Vorkommen natürlicher und synthetischer östrogener Steroide in Wässern des süd‐ und mitteldeutschen Raumes

Distribution of Natural and Synthetic Estrogenic Steroid Hormones in Water Samples from Southern and Middle Germany Natural and synthetic hormones can reach surface waters via domestic sewage effluents. For drinking water production, bank filtration of river waters is a common procedure and hormone contaminations can potentially reach groundwater levels and drinking water sources. In order to analyse steroid hormones in the different aquatic compartments (raw sewage and effluent, surface water, groundwater, raw and drinking water) of South and Middle Germany, a sensitive analytical method was developed and employed to detect the natural steroid hormones estradiol (E2) and estrone and the synthetic estrogen ethinylestradiol (EE2). Samples which were taken in two subsequent series were subjected to clean‐up and enrichment procedure and subsequently analysed by HPLC‐MS. The limit of quantitation for the method was determined to be 0.05 to 0.5 ng/L, depending on the matrix. By treating the samples with glucuronidases/arylsulfatases, conjugates were amenable to analysis and the sum of conjugates and unconjugated steroids was calculated. In raw sewage, the median of the concentrations of the unconjugated steroids was 7 ng/L for EE2, 1.5 ng/L for E2, and 5.5 ng/L for estrone. After cleavage of conjugates, the medians of total steroids were 9.5 ng/L (EE2), 3 ng/L (E2), and 13 ng/l (estrone). Conjugates therefore contributed up to 50 % of the total steroid concentration in raw sewage. In treated effluents, the concentrations of steroids were much lower than in the raw sewage. The medians of free steroids were determined to be 0.3 ng/L for EE2, 0.2 ng/L for E2, and 2.5 ng/L for estrone. Overall the medians in the effluent were thus less than 10% of those in the influent. Conjugates still contributed significantly (40% and more) to the steroid concentrations (medians: EE2: 0.5 ng/L, E2: 0.8 ng/L, and estrone: 8 ng/L).     

Occurrence of Phthalates in Sewage Sludge from Three Wastewater Treatment Plants in Istanbul,Turkey

Phthalates are considered priority pollutants because of their potential adverse effects on ecosystems and human health. The objectives of this study were to determine the occurrence of five phthalates (DMP, DEP, DBP, BBP, and DEHP) in sewage sludge and to determine the seasonal variability of these contaminants at three (Bahçe?ehir, Pa?aköy, and Tuzla) full‐scale municipal and domestic wastewater treatment plants (WWTP) in Istanbul, Turkey. Mass balance was also calculated for DEHP at Tuzla WWTP sludge treatment units. DMP, DEP, DBP, BBP, and DEHP concentrations in sewage sludge ranged from 1.4 to 2.7 mg/kg dry weight (dw), 1.1 to 2.8, 0.6 to 4.6, 2.8 to 6.2, 18 to 490 mg/kg dw, respectively. Phthalate concentrations from the Bahçe?ehir and Pa?aköy WWTPs met the limit (100 mg/kg dw) of Turkey national sludge regulation and the Europe Union draft of sludge directive for land application, whereas phthalate concentrations from Tuzla WWTP exceeded the maximum permissible concentration. Phthalate concentrations did not show seasonal variations for Bahçe?ehir and Pa?aköy WWTPs, which receive mainly household wastewater while some fluctuations were observed DEP, DBP, and DEHP at Tuzla WWTP which has a lot of industrial wastewater contribution. The mass balance showed that approximately 17% of DEHP in the primary and secondary sludge was removed by anaerobic digestion, while 43% returned back to the beginning of the WWTP and 40% remained in the dewatered sludge. This study suggests that phthalates in sludge from WWTPs with industrial wastewater contribution may limit the use of sludge for land application.     

