Phenolic endocrine disrupting chemicals (EDCs) in Anzali Wetland, Iran: elevated concentrations of 4-nonylphenol, octhylphenol and bisphenol A

We have studied the distribution and value of phenolic endocrine disrupting chemicals (EDCs) in surface sediment samples taken from Anzali Wetland, Iran. These samples were collected from 22 stations during the time span of June-May 2010. In each of the sampling stations, we detected 4-nonylphenol (4-NP), octylphenol (OP), and bisphenol A (BPA) with maximal concentrations of 29, 4.3, and 7 μg g(-1) dry weight (dw), respectively. High levels of alkylphenols (APs) and BPA were also found near urban areas. Furthermore there were no significant differences between those stations in terms of the detected levels. One of the important factors in controlling the fate of these compounds in the aquatic environment appeared to be Total Organic Carbon (TOC). Hierarchical cluster analysis showed differences in the biomarker characteristics of EDCs and TOC between the stations. Our findings indicate that EDCs are ubiquitous in sediments from northeast Wetlands of Iran, contaminating the aquatic habitats in this area.     

Determination of dioxin and dioxin-like compounds in sediments from UK estuaries using a bio-analytical approach: chemical-activated luciferase expression (CALUX) assay

The DR-CALUX assay has been utilised for the bio-analytical screening of a number of estuarine sediments for dioxin-like activity. Total sediment extracts (samples containing all extracted compounds) and cleaned-up extracts (samples with the most stable compounds isolated from the total extracts) were screened. The concentration of the stable dioxin-like compounds in the cleaned-up sediment extracts was between 1.0 and 106 pgTEQCALUX g(-1) dry weight. The majority of sediments contained levels of dioxin-like compounds that were above concentrations that are considered to be a low risk to aquatic organisms. The CALUX bio-analytical approach showed some disparity with the traditional analytical approach. The reasons for these differences have been identified tentatively: firstly, the DR-CALUX assay responds to all dioxin-like compounds, and secondly, it measures non-additive effects. The dioxin-like activity of compounds in sediment total extracts, which contain both labile and stable compounds, were also assessed and were six orders of magnitude higher than the cleaned-up samples. This suggests the vast majority of the total dioxin-like activity is attributable to labile compounds. Overall, the DR-CALUX assay is shown to be a useful tool in the assessment of dioxin-like activity in estuarine sediments.     

Levels of endocrine disrupting compounds in South China Sea

The occurrence of estrogens in the aquatic environment has become a major concern worldwide because of their strong endocrine disrupting potency. In this study, concentrations of four estrogenic compounds, estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), estriol (E3) were determined with liquid chromatography-tandem mass spectrometry analyses in surface water from South China Sea, and distributions and potential risks of their estrogenic activity were assessed. The estrogenic compounds E1, E2 and E3 were detected in most of the samples, with their concentrations up to 11.16, 3.71 and 21.63 ng L⁻¹. However, EE2 was only detected in 3 samples. Causality analysis, EEQ values from chemical analysis identified E2 as the main responsible compounds. Based on the EEQ values in the surface water, high estrogenic risks were in the coastal water, and low estrogenic risks in the open sea.     

Occurrence of xenobiotic ligands for retinoid X receptors and thyroid hormone receptors in the aquatic environment of Taiwan

Various synthetic compounds are frequently discharged into the environment via human activities. Among them, certain contaminants may disrupt normal physiological functions of wildlife and humans via interactions with nuclear receptors. To protect human health and the environment, it is important to detect environmental ligands for human nuclear receptors. In this study, yeast-based reporter gene assays were used to investigate the occurrence of xenobiotic ligands for retinoid X receptors (RXR) and thyroid hormone receptors (TR) in the aquatic environment of Taiwan. Experimental results revealed that RXR agonist/antagonist activity was detected in river water and sediment samples. In particular, high RXR agonist/antagonist activity was found in the samples collected near river mouths. Additionally, few samples also elicited significant TR antagonist activity. Our findings show that the aquatic environment of Taiwan was contaminated with RXR and TR ligands. Further study is necessary to identify these xenobiotic RXR and TR agonists and antagonists.     

