlorine compounds (OCs) on specimens of swordfish and tuna fish (Thunnus thynnus thynnus), caught in the spawning seasons from 1999 to 2002 in the Straits of Messina, Sicily (Italy), were investigated using vitellogenin (Vtg), Zona radiata proteins (Zrp), and cytochrome P4501A (CYP1A) activities (EROD, BPMO). Tissues (skin and blubber) were obtained from Stenella coeruleoalba, Tursiops truncatus, Delphinus delphis and Balaenoptera physalus from the western Ligurian Sea, between Corsica and the French-Italian coast, and Ionic Sea using biopsy darts launched with a crossbow. Benzo(á)pyrene monoxigenase (BPMO) activity was mesured in biopsies and cholrinated hydrocarbon levels were detected. Results and Discussion We illustrate the need to develop and apply sensitive methodological tools, such as biomarkers (Vitellogenin, Zona Radiata proteins and CYP1A activities) for evaluation of toxicological risk in Xiphias gladius and Thunnus thynnus thynnus), and nondestructive biomarkers (CYP1A activities and fibroblast cell culture in skin biopsy), for the hazard assessment of threatened marine mammals species (Stenella coeruleoalba, Tursiops truncatus, Delphinus delphis and Balaenoptera physalus) exposed to EDs. Conclusion The present research shows that: a) Vtg and Zrp can be used as diagnostic tools for fish stocks hazard assessment in the Mediterranean Sea; b) that CYP1A1 (BPMO) induction in cetaceans skin biopsy may be an early sign of exposure to EDs such as OCs and a potential alert for transgenerational effects. Recommendation and Outlook This research represents a warning signal of the potential reproductive alterations in marine top predators and suggest the need for continuous monitoring to avoid reductions in population and biodiversity in the Mediterranean Sea.     

Bioanalytical characterisation of multiple endocrine- and dioxin-like activities in sediments from reference and impacted small rivers

A comprehensive evaluation of organic contamination was performed in sediments sampled in two reference and three impacted small streams where endocrine disruptive (ED) effects in fish have been evidenced. The approach combined quantitative chemical analyses of more than 50 ED chemicals (EDCs) and a battery of in vitro bioassays allowing the quantification of receptor-mediated activities, namely estrogen (ER), androgen (AR), dioxin (AhR) and pregnane X (PXR) receptors. At the most impacted sites, chemical analyses showed the presence of natural estrogens, organochlorine pesticides, parabens, polycyclic aromatic hydrocarbons (16 PAHs), bisphenol A and alkylphenols, while synthetic steroids, myco-estrogens and phyto-estrogens were not detected. Determination of toxic-equivalent amounts showed that 28-96% of estrogenic activities in bioassays (0.2-6.3 ng/g 17β-estradiol equivalents) were explained by 17β-estradiol and estrone. PAHs were major contributors (20-60%) to the total dioxin-like activities. Interestingly, high PXR and (anti)AR activities were detected; however, the targeted analysed compounds could not explain the measured biological activities. This study highlighted the presence of multiple organic EDCs in French river sediments subjected to mixed diffuse pollution, and argues for the need to further identify AR and PXR active compounds in the aquatic environment.     

Status and trends of circumpolar peregrine falcon and gyrfalcon populations

Ambio - The peregrine falcon (Falco peregrinus) and the gyrfalcon (Falco rusticolus) are top avian predators of Arctic ecosystems. Although existing monitoring efforts are well established for both...     