Analysis of Endocrine Disrupting Steroids: Investigation of Their Release into the Environment and Their Behavior During Bank Filtration

A reliable and sensitive analytical method for the determination of estrone (E1), 17β-estradiol (E2), and the synthetic hormone 17α-ethinylestradiol (EE2) has been established. Samples are concentrated using automated solid-phase extraction and analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Recoveries of all analytes were between 93% and 107%, and limits of quantification (LOQs) between 0.1 and 0.4 ng/L for purified sewage, and surface, ground, and drinking water, and between 1 and 2 ng/L in case of raw sewage. For the investigation of estrogen release into the environment and its behavior during sewage and surface water treatment, and during ground water recharge, samples from municipal waste water treatment plants (WWTPs), a surface water treatment plant, a bank filtration site, and a ground water enrichment (GWE) pond were analyzed. El was found in the raw waste water with an average concentration of 157 ng/L, whereas E2 and EE2 were found with mean concentrations of only 18 and 9 ng/L, respectively. Sewage treatment by municipal WWTPs affected a removal of EE2 (76%), El (92%), and E2 (94%). In the investigated surface water of Berlin, only E1 could be detected at concentrations around or below 1 ng/L. E2 and EE2 were not present in the Berlin surface water above the LOQ of 0.2 ng/L, respectively. Surface water treatment also leads to a significant removal of E1 (> 80%). In the ground water samples from the GWE site near Lake Tegel, only a few samples contained detectable concentrations of E1. These samples were collected from a shallow monitoring well located very close to the bank of the pond. Even a short distance between the bank and observation wells led to concentrations of El below the LOQ showing the potential of ground water recharge systems for the retention of estrogenic steroids depending on the environmental setting.     

Bioassay‐directed fractionation for analyzing estrogens in surface waters of the German Baltic Sea

A reversed‐phase fractionation method with subsequent biological and chemical analysis has been developed to estimate the contributions of the most potent estrogens to observed estrogenic effect potentials. Surface water samples were taken in the German Baltic Sea (Inner Wismar Bay and Darss Peninsula, sampling campaign July 2003) and were separated into seven individual fractions. Three fractions showed significant estrogenic activities and clear dose‐dependant responses were obtained in the yeast estrogen screen (YES). In the 2nd fractions liquid chromatographic‐electrospray‐tandem mass spectrometric (LC‐ESI‐MS‐MS) analyses showed the presence of bisphenol A (Inner Wismar Bay: 4.8 ng L^–1 and 6 ng L^–1; Darss Peninsula: 0.91 ng L^–1 and 1.7 ng L^–1) and ethinylestradiol (Inner Wismar Bay: 2.0 ng L^–1 and 6.0 ng L^–1; Darss Peninsula: < MDL and 1.7 ng L^–1), whereas estrogenic activities in the YES were only around 10% of the positive control E2. Although not identified prior in the total extract the natural hormones estradiol (Inner Wismar Bay: 0.13 ng L^–1 and 0.19 ng L^–1; Darss Peninsula: 0.12 ng L^–1 and 0.16 ng L^–1) and estriol (Inner Wismar Bay: < MDL and 0.33 ng L^–1; Darss Peninsula: < MDL) could be detected in the 3rd fractions, where high estrogenic potentials could be observed. The 4th fractions showed high responses as well and estrone were herein quantified with concentrations of 0.16 ng L^–1 and 0.18 ng L^–1 (Darss Peninsula) up to 0.37 ng L^–1 (Inner Wismar Bay). Measured and calculated estradiol equivalents for individual fractions correlated very well (R² = 0.78), when disregarding results of the 2nd fraction, where high deviations occurred.     

Estrogen pollution in a highly productive ecosystem off central-south Chile

While the presence of steroid estrogens in the environment has become a major environmental and health concern, their occurrence in coastal sediments remains poorly characterized. In this study, we measured the levels of three natural (estrone, 17β-estradiol, estriol) and one synthetic (17α-ethinylestradiol) estrogens in 54 coastal sediment samples collected from nine locations off central-southern Chile. Steroid estrogens were found in every sample. Remarkably high levels of 17α-ethinylestradiol were detected, reaching up to 48.14 ng/g dry weight. As a result, the global estrogenic loads were estimated to be high at all sites. Interestingly, they were found to correlate with the size of human populations served by sewage plants. Our study indicates that 17α-ethinylestradiol may accumulate in coastal sediments. The possible impact of this highly potent synthetic estrogen on the biota of the marine ecosystem off central-south Chile and on human health remains an open question.     