Development of a SPME-GC Method for the Determination of Organic Compounds in Wastewater

A manual SPME method is presented for the analysis of organic compounds in industrial wastewater. 24 compounds commonly found in the wastewater of a chemical plant in northern Germany have been selected as reference compounds. Precision, linearity, and detection limits have been determined. Moreover, the effect of methanol content, pH value, salt content, and an excess of compounds on the extraction process have been studied. Several compounds have been investigated for their applicability as internal standards to quantify the compounds of interest. Since the method will later be transferred to a fully automated SPME-GC system, which will be operated directly on-site at an industrial wastewater purification plant, special attention has been paid to the analysis of real wastewater samples. In this context, the fibre stability has been studied by performing 53 extraction/desorption cycles from one wastewater sample. Neither a decrease in fibre performance nor in precision has been observed indicating that the proposed method is suitable for the analysis of real wastewater.     

Agrochemical and polychlorobyphenyl (PCB) residues in the Mekong River delta, Vietnam

An environmental survey on pesticide residues and polychlorobyphenyl compounds (PCBs), encompassing more than 70 polar and non-polar compounds quantifiable by the techniques used, was performed in the Mekong River delta based on analyses of water, sediment and bivalve mollusc samples. Few polar compounds, such as diazinon and fenotrothion, were detected in water but a high number of non-polar chlorinated compounds, such as DDT, HCH, endosulfan and PCBs, were detected in sediments and biota. The highest concentrations measured were of DDT with an average 6.3 ng g(-1) dry weight (range 0.32-67 ng g(-1)) in sediments and 38.6 ng g(-1) (range 5.5-123 ng g(-1)) in molluscs' soft tissues. Amongst chlorinated compounds, DDT concentrations were followed in decreasing order by those of PCB, endosulfan, hexachlorocyclohexane and chlordane. Residues of organochlorine compounds originate from local usage of agrochemicals although with a likely contribution also of atmospheric deposition of residues (not measured) originated elsewhere. Concentrations of PCB and pesticide residues in the aquatic environment of the Mekong River delta are lower than values reported for other regions of Vietnam and Asia. Nevertheless, current concerns about the effects of chlorinated compounds on public health advise improved control of chemical residue discharges in order to abate environmental contamination.     

Role of a moderately halophilic bacterial consortium in the biodegradation of polyaromatic hydrocarbons

Polycyclic aromatic hydrocarbons are ubiquitous pollutants in the environment, and most high molecular weight PAHs cause mutagenic, teratogenic and potentially carcinogenic effects. While several strains have been identified that degrade PAHs, the present study is focused on the degradation of PAHs in a marine environment by a moderately halophilic bacterial consortium. The bacterial consortium was isolated from a mixture of marine water samples collected from seven different sites in Chennai, India. The low molecular weight (LMW) PAHs phenanthrene and fluorine, and the high molecular weight (HMW) PAHs pyrene and benzo(e)pyrene were selected for the degradation study. The consortium metabolized both LMW and HMW PAHs. The consortium was also able to degrade PAHs present in crude oil-contaminated saline wastewater. The bacterial consortium was able to degrade 80% of HMW PAHs and 100% of LMW PAHs in the saline wastewater. The strains present in the consortium were identified as Ochrobactrum sp., Enterobacter cloacae and Stenotrophomonas maltophilia. This study reveals that these bacteria have the potential to degrade different PAHs in saline wastewater.     

Differences between Humic Substances from Riverine,Estuarine, and Marine Environments Observed by Fluorescence Spectroscopy

Sixteen samples of fulvic acids and XAD‐4 fractions of riverine, estuarine, coastal, and open ocean origin have been studied by emission and synchronous molecular fluorescence spectroscopy. Certain features of the molecular fluorescence are related to the nature, the content, and the origin of those aquatic humic substances (HS). Riverine HS appear several times richer in fluorophores than marine HS, which can be well observed by emission fluorescence spectroscopy. Synchronous‐scan spectra of fulvic acids and of XAD‐4 fractions from the aquatic environments studied, emphasized the quality differences of their fluorophores. These features are useful as tracers of humic substances related with their natural environment source or even with their anthropogenic origin.     

Organic compounds in thermal water: The Mutnovskii area and the Uzon caldera

New data are reported relating to the presence and relative concentrations of organic compounds of medium volatility in samples from the water of hot springs and in the condensate of a steam–water mixture from wells drilled in the Mutnovskii geothermal area and from a well and springs in the Uzon caldera. The Mutnovskii area was found to contain 95 compounds belonging to 16 homologous series, with 71 compounds (12 series) in the Uzon caldera. Among these we found homologous series of biologically important compounds: carbonic acids, alcohols, ethers, aldehydes, ketones, and others. Evidence was obtained for a contribution of the abiogenic component in organic matter from sterile condensates of an overheated steam–water mixture from wells (alkanes, aromatic hydrocarbons, ketones, alcohols, and others) and in thermal water from natural discharges (in particular, alkanes and chlorine-containing hydrocarbons). The results of this study can be used for the preparation and conduction of laboratory experiments in prebiological chemistry under conditions that simulate a hydrothermal environment.     

