Distribution of endocrine disruptors in the Llobregat River basin (Catalonia,NE Spain)

The Llobregat basin is a Mediterranean fluvial system with major agricultural, urban and industrial impacts. We combined chemical quantification by liquid chromatography–mass spectrometry with electrospray interface (LC-ESI-MS) and the recombinant yeast assay (RYA) assays to estimate the loads of endocrine disrupting compounds (EDCs) along the basin. Chemical analysis revealed maximum concentrations (at μg l⁻¹ level) of alkylphenols at the lower course of the Llobregat River, which correlated with high levels of estrogenic activity detected by RYA. Analysis by RYA and LC-ESI-MS of influent and effluent waters from four sewage treatment plants (STP) discharging into the basin showed the removal of 80–95% of EDCs by STP treatment. Chemical analysis data and RYA data showed a quasi-linear correlation, demonstrating the complementariness of both methods. Our data suggest that the concentrations of the analysed compounds were enough to explain the total estrogenicity of water and STP samples from the Llobregat basin.     

Broad range analysis of endocrine disruptors and pharmaceuticals using gas chromatography and liquid chromatography tandem mass spectrometry

Endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have been globally detected in impacted natural waters. The detection of trace quantities of EDCs and PPCPs in the environment is of great concern since some of these compounds have known physiological responses at low concentrations. EDCs can have a wide range of polarities, acidic and basic moieties, and exist in trace quantities, which often requires numerous complex extractions, large sample collection volumes, and multiple instrumental analyses. A comprehensive method has been developed allowing for the analysis of 58 potential EDCs in various water matrices using a single solid-phase extraction (SPE) of a 1 L sample with subsequent analyses using both gas chromatography and liquid chromatography, each coupled with tandem mass spectrometry (GC–MS/MS and LC–MS/MS). Instrument detection limits ranged between 0.12–7.5 pg with corresponding method reporting limits of 1–10 ng l⁻¹ in water. Recoveries for most compounds were between 50% and 112% with good reproducibility (RSD 6–22%).     

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.     

Occurrence of endocrine disrupters and selected pharmaceuticals in Aisonas River (Greece) and environmental risk assessment using hazard indexes

Purpose

The presence of four phenolic endocrine disrupting compounds (EDCs: nonylphenol [NP], NP monoethoxylate[NP1EO], bisphenol A [BPA], triclosan, [TCS]) and four nonsteroidal anti-inflammatory drugs (NSAIDs: ibuprofen[IBF], ketoprofen [KFN], naproxen [NPX], diclofenac [DCF]) in a Greek river receiving treated municipal wastewater was investigated in this study.

Methods

Samples were taken from four different points of the river and from the outlet of a sewage treatment plant (STP) during six sampling campaigns, and they were analyzed using gas chromatography?Cmass spectrometry.

Results

According to the results, EDCs were detected in almost all samples, whereas NSAIDs were detected mainly in wastewater and in the part of the river that receives wastewater from the STP. Among the target compounds, the highest mean concentrations in the river were detected for NP (1,345?ng?L^?1) and DCF (432?ng?L^?1). Calculation of daily loads of the target compounds showed that STP seems to be the major source of NSAIDs to the river, whereas other sources contribute significantly to the occurrence of EDCs. The environmental risk due to the presence of target compounds in river water was estimated, calculating risk quotients for different aquatic organisms (algae, daphnids, and fish). Results denoted the possible threat for the aquatic environment due to the presence of NP and TCS in the river.     

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.     

Use of fugacity model to analyze temperature-dependent removal of micro-contaminants in sewage treatment plants