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.     

Study on a comprehensive evaluation method for the assessment of the operational efficiency of wastewater treatment plants

A fuzzy matter-element model, combined with the entropy weight of an index, has been used as an evaluation method to achieve a comprehensive assessment and analysis of the operational efficiency of wastewater treatment plants (WWTPs). The feasibility of the method had been validated based on actual operational data and instance from eight WWTPs located in a city in Northern China. According to the results of the comprehensive evaluation, the operational efficiency of the WWTP using an anaerobic/anoxic/oxic process was generally better than other wastewater treating technologies. And especially, the removal efficiencies of nitrogen and phosphorus pollutants were much higher for the process, which suits well the actual operational situation of Chinese WWTPs. Total nitrogen (TN) removal rate and the productive quantity of the excess sludge cake were identified as important factors in the evaluation of the operational efficiency for a WWTP. So the operation level of WWTP could be improved by increasing the TN removal rate and decreasing the excess sludge cake quantity. The developed method can evaluate and analyze the operational efficiency scientifically and objectively, and the evaluation results can be used to guide the construction, operation and management of WWTPs in The Three Gorge reservoir district of China.     

Assessment of Urban Source Metal Levels in Influent,Effluent, and Sludge of Two Municipal Biological Nutrient Removal Wastewater Treatment Plants of Bursa,an Industrial City in Turkey

Removal of Al, As, Cd, total Cr (Tot. Cr), Cu, Total Fe (Tot. Fe), Mn, Ni, Pb, Sb, Sn, and Zn from urban effluent by wastewater treatment plants (WWTPs) operated under five‐stage Bardenpho® process were investigated and water soluble metals in the dewatered sludge were quantified. Samples were collected from two WWTPs on a weekly basis over an approximately 2.5‐year time span. Tot. Fe and Al were the most abundant, As, Pb, Ni, Cu, and Cd were the least abundant metals in the influents of both WWTPs. Removal efficiencies above 75% were achieved for Tot. Cr, Tot. Fe, Al, and Cu, whereas, no significant removal was observed for As, Cd, Pb, Sb, and Sn. Removal of Tot. Cr, Cu, Tot. Fe, Zn, Al, Mn, and Ni were influenced by influent suspended solids concentrations, and of Tot. Cr, Zn, and Cd were influenced by their initial content in the influent. Zn removal efficiency of biological nutrient removal (BNR) system in this study was higher and Cd removal efficiency was lower than that of conventional activated sludge reported in the literature. No remarkable difference for metals such as Cu, Mn, Ni, and Pb was observed between the removal efficiencies of conventional system and BNR system.     

Typology of Municipal Wastewater Treatment Technologies in Latin America

This paper presents an analysis of the wastewater treatment plants in six Latin American and Caribbean countries. Based on a sample of 2734 municipal treatment facilities, the applied processes are classified by sizes (influent flow) and type of technologies. The distribution of the technologies is also presented for each of the six countries. In addition, a representative municipal wastewater characterization, based on influent data from 174 treatment plants, is proposed. Results show that stabilization ponds, activated sludge, and the upflow anaerobic sludge blanket reactors represent 80% of the treatment facilities of the sample, providing treatment to 81% of the total flow considered. Moreover, 67% of the plants in the sample are small (flow <25 L/s) and the very small facilities (influent flow <5 L/s) are extensively applied in the region (34% of the sample), especially in Mexico and Brazil. The use of very small treatment plants may result in low energy efficiency systems and on possible incompliance of the discharge standards. This common practice in several countries in Latin America should be revised in order to improve the environmental performance of such facilities.     