Assessing breeding potential of peregrine falcons based on chlorinated hydrocarbon concentrations in prey

Peregrine falcons (Falco peregrinus) now breed successfully in most areas of North America from which they were previously extirpated. The loss during the mid-part of the last century of many of the world's peregrine populations was largely a consequence of impaired reproduction caused by the effects of DDE on eggshell quality and embryo hatchability. Population recovery has been attributed to re-introduction efforts, coupled with regulatory restrictions on the use of organochlorine pesticides. Peregrines have not returned to breed in some areas, such as the Okanagan Valley of British Columbia. That region has been extensively planted in fruit orchards which were treated annually with DDT during the early 1950s to the 1970s. Ongoing contamination of avian species, including potential peregrine prey, inhabiting orchards has been documented. In response to an initiative to release peregrines around the city of Kelowna in the Okanagan Valley, we collected potential peregrine prey species and analyzed whole bodies for chlorinated hydrocarbon residues. We used a simple bioaccumulation model to predict concentrations of DDE in peregrine eggs using concentrations in prey and estimates of dietary makeup as input. Peregrines would be expected to breed successfully only if they fed on a diet primarily of doves. Feeding on as little as 10% of other species such as starlings, robins, gulls and magpies would produce DDE concentrations in peregrine eggs greater than the threshold of 15 mg/kg. We also estimated the critical concentration of DDE in total prey to be about 0.5 mg/kg, one half of the previous most conservative criterion for peregrine prey. Concentrations of dieldrin and PCBs in peregrine prey are less than suggested critical levels.     

Nondestructive biomarkers of exposure to endocrine disrupting chemicals in endangered species of wildlife.

This paper explores the problem of endocrine disrupting chemicals (EDCs) from the ecotoxicological point of view, focusing on nondestructive biomarkers of exposure to EDCs for risk assessment of endangered species of wildlife. Several EDCs, such as polyhalogenated aromatic hydrocarbons and toxic metals, tend to be biomagnified in the terrestrial and particularly the marine food chains. Top predators tend to accumulate high concentrations of these contaminants which places them in a situation of high toxicological risk. Hence, there is a need to develop nondestructive techniques, such as nondestructive biomarkers, for hazard assessment, protection, and conservation of endangered species exposed to EDCs. The biological materials proposed for this approach (for example blood, faeces, fur, skin biopsy specimens) are easily obtained with minimal stress for individuals and populations. Some validation data are reported on porphyrins in sea bird excreta (Larus dominicanus, Phalacrocorax olivaceus, Pelecanus occidentalis thagus), as nondestructive biomarkers of exposure to organochlorines, and on benzopyrene monooxygenase activities in marine mammal skin biopsy specimens (Stenella coeruleoalba, Balaenoptera physalus), as early indicators of exposure to p,p'-DDE and other endocrine disrupting organochlorines.     

Study of the adsorption of endocrine disruptor compounds on typical filter materials using a quartz crystal microbalance

Environmental Science and Pollution Research - Drinking water containing environmental endocrine disruptor compounds (EDCs) endangers human health, and researching the purification process of...     

Partitioning of endocrine disrupting compounds in inland waters and wastewaters discharged into the coastal area of Thessaloniki,Northern Greece

Background, aim, and scope  

In the Water Framework Directive 2000/60/EC, environmental objectives for the proper quality of inland, surface, transitional, coastal, and ground waters have been set. Member states are required to identify chemical pollutants of significance in the water bodies, to establish emission control measures, and to achieve quality standards. A specific category of pollutants are the compounds that may possess endocrine-related functions known as endocrine disrupting compounds (EDCs). This means that member states have the obligation to take action in order to prevent human exposure to these compounds via aquatic environment. The objective of this research was to study the occurrence and distribution of phenolic and steroid EDCs in inland waters and wastewaters discharged in the area of Thermaikos Gulf, Thessaloniki, Northern Greece.     

Endocrine disrupting compounds in municipal and industrial wastewater treatment plants in Northern Greece