Effluents from sewage treatment plants (STPs) are known to contain residual micro-contaminants including endocrine disrupting chemicals (EDCs) despite the utilization of various removal processes. Temperature alters the efficacy of removal processes; however, experimental measurements of EDC removal at various temperatures are limited. Extrapolation of EDC behavior over a wide temperature range is possible using available physicochemical property data followed by the correction of temperature dependency. A level II fugacity-based STP model was employed by inputting parameters obtained from the literature and estimated by the US EPA’s Estimations Programs Interface (EPI) including EPI’s BIOWIN for temperature-dependent biodegradation half-lives. EDC removals in a three-stage activated sludge system were modeled under various temperatures and hydraulic retention times (HRTs) for representative compounds of various properties. Sensitivity analysis indicates that temperature plays a significant role in the model outcomes. Increasing temperature considerably enhances the removal of β-estradiol, ethinyestradiol, bisphenol, phenol, and tetrachloroethylene, but not testosterone with the highest biodegradation rate. The shortcomings of BIOWIN were mitigated by the correction of highly temperature-dependent biodegradation rates using the Arrhenius equation. The model predicts well the effects of operating temperature and HRTs on the removal via volatilization, adsorption, and biodegradation. The model also reveals that an impractically long HRT is needed to achieve a high EDC removal. The STP model along with temperature corrections is able to provide some useful insight into the different patterns of STP performance, and useful operational considerations relevant to EDC removal at winter low temperatures.     

Combining passive samplers and biomonitors to evaluate endocrine disrupting compounds in a wastewater treatment plant by LC/MS/MS and bioassay analyses

Two types of integrative sampling approaches (passive samplers and biomonitors) were tested for their sampling characteristics of selected endocrine disrupting compounds (EDCs). Chemical analyses (LC/MS/MS) were used to determine the amounts of five EDCs (nonylphenol, bisphenol A, estrone, 17β-estradiol and 17α-ethinylestradiol) in polar organic chemical integrative samplers (POCIS) and freshwater mussels (Unio pictorum); both had been deployed in the influent and effluent of a municipal wastewater treatment plant (WWTP) in Genoa, Italy. Estrogenicity of the POCIS samples was assessed using the yeast estrogen screen (YES). Estradiol equivalent values derived from the bioassay showed a positive correlation with estradiol equivalents calculated from chemical analyses data. As expected, the amount of estrogens and EEQ values in the effluent were lower than those in the influent. Passive sampling proved to be the preferred method for assessing the presence of these compounds since employing mussels had several disadvantages both in sampling efficiency and sample analyses.     

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.     

Possible alkylation of inorganic Hg(II) by photochemical processes in the environment

Contamination of surface waters by pesticides continues to be the focus of concern for water authorities due to the growing evidence of their deleterious effects on aquatic life. In this context, the present work investigates the occurrence of 16 selected pesticides belonging to the classes of triazines, phenylureas, organophosphates, chloroacetanilides and thiocarbamates in surface waters from the Llobregat River (NE Spain) and some of its tributaries (Anoia and Rubí) and assesses their potential impact on the aquatic organisms by applying a recently developed index, the Short-term Pesticide Risk Index for the Surface Water System (PRISW-1), which takes into account the pesticides concentrations and their overall toxicity against three aquatic organisms (algae, Daphnia, and fish). Chemical analysis, performed by means of a fully automated method based on isotope dilution on-line solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry (on-line SPE-LC-ESI-MS/MS), revealed diuron and diazinon as the most ubiquitous and abundant compounds with levels up to 818 and 132 ng L⁻¹, respectively. Total pesticide concentrations, which in only 1 out of 66 samples surpassed 500 ng L⁻¹, were higher in the tributaries than in the river but their contribution in terms of mass-loads to the overall pesticide pollution of the Llobregat River was relatively small. Contamination increased downstream of the river and was clearly influenced by rainfall and hence river flow. Application of the PRISW-1 index indicated that, although pesticides levels fulfilled the European Union Environmental Quality Standards (EQS) for surface waters, the existing pesticide contamination poses a low to high ecotoxicological risk for aquatic organisms, that algae and macro-invertebrates are at higher risk than fish, and that the organophosphates diazinon and malathion and the phenylurea diuron are the major contributors to the overall toxicity and therefore the most problematic compounds.     