Polybrominated diphenyl ethers and their hydroxylated/methoxylated analogs: Environmental sources,metabolic relationships,and relative toxicities

Brominated compounds are ubiquitous in the aquatic environment. The polybrominated diphenyl ether (PBDE) flame retardants are anthropogenic compounds of concern. Studies suggest that PBDEs can be biotransformed to hydroxylated brominated diphenyl ethers (OH-BDE). However, the rate of OH-BDE formation observed has been extremely small. OH-BDEs have also been identified as natural compounds produced by some marine invertebrates. Another class of compounds, the methoxylated BDEs (MeO-BDEs), has also been identified as natural compounds in the marine environment. Both the OH-BDEs and MeO-BDEs bioaccumulate in higher marine organisms. Recent studies have demonstrated that MeO-BDEs can be biotransformed to OH-BDEs and this generates greater amounts of OH-BDEs than could be generated from PBDEs. Consequently, MeO-BDEs likely represent the primary source of metabolically derived OH-BDEs. Given that for some endpoints OH-BDEs often exhibit greater toxicity compared to PBDEs, it is prudent to consider OH-BDEs as chemicals of concern, despite their seemingly “natural” origins.     

Polybrominated diphenyl ethers and their hydroxylated/methoxylated analogs: environmental sources, metabolic relationships, and relative toxicities

Brominated compounds are ubiquitous in the aquatic environment. The polybrominated diphenyl ether (PBDE) flame retardants are anthropogenic compounds of concern. Studies suggest that PBDEs can be biotransformed to hydroxylated brominated diphenyl ethers (OH-BDE). However, the rate of OH-BDE formation observed has been extremely small. OH-BDEs have also been identified as natural compounds produced by some marine invertebrates. Another class of compounds, the methoxylated BDEs (MeO-BDEs), has also been identified as natural compounds in the marine environment. Both the OH-BDEs and MeO-BDEs bioaccumulate in higher marine organisms. Recent studies have demonstrated that MeO-BDEs can be biotransformed to OH-BDEs and this generates greater amounts of OH-BDEs than could be generated from PBDEs. Consequently, MeO-BDEs likely represent the primary source of metabolically derived OH-BDEs. Given that for some endpoints OH-BDEs often exhibit greater toxicity compared to PBDEs, it is prudent to consider OH-BDEs as chemicals of concern, despite their seemingly "natural" origins.     

Detection of Pharmaceuticals and Personal Care Products in Agricultural Soils Receiving Biosolids Application

Increasing research has suggested that biosolids generated from municipal wastewater treatment can be a major sink for many pharmaceuticals and personal care products (PPCPs) and their land application potentially introduces these contaminants into the terrestrial and aquatic environments. In this study, methods were developed for the analysis of 14 PPCPs in biosolids and soils using pressurized liquid extraction, solid phase extraction and liquid chromatography‐tandem mass spectrometry. Recoveries were over 50% for all analytes except diphenhydramine (?30%) in soils. Soil properties or type of biosolids showed minor effects on method recoveries. Estimated method limits of quantification (LOQ) range from 0.1–15 ng g^–1 for soil and 0.3–27 ng g^–1 for biosolids. A field study utilizing the methods revealed that other than carbamazepine‐10,11‐epoxide, all targeted compounds were detected in biosolids. Diphenhydramine, fluoxetine, triclosan and triclocarban were detected up to the μg g^–1 range with the highest concentration of 23 μg g^–1 for triclocarban. Seven of the PCCPs found in biosolids were also detected in agricultural soils amended with these biosolids and several (carbamazepine, diphenhydramine, and triclocarban) appeared to be persistent in soils. Triclocarban was also found most abundant in soils with the highest average concentration of 0.2 μg g^–1 while the rest of compounds were in the lower ng g^–1 range. Generally, the concentrations found on the fields were 2–3 degrees of magnitude lower than in the biosolids, which is likely to be due to dilution, degradation and leaching processes.     

