Removal of steroid estrogens from municipal wastewater in a pilot scale expanded granular sludge blanket reactor and anaerobic membrane bioreactor.

Anaerobic treatment of municipal wastewater offers the prospect of a new paradigm by reducing aeration costs and minimizing sludge production. It has been successfully applied in warm climates, but does not always achieve the desired outcomes in temperate climates at the biochemical oxygen demand (BOD) values of municipal crude wastewater. Recently the concept of 'fortification' has been proposed to increase organic strength and has been demonstrated at the laboratory and pilot scale treating municipal wastewater at temperatures of 10-17°C. The process treats a proportion of the flow anaerobically by combining it with primary sludge from the residual flow and then polishing it to a high effluent standard aerobically. Energy consumption is reduced as is sludge production. However, no new treatment process is viable if it only addresses the problems of traditional pollutants (suspended solids - SS, BOD, nitrogen - N and phosphorus - P); it must also treat hazardous substances. This study compared three potential municipal anaerobic treatment regimes, crude wastewater in an expanded granular sludge blanket (EGSB) reactor, fortified crude wastewater in an EGSB and crude wastewater in an anaerobic membrane bioreactor. The benefits of fortification were demonstrated for the removal of SS, BOD, N and P. These three systems were further challenged with the removal of steroid estrogens at environmental concentrations from natural indigenous sources. All three systems removed these compounds to a significant degree, confirming that estrogen removal is not restricted to highly aerobic autotrophs, or aerobic heterotrophs, but is also a faculty of anaerobic bacteria.

Facile and Efficient Preparation of Tri-component Fluorescent Glycopolymers via RAFT-controlled Polymerization.

Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and efficient synthesis of well-controlled fluorescent statistical glycopolymers using reversible addition-fragmentation chain-transfer (RAFT)-based polymerization is demonstrated. The synthesis starts with the preparation of ß-galactose-containing glycomonomer 2-lactobionamidoethyl methacrylamide obtained by reaction of lactobionolactone and N-(2-aminoethyl) methacrylamide (AEMA). 2-Gluconamidoethyl methacrylamide (GAEMA) is used as a structural analog lacking a terminal ß-galactoside. The following RAFT-mediated copolymerization reaction involves three different monomers: N-(2-hydroxyethyl) acrylamide as spacer, AEMA as target for further fluorescence labeling, and the glycomonomers. Tolerant of aqueous systems, the RAFT agent used in the reaction is (4-cyanopentanoic acid)-4-dithiobenzoate. Low dispersities (≤1.32), predictable copolymer compositions, and high reproducibility of the polymerizations were observed among the products. Fluorescent polymers are obtained by modifying the glycopolymers with carboxyfluorescein succinimidyl ester targeting the primary amine functional groups on AEMA. Lectin-binding specificities of the resulting glycopolymers are verified by testing with corresponding agarose beads coated with specific glycoepitope recognizing lectins. Because of the ease of the synthesis, the tight control of the product compositions and the good reproducibility of the reaction, this protocol can be translated towards preparation of other RAFT-based glycopolymers with specific structures and compositions, as desired.

Obtaining process mass balances of pharmaceuticals and triclosan to determine their fate during wastewater treatment.

To better understand pharmaceutical fate during wastewater treatment, analysis in both aqueous and particulate phases is needed. Reported herein is a multi-residue method for the determination of ten pharmaceutical drugs and the personal care product triclosan in wastewater matrices. Method quantitation limits ranged from 7.6 to 76.6 ng l(-1) for aqueous phases and from 7.0 to 96.7 ng g(-1) for particulate phases. The analytical method was applied to attain a complete process mass balance of a pilot-scale activated sludge plant (ASP) operated under controlled conditions. The mass balance (inclusive of aqueous and particulate concentrations at all sample points) was used to diagnose removal, revealing pharmaceuticals to be separable into three fate pathways: (a) biological degradation, (b) sorption onto activated sludge and (c) resistant to removal from the aqueous phase. These differences in fate behaviour explained a broad range of secondary removal observed (-8 to 99%). The ASP was also simultaneously compared to a full-scale trickling filter (TF) works whilst receiving the same influent wastewater. Performance of the ASP and TF was similar, achieving total pharmaceutical removals of 253 and 249 µg g(-1) biochemical oxygen demand (BOD) removed, respectively. This corresponded with reductions in total pharmaceutical load of 91 and 90% (ANOVA, p-value>0.05). Interestingly, despite low suspended solid concentrations final effluents of both the ASP and TF contained significant concentrations of some chemicals in the particulate phase. Individually, triclosan and the antibiotics ofloxacin and ciprofloxacin were within the particulate phase of effluents at concentrations ranging from 26 to 296 ng l(-1).

Diagnostic investigation of steroid estrogen removal by activated sludge at varying solids retention time.