Occurrence, distribution, and sources of six phenolic endocrine disrupting chemicals in the 22 river estuaries around Dianchi Lake in China

The objectives of this study are to track the occurrence, distribution, and sources of phenolic endocrine disrupting compounds (EDCs) in the 22 rivers around Dianchi Lake in China, to estimate the input and output amounts of phenolic EDCs in the water system, and to provide more comprehensive fundamental data for risk assessment and contamination control of phenolic EDCs in aquatic environment. Six phenolic EDCs were systematically evaluated in water and surface sediment in the estuaries of those rivers. The water and sediment samples were preconcentrated by solid-phase extraction system and microwave-assisted extraction system, respectively. Phenolic EDCs were analyzed by GC-MS (Thermo Fisher Scientific, USA) after derivatization. Phenolic EDCs were found ubiquitously in the aquatic environment. The total concentrations ranged from 248 to 4,650 ng/L in water, and 113 to 3,576 ng/g dry weight in surface sediment. The residue amount of phenolic EDCs in Dianchi Lake was 258 kg/a. Concentrations of the phenolic EDCs in the Lake decreased with increase in distance to the estuaries of those rivers which run through urban and industrial areas. The rivers seriously contaminated by phenolic EDCs were Xin River, Yunliang River, Chuanfang River, Cailian River, Jinjia River, Zhengda River, and Daqing River which run through the old area of Kunming City. Satisfying correlations were observed between the concentrations of the target compounds in water and in surface sediment. NP1EO, NP2EO, and BPA were identified as the three predominant phenolic EDCs. There were significant correlations between phenolic EDCs and many basic water quality parameters. Urban and industrial areas are the major contributors for phenolic EDCs, especially in Kunming City. Compositional profiles of phenolic EDCs in surface sediment were similar to those in river water. The concentrations of phenolic EDCs in the rivers located in the northwest part of the valley were very high, and posed a potential risk to aquatic organisms and even human. The concentrations of NP2EO, NP1EO, and BPA were at moderate levels of other areas. The basic water quality parameters (TOC, TN, DO, and pH) play important roles on the distribution, fate, and behavior of phenolic EDCs in the valley.     

A chemical and toxicological profile of Dutch North Sea surface sediments

Chemical and toxicological profiles were assessed in surface sediments (fraction <63 μm) from the southern North Sea. In extracts of freeze-dried samples, polybrominated biphenyl (PBB), Irgarol 1051 and phthalate concentrations were below the respective detection limits (except di(2-ethylhexyl)phthalate, which was between 170 and 3300 μg kg⁻¹ dry weight (dw)). Hexabromocyclododecane (HBCD) concentrations were between 0.8 and 6.9 μg kg⁻¹ dw, with highest concentrations at river mouths. Polybrominated diphenylethers (PBDE) concentrations were 0.4–0.6 μg kg⁻¹ dw, decabromodiphenylether (BDE209) 1–32 μg kg⁻¹ dw. The ratio BDE209/PCB153 was used as a tracer for recent emissions, and pointed towards a BDE209 source in the Western Scheldt’s upper estuary. PCBs and PAHs were between 0.19–4.7 and 2.6–200 μg kg⁻¹ dw respectively and generally had highest concentrations at near-shore locations and river mouths.

Responses in the Microtox broad-spectrum and the Mutatox genotoxicity assays were generally low, with near-shore locations giving higher responses. The umu-C genotoxicity and the ER-CALUX assay for estrogenicity showed no response, with the exception of one near-shore location (IJmuiden outer harbour, ER-CALUX).

Highest dioxin-like toxicity (DR-CALUX) was found at near-shore locations, in the outflow of the Rhine/Meuse estuary including a dumping site of harbour sludge. At the Oyster Grounds, DR-CALUX responses appeared to be linked to the occurrence of larger PAHs (4–6 rings). A new, non-destructive clean up procedure resulted in significantly higher DR-CALUX responses than the current protocol. The Dutch legislation on disposal of harbour sludge at sea, dictates the use of the conventional clean up procedure. Our results therefore indicate that probably more dioxin-like toxicity associated with harbour sludge is disposed off at sea than assumed.     