The occurrence and fate of endocrine disrupting compounds (EDCs) in a sewage treatment plant and two industrial wastewater treatment plants from textile and tannery factories were investigated. EDCs of interest are 4-nonylphenol, 4-octylphenol, their ethoxylate oligomers (mono- and di-ethoxylates of nonylphenol and octylphenol), bisphenol A, triclosan and steroid estrogens. Target compounds were determined in dissolved fraction, total suspended solids and sludge by employing solid phase extraction and ultrasonication followed by gas chromatography–mass spectrometry.Nonylphenols and oligomers with one or two ethoxy groups were the most abundant compounds in raw wastewater as well as in effluents from all the treatment stages of sewage treatment plant, followed by triclosan and bisphenol A. Steroids were found at very low concentrations. Almost all phenolic EDCs compounds were predominantly associated to suspended solids in influents whereas the dissolved fraction dominated the treated effluents. High removal rates, ranging from 86% to 99%, were observed throughout the whole treatment process. Biodegradation was the main removal pathway of EDCs. Tannery wastewaters exhibited high concentrations of nonylphenolic compounds. This type of wastewaters could pose a significant risk to the aquatic and terrestrial environment.     

Passive sampling of selected endocrine disrupting compounds using polar organic chemical integrative samplers

Two types of polar organic chemical integrative samplers (pharmaceutical POCIS and pesticide POCIS) were examined for their sampling efficiency of selected endocrine disrupting compounds (EDCs). Laboratory-based calibration of POCISs was conducted by exposing them at high and low concentrations of 14 EDCs (4-alkyl-phenols, their ethoxylate oligomers, bisphenol A, selected estrogens and synthetic steroids) for different time periods. The kinetic studies showed an integrative uptake up to 28 days. The sampling rates for the individual compounds were obtained. The use of POCISs could result in an integrative approach to the quality status of the aquatic systems especially in the case of high variation of water concentrations of EDCs. The sampling efficiency of POCISs under various field conditions was assessed after their deployment in different aquatic environments.     

Effects of organochlorine xenobiotics on human spermatozoa.

The organochlorine insecticide lindane is a widely distributed environmental pollutant belonging to the growing family of endocrine disrupting chemicals (EDCs). Lindane intercalates into the sperm membrane and alters the molecular dynamics of the bilayer. In the present paper, preliminary data are reported showing that doses of lindane as low as those found in the female genital tract secretions inhibit the sperm cytological responsiveness to progesterone, the physiological agonist which stimulates the onset of acrosome reactions at the site of fertilization. The hypothesis is put forth that even background levels of lindane may exert antifertility effects independently on the health status of either the male and female reproductive organs.     

中国地表饮用水水源地有机类内分泌干扰物污染现况分析

有机类内分泌干扰物(EDCs)是一类对人类和生物内分泌系统产生干扰,并可造成其紊乱的特殊外来物质,对人类和生物健康有极大的危害.以与人类生活密切相关的地表饮用水水源地中的有机类EDCs为研究重点,对中国目前地表饮用水水源地EDCs污染状况、污染物种类及其来源及可能的污染途径进行了评述.目前,中国各地区地表饮用水水源地均有有机类EDCs检出.其中以有机氯农药六六六及其异构体、DDT及其代谢产物和多氯联苯检出率最高,且某些地区检测浓度相当高,主要来源是农药使用和污水排放.国内外对地表饮用水水源地EDCs突发污染事件的研究均较少,应引起高度重视.     

Endocrine disrupting chemicals accumulate in earthworms exposed to sewage effluent

Endocrine disrupting chemicals (EDCs) can alter endocrine function in exposed animals. Such critical effects, combined with the ubiquity of EDCs in sewage effluent and potentially in tapwater, have led to concerns that they could be major physiological disruptors for wildlife and more controversially for humans. Although sewage effluent is known to be a rich source of EDCs, there is as yet no evidence for EDC uptake by invertebrates that live within the sewage treatment system. Here, we describe the use of an extraction method and GC-MS for the first time to determine levels of EDCs (e.g., dibutylphthalate, dioctylphthalate, bisphenol-A and 17beta-estradiol) in tissue samples from earthworms (Eisenia fetida) living in sewage percolating filter beds and garden soil. To the best of our knowledge, this is the first such use of these techniques to determine EDCs in tissue samples in any organism. We found significantly higher concentrations of these chemicals in the animals from sewage percolating filter beds. Our data suggest that earthworms can be used as bioindicators for EDCs in these substrates and that the animals accumulate these compounds to levels well above those reported for waste water. The potential transfer into the terrestrial food chain and effects on wildlife are discussed.     