Fate of antibiotics during wastewater treatment and antibiotic distribution in the effluent-receiving waters of the Yellow Sea,northern China

Antibiotics including three β-lactams, two fluoroquinolones and two macrolides, which were the top seven most prescribed antibiotics in Dalian, China, were selected to investigate their occurrence in six municipal wastewater treatment plants (WWTPs) and their distribution in the effluent-receiving waters of the Yellow Sea. Four WWTPs employing different treatment technologies were selected to explore the mechanism of antibiotics elimination during wastewater treatment. Results showed that fluoroquinolones and macrolides were dominant species in both WWTPs effluents and the surveyed coastal waters. Biodegradation was the main pathway for β-lactams removal, however, primary treatment performed better than biological treatment for fluoroquinolones removal. Concentrations of macrolides increased dramatically after the biological treatment, which was probably due to the release of macrolides enclosed in feces particles. In the surveyed coastal waters, reduction of antibiotic concentration with distance was observed. Potential environmental risk caused by the occurrence of these antibiotics should be evaluated in future work.     

Removal of Aromatic Volatile Organic Compounds in the Sequencing Batch Reactor of Petroleum Refinery Wastewater Treatment Plant

This paper presents a field investigation of aromatic volatile organic compounds (AVOCs) emissions from a sequence batch reactor (SBR) with powdered activated carbon (PAC) to treat the wastewater in a large petroleum refinery plant. AVOC with high Henry's constant preferred to transfer from liquid‐phase into air‐phase so that might cause the emission and odor problem. During SBR operation, AVOC concentrations and distributions in wastewater, sludge and off‐gas were analyzed. The total AVOC removal from wastewater was >99% under the kinetic parameters of SBR operated. Batch experiments were carried out in the laboratory to obtain the adsorptive characteristic of AVOC onto PAC, but the results showed that bio‐degradation was the main removal mechanism (85%). Nevertheless, off‐gas emission (<1%) and AVOC in the sludge (<0.1%) remained a stable level. Oxidation/reduction potential (ORP) was correlated to the logarithm of the dissolved oxygen (DO) concentration in a linear relationship so that ORP profile could indirectly reflect the DO and biomass concentrations. Since the influent AVOC concentration was varied and difficultly to measure, ORP could be used as real‐time parameter for optimizing SBR operation. The results provided useful information for future evaluation of AVOC emissions from wastewater treatment plants.     

Occurrence of endocrine-disrupting chemicals in riverine sediments from the Pearl River Delta, China

The endocrine-disrupting chemicals (EDCs) was investigated in 28 riverine sediments from the Pearl River system, China and analyzed by an ultrasonication extraction and GC-MS method. The concentrations of 4-tert-octylphenol (OP), 4-nonylphenol (NP), and bisphenol A (BPA) in the sediments were in the ranges of <2.0-210, 107-16198 and <1.7-430 ng/g dw, respectively. The steroid estrogens estrone (E1) and 17β-estradiol (E2) in the sediments ranged from <1.3 to 10.9 ng/gdw and from <0.9 to 2.6 ng/gdw, respectively. The spatial distribution of these chemicals was related to the discharge of domestic and industrial wastewater along the rivers. The positive correlation between EDCs and total organic carbon indicates that sedimentary organic carbon is an important factor in controlling the distributions of EDCs. Compared with other previous studies, the ZR and DR rivers from the PRD were heavily contaminated by APs and BPA.     

POPs and their ecological risk in sewage sludge of waste water treatment plants in Beijing, China

The concentrations of three classes of persistent organic compounds (POPs) in the sewage sludge from 12 Beijing wastewater treatment plants (WWTPs) were investigated and their ecological risks were assessed. The concentrations of 15 polycyclic aromatic hydrocarbons (PAHs), 27 polychlorinated biphenyl congeners (PCBs) and 15 organochlorine pesticides (OCPs) in sewage sludge were measured using gas chromatography–tandem mass spectrometry (GC–MS/MS) technique. Total PAHs concentrations ranged from 445.1 to 3,586.4 ng g^?1 dry weight (dw), and the sum of the phenanthrene (Phe), anthracene (Ant), naphthalene (Nap), fluoranthene and chrysene accounted for 69.3–97.0 % of the total PAHs. The most abundant compounds present were 2-ring and 3-ring Ant, Phe and Nap, indicating a possible petrogenic source. Total PCBs concentrations were ranged between 3.2 and 21.8 ng g^?1 dw. Total OCPs concentrations ranged from 38.0 to 143.3 ng g^?1 dw, and the sum of total DDT, HCB and HCHs accounted for 69.6–97.7 % of the total OCPs. The levels of PAHs, PCBs and OCPs in this study were comparable to or lower than those reported in relatively WWTPs from other regions. In addition, they were also shown to have various distribution patterns, possibly due to their different wastewater sources. The 12 WWTPs may be classified into 4 groups because of their different sources of waste water based on cluster analysis. The ecological risk assessment shows that the concentrations of Ant or Fla at two sites, p,p′-DDE and ∑DDT at 83 % of the 12 sites may cause adverse ecological effects.     