Bioassaying in the assessment of wastewater treatment process efficiency

The results of studies with the use of bioassaying methods for evaluating the efficiency of wastewater treatment processes and their effect on the biological adequacy of the natural aquatic environment are given. It is stressed that a test for wastewater toxicity with the use of most informative bioassaying methods should be included in the regulatory requirements.     

Identifizierung von Stickstoffverbindungen niederer molarer Masse in Abläufen einer kommunalen Kläranlage mit biologischer Reinigungsstufe

Identification of Nitrogen-containing Compounds of Low Molecular Weight in Effluents of Biologically Treated Municipal Wastewater Enriching methods based on reversed phases were developed for the investigation of low-molecular compounds containing nitrogen in municipal wastewater effluent. The enriched mixtures were treated gas chromatographically without derivatization under different conditions. By application of the PBM-algorithm to the GC/MS spectra of the enriched samples (concentration factor 1000...20000), 133 nitrogen-containing compounds could be identified with a probability of occurence of at least 30% put out. Seventeen of these compounds were identified with > 90% probability and another ten with 80...90% probability. 9-Methylacridine was found in nine of ten processed samples investigated. The nitrogen content of the 133 identified compounds was estimated at about 20% of the low-molecular fraction of DON (dissolved organic nitrogen).     

Perfluorinated compounds in blood of Caretta caretta from the Mediterranean Sea

Perfluorinated compounds (PFCs), widely used for their hydro-oil repellent properties, are almost non-degradable in the environment; there is scientific evidence that indicate bioaccumulation. They represent a threat to many organisms, because they are toxic and are endocrine disruptors. Scientific studies have demonstrated the presence of PFCs in blood and liver samples of fish, turtles, birds and mammals of marine ecosystems in different geographical areas. The aim of this study was to determine the distribution of PFOS and PFOA in blood samples of the marine turtle Caretta caretta, using a minimally invasive sampling procedure. 49 blood samples of marine turtle, taken from several Italian marine turtle rescue centers, were analyzed. While PFOA was never detected, measurable concentrations of PFOS were found in 15 blood samples; the values show a range from 1.14 ng/g to 28.51 ng/g (wet wt.). No differences between groups of samples taken from different areas were found.     

Belastung von Krankenhausabwasser mit gefährlichen Stoffen im Sinne § 7a WHG

Contamination of Hospital Wastewater with Hazardous Compounds as Defined by § 7a WHG In total, 45 samples of hospital wastewater obtained from different origins (total wastewater, nursing, and laboratories) were investigated using chemical analyses as well as biological testing methods. In parallel, the consumption of several product groups relevant to the wastewater has been calculated. The water consumption strongly influenced the quality of the corresponding wastewater. Most of the values of the chemical parameters determined were found within a range as would have been expected for municipal wastewater. The AOX concentrations were distinctly elevated (0.41 mg/L in total wastewater and 0.95 mg/L in nursing wastewater). As could be shown by the calculated consumption of different compounds, the iodoferous X-ray contrast media represented a predominant proportion of the total AOX load of the clinical wastewaters tested. The values of some of the total wastewater samples and the laboratory wastewater samples showed a high toxicity as determined using the daphnia and luminescent bacteria tests. Using Ames and hamster cell tests, 5 out of 23 samples in the clinical area and 7 out of 9 samples from the laboratories turned out to be mutagenic. The origin of this mutagenic potential could not be determined though.     

Bestimmung von Umweltqualitätsnormen für potenziell gewässerrelevante Stoffe

With the Water Framework Directive (WFD) the European Commission (EC) is requested to define environmental quality standards for pollutants to protect aquatic life in surface waters. Quality standards have to be derived by a scientific risk assessment and should not be exceeded. The recommended quality standards are mainly based on long term toxicological tests with algae, crustaceans and fish. The lowest effect concentration is divided by an assessment factor between 10 and 1000, which considers the data quality and quantity. In this work funded by the German Länder Working Party on Water (Länderarbeitsgemeinschaft Wasser – LAWA) environmental quality standards for 40 considered relevant substances were derived for aquatic ecosystems. The data sheets cover the identification of the compounds, their behaviour in the environment (physical‐chemical properties, biotic and abiotic degradation, sorption, bioaccumulation), information about mode of action, uses, analytical determination and available quality criteria. Ecotoxicological effect concentrations for bacteria, algae, protozoa, aquatic plants, crustaceans, fish, amphibians, insects and molluscs are listed. For 17 of the 40 hazardous substances investigated, quality objectives above 1 μg/L were derived. For 12 substances the values were between 0.1 μg/L and 1 μg/L and for 5 substances lower than 0.1 μg/L. Incomplete ecotoxicological data sets of the remaining compounds do not allow the derivation of quality standards. Especially for drugs further ecotoxicological test results are needed.     