Occurrence and removal of endocrine disrupting chemicals in wastewater

This paper discusses the occurrence and removal of endocrine disrupting chemicals (EDCs) in Horsham sewage treatment plant (STP), West Sussex, UK. Photodegradation aided by a catalyst (TiO(2)) was studied for its efficiency of removing EDCs from wastewater. The degradation of estrone and 17beta-estradiol under natural sunlight followed a pseudo-first-order kinetics, with a rate constant of 0.01h(-1). The degradation by sunlight is also independent of initial chemical concentration, suggesting some potential of using this environmentally friendly method for waste minimisation. In comparison, more efficient degradation was observed with UV irradiation (253nm), with the rate constants being increased to 2.7 and 2.5h(-1) for the two compounds. Subsequent application of the photocatalysis method to real effluent treatment at Horsham STP was successful, as demonstrated by the non-detection of the target compounds following treatment.     

Removal of estrone, 17α-ethinylestradiol,and 17ß-estradiol in algae and duckweed-based wastewater treatment systems

Background, aim, and scope  

Many pollutants have received significant attention due to their potential estrogenic effect and are classified as endocrine disrupting compounds (EDCs). Because of possible ecological effects and increased attention for water reuse schemes, it is important to increase our understanding of the EDC removal capacities of various wastewater treatment systems. However, there has so far been little research on the fate and behavior of EDCs in stabilization pond systems for wastewater treatment, which represent an important class of wastewater treatment systems in developing countries because of their cost-effectiveness. The aim of this work is to study the fate and behavior of EDCs in algae and duckweed ponds. Because the synthetic hormone 17α-ethinylestradiol (EE2) and the natural hormones estrone (E1), as well as 17β-estradiol (E2), have been detected in effluents of sewage treatment plants and been suggested as the major compounds responsible for endocrine disruption in domestic sewage; E1, E2, and EE2 were therefore chosen as target chemicals in this current work.     

Evaluation of the Daphnia magna reproduction test for detecting endocrine disruptors

The Daphnia 21 d reproduction test is considered as a comprehensive and decisive test in the OECD Conceptual Framework for testing and assessment of endocrine disrupting chemicals (EDCs). However, how to interpret results of the Daphnia 21 d reproduction test for identification, risk assessment and testing strategy of EDCs remains an unsolved issue. This study analysed a total number of 135 published studies encompassing 86 known EDCs and non-EDCs with different modes of action. Our results show that the majority of effects on apical endpoints (survival, molting, growth, time to reproductive maturity, brood size, the number of broods, and the total number of offspring) do not seem to be EDC-specific. In contrast, the endpoint sex ratio is likely specific to juvenile hormones and their mimics. Variability is quantified for three most reported endpoints survival, the total number of offspring and sex ratio. Quantification of the endpoint sensitivity shows that the sensitivity of the sex ratio is lower than that of the total number of offspring. The Daphnia 21 d reproduction test gives insufficient information to conclude if a substance is an EDC or not. EDCs that are potent in assays in vitro may not be potent in the Daphnia 21 d reproduction test. We conclude that the Daphnia 21 d reproduction test is important for deriving No Observed Effect Concentrations for risk assessment but may produce false negatives in identification of EDCs when used on its own. A targeted testing strategy for selection of species, tests, and endpoints is suggested for identifying EDCs.     

Selected endocrine disrupting compounds (Vinclozolin,Flutamide, Ketoconazole and Dicofol): Effects on survival,occurrence of males,growth, molting and reproduction of <Emphasis Type="Italic">Daphnia magna</Emphasis>