Hormone loads exported by a tile‐drained agroecosystem receiving animal wastes

Little is known regarding hormone export from tile‐drained agricultural fields despite the widespread presence of tile drains in the Midwestern United States. By intensively measuring water flow rates and hormone concentrations in four subsurface tile drains and three receiving ditches at a working Midwest farm, hormone fluxes and loads from the tile‐drained fields were quantified. Before and during the 17‐month study period (January 2009 – May 2010), the associated farm fields received various animal waste applications (beef, dairy, poultry, sheep, and swine). Hormones monitored included the estrogens17β‐ and 17α‐estradiol, estrone, and estriol; the natural androgens testosterone, and androstenedione; and the synthetic androgens 17β‐ and 17α‐trenbolone, and trendione. Hormone loads measured in the ditches for three drainage areas during the entire 17‐month study period were in ranges of 16–58 mg/ha for total estrogens, 6.8–19 mg/ha for natural androgens, and 4.2–44 mg/ha for synthetic androgens. Because higher hormone concentrations generally occurred during discrete periods of increased flow, high flow rates often were associated with a disproportionately high hormone flux. For example, 80% of total estrogens and natural androgens exported into the ditches occurred during only 9–26% of the study period, coinciding with the most significant storm events. In addition, hormone fluxes were highest during storm events that occurred shortly after animal waste applications. Therefore, to effectively reduce hormone loads exported to downstream aquatic ecosystems in the absence of any application reduction, the short periods during which high‐flow events occur must be targeted. Copyright © 2012 John Wiley & Sons, Ltd.     

Assessing Environmental Impacts of Wastewater Treatment Alternatives for Small‐Scale Communities

The effluents of wastewater treatment plants in small sized communities of less than 2000 population equivalent (PE), which are discharged into sensitive receiving water environments, must receive “appropriate treatment” according to the EU Urban Wastewater Treatment Directive. Appropriate treatment depends on the quality objectives of the receiving waters as well as the relevant provisions of the member states. In this study, wastewater treatment options, such as vegetated land treatment (VLT), constructed wetlands (CW), and activated sludge treatment (AST), by which effluents are discharged to sensitive and less sensitive areas are evaluated by the life cycle assessment (LCA) approach. For this purpose, data related to energy usage, land requirement, raw material consumption, and released emissions from the life phases were collected with an inventory study and the environmental impacts were assessed by using SimaPro 7.1 LCA software. The results obtained from the assessments were compared with each other, which indicated that for small‐scale communities VLT and CW are the most environmentally friendly wastewater treatment option.     

Wastewater treatment for small communities in Catalonia (Mediterranean region)

An evaluation of small wastewater treatment plants (WWTPs) treating the effluents of communities with <2000 inhabitants in Catalonia (north-east of Spain) was carried out to establish the definition of appropriate wastewater treatment (AWT) and the criteria for the selection of the alternative processes that can achieve the AWT. The implementation of an AWT in these communities before the end of the year 2005 is necessary to comply with the European Directive 91/271. The AWT is that which permits the accomplishment of quality objectives in receiving waters after the discharge of the effluents. The standards for the AWT in each particular case are set out through a contaminant loading balance. Nevertheless, the final applied standards can only be as strict as they are for larger WWTPs. These criteria are very close to those stated in the French legislation, and it is felt that they are at the same time environment-friendly and realistic for small WWTPs. Secondary treatments are generally recommended to achieve the AWT. Natural wastewater treatment systems are preferred over conventional treatments to achieve the appropriate treatment because they are simple to operate, can reach the same level of treatment efficiency and have lower operation and maintenance costs. The policy debate that has produced all these statements is described.     