eDNA监测方法标准化框架及未来图景

eDNA (environmental DNA)是指从环境样品（水体、土壤、沉积物、空气、混合物等）中提取的DNA,是各种生物的DNA混合物,区别于传统从单物种样品中提取的DNA。eDNA监测是指从环境样品中提取DNA,用物种特异性引物或特定DNA metabarcoding引物对其进行扩增测序、分类学分析、相对丰度分析、功能预测等,以监测环境中是否存在某特定物种,或者获得环境中物种组成、群落结构、生态功能等相关信息。eDNA监测主要应用在特定物种监测检出、生物多样性调查评估、群落结构和功能分析、生态系统过程分析评估等领域。eDNA监测可以应用在陆地、水体、空气、器物表面、生物（内）表面等任何有可能存在不确定DNA的场景。因为eDNA监测的非侵入性、灵敏检出、大类群检出、易标准化方法与结果、低人力物力时间成本、结果可核查等特点,未来很有希望发展成为一种常规的物种监测、群落功能预测、生态过程分析的方法,对象可涵盖所有生境条件下的所有生物类群。但要实现这个图景,需要从普遍性和特殊性层面完成eDNA监测技术链条中10个关键环节的技术标准化：样品重复数设计、采样时间设计、采样点设计、采样方法设...     

Determination of Selected Endocrine Disrupter Compounds at Trace Levels in Sewage Sludge Samples

Simultaneous determination of endocrine disrupter compounds (EDCs), namely diltiazem, progesterone, benzylbutylphthalate (BBP), estrone, and carbamazepine (Cbz) were performed by using high performance LC–electrospray tandem MS. The ultrasound‐aided sequential extraction of sludge samples was optimized to increase extraction efficiencies of the analytes; ranging between 93.0–98.3% recovery. The limit of detection values for diltiazem, progesterone, BBP, estrone, and Cbz were found as 0.78, 0.72, 0.24, 0.75, and 0.72 µg/kg, respectively. Sludge samples taken from Ankara Tatlar; Hurma, Lara and Kemer of Antalya, and Middle East Technical University‐vacuum rotating membrane wastewater treatment plant (WWTP) aeration tanks were analyzed for their EDCs contents under optimized conditions. Diltiazem was found in all the samples in the range between 116.4–180.8 ng/g while progesterone and estrone were not detected in any of the samples analyzed with the exception of Tatlar WWTP. The BBP concentration was between beyond detection and 9195.5 ng/g. In addition, Cbz was found in all the samples ranging from 25.6 to 118.8 ng/g.     

Determination of Polar Organic Pollutants in Aqueous Samples of Former Ammunition Sites in Lower Saxony by Means of HPLC/Photodiode Array Detection (HPLC/PDA) and Proton Nuclear Magnetic Resonance Spectroscopy ( 1H-NMR)

Leachate, ground-, and surface water from former ammunition sites and areas which are known to be contaminated by nitroaromatic compounds in Lower Saxony (Germany) were investigated in order to identify and quantify acidic nitroaromatic compounds (e.g., nitrobenzoic acids, aminonitrobenzoic acids, nitrophenols, and nitrocresols). Acidic and neutral nitroaromatic compounds were enriched by solid-phase extraction (SPE) on a polystyrenedivinylbenzene copolymer and routinely screened for acidic compounds by means of HPLC/photodiode array detection (HPLC/PDA). Qualitative and quantitative results obtained in this way were corroborated by proton nuclear magnetic resonance spectroscopy (¹H-NMR). Validation data for the quantification procedure using this technique are given. The results show that all samples contaminated with 2,4,6-trinitrotoluene (TNT) and related compounds are also contaminated by acidic nitroaromatic compounds (e.g., 2,4-dinitrobenzoic acid, 3,5-dinitrophenol, and especially with 2-amino-4,6-dinitrobenzoic acid) in the μg/L range. This current work shows that 1 H-NMR allows the quantitative determination of protoncarrying analytes in mixtures after solid-phase extraction down to the upper ng/L range after addition of an internal standard to the SPE extract. This is even possible when reference compounds are not commercially available.