BACKGROUND, AIM AND SCOPE: Pollution-induced endocrine disruption in vertebrates and invertebrates is a worldwide environmental problem, but relatively little is known about effects of endocrine disrupting compounds (EDCs) in planktonic crustaceans (including Daphnia magna). Aims of the present study were to investigate acute 48 h toxicity and sub-chronic (4-6 days) and chronic (21 days) effects of selected EDCs in D. magna. We have investigated both traditional endpoints as well as other parameters such as sex determination, maturation, molting or embryogenesis in order to evaluate the sensitivity and possible use of these endpoints in ecological risk assessment. MATERIALS AND METHODS: We have studied effects of four model EDCs (vinclozolin, flutamide, ketoconazole and dicofol) on D. magna using (i) an acute 48 h immobilization assay, (ii) a sub-chronic, 4-6 day assay evaluating development and the sex ratio of neonates, and (iii) a chronic, 21 day assay studying number of neonates, sex of neonates, molting frequency, day of maturation and the growth of maternal organisms. RESULTS: Acute EC50 values in the 48 h immobilization test were as follows (mg/L): dicofol 0.2, ketoconazole 1.5, flutamide 2.7, vinclozolin >3. Short-term, 4-6 day assays with sublethal concentrations showed that the sex ratio in Daphnia was modulated by vinclozolin (decreased number of neonate males at 1 mg/L) and dicofol (increase in males at 0.1 mg/L). Flutamide (up to 1 mg/L) had no effect on the sex of neonates, but inhibited embryonic development at certain stages during chronic assay, resulting in abortions. Ketoconazole had no significant effects on the studied processes up to 1 mg/L. DISCUSSION: Sex ratio modulations by some chemicals (vinclozolin and dicofol) corresponded to the known action of these compounds in vertebrates (i.e. anti-androgenicity and anti-oestrogenicity, respectively). Our study revealed that some chemicals known to affect steroid-regulated processes in vertebrates can also affect sublethal endpoints (e.g. embryonic sex determination and/or reproduction) in invertebrates such as D. magna. CONCLUSIONS: A series of model vertebrate endocrine disrupters affected various sub-chronic and chronic parameters in D. magna including several endpoints that have not been previously studied in detail (such as sex determination in neonates, embryogenesis, molting and maturation). Evaluations of traditional reproduction parameters (obtained from the 21 day chronic assay). as well as the results from a rapid, 4-6 day, sub-chronic assay provide complementary information on non-lethal effects of suspected organic endocrine disrupters. RECOMMENDATIONS AND PERSPECTIVES: It seems that there are analogies between vertebrates and invertebrates in toxicity mechanisms and in vivo effects of endocrine disruptors. However, general physiological status of organisms may also indirectly affect endpoints that are traditionally considered 'hormone regulated' (especially at higher effective concentrations as observed in this study) and these factors should be carefully considered. Further research of D. magna physiology and comparative studies with various EDCs will help to understand mechanisms of action as well as ecological risks of EDCs in the environment.     

Decabromodiphenylether and hexabromocyclododecane in wild birds from the United Kingdom, Sweden and The Netherlands: Screening and time trends

The brominated flame retardant decabromodiphenylether (DBDE) was analysed in wild birds to identify the most suitable species for monitoring time trends in DBDE contamination. This information was later used for the design of a 10-year trend study on DBDE in the European Union. DBDE was measured in muscle tissue, liver, and eggs from 10 terrestrial and four aquatic bird species. DBDE was detected in 47% of the terrestrial bird samples (nine species) and in 9% of the aquatic bird samples (six species). Peregrine falcon and sparrowhawk specimens were selected as most suitable species to determine temporal trends of DBDE. For sparrowhawks, no significant change in DBDE concentrations between 1973 and 2001 was found, although in later years more DBDE concentrations were above the detection limit. Peak DBDE levels measured in peregrines in 1995, were followed by a decline in concentrations until 2001. The same species were used for a trend study on hexabromocylcododecane (HBCD). Twenty-four percent of peregrine falcon eggs and 12% of sparrowhawk muscle samples demonstrated measurable HBCD residues. Three diastereomers of HBCD were analysed and the α-diastereomer was the predominant one in most samples. No clear time trends were observed for HBCD in either species. This study demonstrated that these DBDE and HBCD are bioavailable to birds of Northern Europe, although bioaccumulation seems to occur to a limited extent.