AOX‐Bildung bei der sonolytischen Oxidation von Salicylsäure in Gegenwart von Chlorid

AOX‐formation by the Sonochemical Treatment of Salicylic Acid in Presence of Chloride Ultrasound shows great potential for improving water, wastewater and sludge treatment processes. However, a number of questions exist: for example the influence of suspended solids or salts. In this paper the influence of chloride in view of AOX‐formation should be investigated. As organic model compound salicylic acid (0.05…1 mmol/L) was used. Formation of AOX (adsorbable organically bound halogens) was measured in dependence upon chloride concentrations (1.4…141 mmol/L) and pH 2 and 9. Ultrasound irradiation was performed in glass reactor (500 mL) at 206 kHz and 353 kHz by continuous bubbling argon:oxgen (4:1) at a flow rate of 1 L/min into the solutions. The elimination of salicylic acid and the formation of hydrogen peroxide were not influenced by the presence of chloride (up to 56 mmol/L). The rate of salicylic acid elimination and the formation rate of hydrogen peroxide are at concentrations of mmol/(L min) levels but those of AOX formation of μmol/(L min) levels. The reactions leading to chlorinated by‐products can be seen as minor reaction paths. The yield of AOX depending on frequency, pH and chloride concentration lies between 10 μg/L and 900 μg/L. In acidic medium they were twice as high as in basic medium. Below the ratio chloride : salicylic acid of 2 mol/mol, AOX could not be identified.     

Simultaneous Analysis of Natural Free Estrogens and Their Conjugates in Wastewater by GC‐MS

A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L^–1, respectively. However, only E1 was detected at a high concentration of 44 ng L^–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.     

Treatment of Synthetic Olefin Plant Wastewater at Various Salt Concentrations in a Membrane Bioreactor

The objective of this study was to investigate the effect of salt concentration on performance of a membrane bioreactor (MBR) for treating an olefin plant wastewater. For this purpose, a lab‐scale submerged MBR with a flat‐sheet ultrafiltration membrane was used for treatment of synthetic wastewater according to oxidation and neutralization unit of olefin plant. The synthetic wastewater was adjusted to have 500 mg/L chemical oxygen demand (COD). Trials on different concentrations of sodium sulfate (Na₂SO₄) (0–20 000 ppm) in the feed were conducted under aerobic conditions in the MBR. The results showed that increasing the salt concentrations causes an increase in the effluent COD, phenol, and oil concentrations. These results are due to reduction of the membrane filtration efficiency and also decline in the microbial activity that it is indicated by decreasing the sOUR in MBR. But in all the trials, the effluent COD and oil concentration was well within the local discharge limit of 100 and 10 mg/L, respectively. These results indicate that the MBR system is highly efficient for treating the olefin plant wastewater, and although high salt concentrations decreased organic contaminant removal rates in the MBR, the effluent still met the discharge limits for treating the olefin plant wastewater.     

Simultaneous Analysis of Natural Free Estrogens and Their Sulfate Conjugates in Wastewater

Natural estrogens from humans increasingly attract attention because of their strong endocrine disrupting potency. The discharge of sewage water is considered as the most important source of these endocrine disrupting chemicals (EDCs) in the environment. Therefore, a GC‐MS method was developed for the simultaneous analysis of six natural free estrogens and their sulfate conjugates in municipal wastewater, in which natural free estrogens and sulfate conjugates were successfully separated from an Oasis HLB solid phase extraction (SPE) cartridge with two different eluents, and the sulfate conjugates were then transformed to their corresponding free estrogens by acid solvolysis. Before the analysis with GC‐MS, samples were derivatized by N,O‐bis (trimethylsilyl) trifluoroacetamide (BSTFA) plus 1% trimethylchlorosilane (TMCS) at 80°C for 40 min. Satisfactory recoveries ranging from 64 to 112.3% were obtained by spiking ultra‐purified water, raw, and treated municipal wastewater with the six estrogens at 50, 100, and 50 ng/L, respectively. The method was successfully applied to wastewater samples from one WWTP, which suggested that E1 was the dominant natural estrogens in effluent and E3‐3S was one of the conjugates possibly occurring in the effluent.