Carbonyls and non-methane hydrocarbons at a rural mountain site in northeastern United States

Measurements of carbonyls and C₂–C₆ non-methane hydrocarbons (NMHCs) were made in ambient air at a rural site at the summit of Whiteface Mountain (WFM) in New York State. Alkanes dominated in the samples, with ethane and propane making up about 55% of the total on a carbon-atom basis. Ethane, the longest-lived of the NMHCs, showed a mixing ratio in the range of 0.86–2.1 ppbv. Photochemical ageing analysis indicated an anthropogenic influence on the NMHC levels. The photochemical reactivity of the hydrocarbons, calculated in terms of propylene-equivalent concentration, was dominated by alkenes (propene and ethene), which accounted for 74% of the total NMHC sum. Air mass back-trajectories have been used to investigate the origin of the observed NMHCs and carbonyls. Higher concentrations were found when air masses arrived from the midwestern US corridor. Acetone was the most abundant species, comprising from 31% to 53% of the total detected carbonyls, followed by MEK (15–53%), HCHO (7–39%), and CH₃CHO (7–19%). Average concentrations were determined to be 1.61 ppbv for CH₃C(O)CH₃, 1.40 ppbv for MEK, 1.16 ppbv for HCHO, and 0.49 ppbv for CH₃CHO. The variations in carbonyl concentrations were observed to follow patterns similar to variations in O₃ concentrations, typical of secondary products. Correlations and statistical analysis of the carbonyls and NMHCs were performed, and showed that most of the compounds derived from mixing and photochemical transformation of long-range transported pollutants from the major source areas. Ranking of the carbonyls with respect to removal of the OH radical showed HCHO to be the most important species, followed by CH₃CHO, MEK, and CH₃C(O)CH₃.     

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.     

Assessing the effects of tertiary treated wastewater reuse on the presence emerging contaminants in a Mediterranean river (Llobregat,NE Spain)

Purpose  

The Llobregat River, which is characterized by important fluctuations of the flow rates, receives treated waters from WWTPs. During the years 2007 and 2008, the Llobregat River basin suffered from a severe drought which affected the supply of drinking water facilities (DWF) that rely on the exploitation of the river water. The Catalan Water Agency implemented a water reuse experiment with the objective of maintaining the river flow rate at sufficiently high level so as to ensure the supply of raw water to Barcelona’s major DWF.     

Biologically directed environmental monitoring, fate, and transport of estrogenic endocrine disrupting compounds in water: A review

Endocrine disrupting compounds (EDCs) are contaminants that may be hormonally active at low concentrations and are emerging as a major concern for water quality. Estrogenic EDCs (e-EDCs) are a subclass of EDCs that, when organisms are exposed to them, function as estrogens. Given that there are numerous e-EDCs that can negatively affect humans and wildlife, general screening techniques like biologically based assays (BBAs) may provide major advantages by estimating the total estrogenic effects of many e-EDCs in the environment. These techniques may potentially be adapted for field portable biologically directed sampling and analyses. This article summarizes available BBAs used to measure estrogenic e-EDCs in the environmental samples and also presents results relating to fate and transport of e-EDCs. Estrogenic EDCs appear to be almost ubiquitous in the environment, despite low solubility and high affinity of organic matter. Potential transport mechanisms may include: (1) transport of more soluble precursors, (2) colloid facilitated transport, (3) enhanced solubility through elevated pH, and (4) the formation of micelles by longer-chain ethoxylates. Due to their persistent and ubiquitous nature, source control strategies for e-EDCs may reduce influent concentration to wastewater treatment plants so that the post treatment effluent will decrease concentrations to estrogenically inactive levels. Alternatively if source reduction is not possible, then more testing is needed on tertiary treatment technologies and treatment efficiencies for e-EDCs. There is still a need for research on remediation and restoration approaches for habitats disturbed by elevated e-EDC concentrations.     

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

Removal of carotene-like colored compounds by liquid-liquid extraction during polycyclic aromatic hydrocarbons analysis of plant tissue

Plants contain a wide variety of chemicals, some of which may have similar chromatographic behavior to polycyclic aromatic hydrocarbons (PAHs). During solid phase extraction (SPE) with Si-gel for instance, the co-elution of carotene-like colored compounds with PAHs has been observed. In this paper, liquid–liquid extraction was applied for the separation and subsequent analysis of PAHs from plant extracts. PAHs containing 2–6 rings, which include naphthalene, phenanthrene, pyrene, benzo[a]pyrene and benzo[ghi]perylene, were used as representative target chemicals. Carotene-like compounds extracted from Komatsuna (Brassica campestris) shoot by acetone followed by Si-gel treatment were incorporated as undesired components in the model matrix. Results showed the feasibility of employing either acetonitrile or 2% (w/v) KOH–methanol as solvents for high PAHs recovery and low extraction of colored fraction. For acetonitrile, 86.9–93.5% of each PAH could be recovered after three extraction cycles (relative standard deviation, RSD < 1.6%) with only about 10% co-extraction of colored fraction. For 2% KOH–methanol, PAHs recoveries ranging from 79.3% to 83.1% after five cycles (RSD < 1.5%) were achieved while the percent extraction of colored fraction was also low at 10%. The relatively higher selectivity of the solvents for PAHs over the colored fraction as well as the solubility of the matrix solution in the solvent may have contributed to these results. On this basis, liquid–liquid extraction is very useful for the pre-treatment of plant extracts for PAHs analysis.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Estrogenic and dioxin-like potency in each step of a controlled landfill leachate treatment plant in Japan

The estrogenic activity (by E-screen bioassay), the concentrations of PCBs, PCDDs/PCDFs (and their resulting toxicity equivalents, TEQ) and several endocrine disrupting chemicals (EDCs: e.g., bisphenol A, nonylphenol, Butyl benzylpthalate (BBP), di-n-butylphthalate (DBP), 17alpha-ethynyl-estradiol or 4-octylphenol) have been analyzed from leachates of each step (before treatment, after biodegradation/sedimentation and after charcoal treatment) of a controlled landfill leachate treatment plant. The comparison of the effluent of the examined landfill leachate treatment plant with water from a nearby river in this study indicated no additional dioxin-like (e.g., TEQ: 0.027 compared to 1.01 pg TEQ/l; PCBs: 1.2 compared to 3.9 ng/l) or estrogenic impact (2.8 compared to 3.5 ng estradiol equivalents EE/l; analyzed by E-screen bioassay) from the leachate treatment plant into the surrounding water environment. The impact of dioxin-like compounds from uncleaned leachates into the final cleaned effluents could be sufficiently reduced by the leachate treatment plant for PCDDs (75%), PCDFs (62%), dioxin-like PCBs (97%), and the sum of TEQ (78%). The leachate treatment plant also achieved a reduction of the estrogenic activity as determined by E-screen (from 4.8 to 2.8 ng EE/l = 42%), by GC/MS for bisphenol A (>96% and nonylphenol (>98%) or by ELISA for estradiol (>80%). Additionally, for the validation of the E-screen, five known endocrine disrupting chemicals (EDCs: bisphenol A, BBP, DBP, 17 alpha-ethynyl-estradiol, 4-octylphenol) were analyzed. The EC50 values and estradiol equivalents factors (EEFs) for the five EDCs determined in this study were comparable to previously published data. The combined biological and chemical trace analysis data have provided valuable information on the relative contribution of natural, synthetic, and non-steroidal anthropogenic chemicals to the estrogenic and dioxin-like activity in leachates from a wastewater treatment plant, and water from a nearby river.     

Degradation of organic pollutants in Mediterranean forest soils amended with sewage sludge

The degradation of two groups of organic pollutants in three different Mediterranean forest soils amended with sewage sludge was studied for nine months. The sewage sludge produced by a domestic water treatment plant was applied to soils developed from limestone, marl and sandstone, showing contrasting alkalinity and texture. The compounds analysed were: linear alkylbenzene sulphonates (LAS) with a 10–13 carbon alkylic chain, and nonylphenolic compounds, including nonylphenol (NP) and nonylphenol ethoxylates with one and two ethoxy groups (NP1EO + NP2EO). These compounds were studied because they frequently exceed the limits proposed for sludge application to land in Europe. After nine months, LAS decomposition was 86–96%, and NP + NP1EO + NP2EO decomposition was 61–84%, which can be considered high. Temporal trends in LAS and NP + NP1EO + NP2EO decomposition were similar, and the concentrations of both types of compounds were highly correlated. The decomposition rates were higher in the period of 6–9 months (summer period) than in the period 0–6 months (winter + spring period) for total LAS and NP + NP1EO + NP2EO. Differences in decay rates with regard to soil type were not significant. The average values of decay rates found are similar to those observed in agricultural soils.