The impact of solids retention time (SRT) on estrone (E1), 17ß-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2) removal in an activated sludge plant (ASP) was examined using a pilot plant to closely control operation. Exsitu analytical methods were simultaneously used to enable discrimination of the dominant mechanisms governing estrogen removal following transitions in SRT from short (3d) to medium (10d) and long (27d) SRTs which broadly represent those encountered at full-scale. Total estrogen (∑EST, i.e., sum of E1, E2, E3 and EE2) removals which account for aqueous and particulate concentrations were 70±8, 95±1 and 93±2% at 3, 10 and 27d SRTs respectively. The improved removal observed following an SRT increase from 3 to 10d was attributable to the augmented biodegradation of the natural estrogens E1 and E2. Interestingly, estrogen biodegradation per bacterial cell increased with SRT. These were 499, 1361 and 1750ng 10(12) viable cells(-1)d(-1). This indicated an improved efficiency of the same group or the development of a more responsive group of bacteria. In this study no improvement in absolute ∑EST removal was observed in the ASP when SRT increased from 10 to 27d. However, batch studies identified an augmented biomass sorption capacity for the more hydrophobic estrogens E2 and EE2 at 27d, equivalent to an order of magnitude. The lack of influence on estrogen removal during pilot plant operation can be ascribed to their distribution within activated sludge being under equilibrium. Consequently, lower wastage of excess sludge inherent of long SRT operation counteracts any improvement in sorption.

Assessing potential modifications to the activated sludge process to improve simultaneous removal of a diverse range of micropollutants.

It is proposed that wastewater treatment facilities meet legislated discharge limits for a range of micropollutants. However, the heterogeneity of these micropollutants in wastewaters make removal difficult to predict since their chemistry is so diverse. In this study, a range of organic and inorganic micropollutants known to be preferentially removed via different mechanisms were selected to challenge the activated sludge process (ASP) and determine its potential to achieve simultaneous micropollutant removal. At a fixed hydraulic retention time (HRT) of 8 h, the influence of an increase in solids retention time (SRT) on removal was evaluated. Maximum achievable micropollutant removal was recorded for all chemicals (estrogens, nonylphenolics and metals) at the highest SRT studied (27 days). Also, optimisation of HRT by extension to 24 h further augmented organic biodegradation. Most notable was the enhancement in removal of the considerably recalcitrant synthetic estrogen 17α-ethinylestradiol which increased to 65 ± 19%. Regression analysis indicates that this enhanced micropollutant behaviour is ostensibly related to the concomitant reduction in food: microorganism ratio. Interestingly, extended HRT also initiated nonylphenol biodegradation which has not been consistently observed previously in real wastewaters. However, extending HRT increased the solubilisation of particulate bound metals, increasing effluent aqueous metals concentrations (i.e., 0.45 µm filtered) by >100%. This is significant as only the aqueous metal phase is to be considered for environmental compliance. Consequently, identification of an optimum process condition for generic micropollutant removal is expected to favour a more integrated approach where upstream process unit optimisation (i.e., primary sedimentation) is demanded to reduce loading of the particle bound metal phase onto the ASP, thereby enabling longer HRT in the ASP to be considered for optimum removal of organic micropollutants.

Performance of UK wastewater treatment works with respect to trace contaminants.

This study examined the performance of 16 wastewater treatment works to provide an overview of trace substance removal in relation to meeting the objectives of the Water Framework Directive (WFD). Collection and analysis of over 2400 samples including sewage influent, process samples at different stages in the treatment process and final effluent has provided data on the performance of current wastewater treatment processes and made it possible to evaluate the need for improved effluent quality. Results for 55 substances, including metals, industrial chemicals and pharmaceuticals are reported. Data for sanitary parameters are also provided. A wide range of removal efficiencies was observed. Removal was not clearly related to the generic process type, indicating that other operational factors tend to be important. Nonetheless, removals for many substances of current concern were high. Despite this, current proposals for stringent water quality standards mean that further improvements in effluent quality are likely to be required.

The determination of nonylphenol and its precursors in a trickling filter wastewater treatment process.

An ultra performance liquid chromatography method coupled to a triple quadrupole mass spectrometer was developed to determine nonylphenol and 15 of its possible precursors (nonylphenol ethoxylates and nonylphenol carboxylates) in aqueous and particulate wastewater matrices. Final effluent method detection limits for all compounds ranged from 1.4 to 17.4 ng l(-1) in aqueous phases and from 1.4 to 39.4 ng g(-1) in particulate phases of samples. The method was used to measure the performance of a trickling filter wastewater treatment works, which are not routinely monitored despite their extensive usage. Relatively good removals of nonylphenol were observed over the biological secondary treatment process, accounting for a 53 % reduction. However, only an 8 % reduction in total nonylphenolic compound load was observed. This was explained by a shortening in ethoxylate chain length which initiated production of shorter polyethoxylates ranging from 1 to 4 ethoxylate units in length in final effluents. Modelling the possible impact of trickling filter discharge demonstrated that the nonylphenol environmental quality standard may be exceeded in receiving waters with low dilution ratios. In addition, there is a possibility that the EQS can be exceeded several kilometres downstream of the mixing zone due to the biotransformation of readily degradable short-chained precursors. This accentuates the need to monitor 'non-priority' parent compounds in wastewater treatment works since monitoring nonylphenol alone can give a false indication of process performance. It is thus recommended that future process performance monitoring and optimisation is undertaken using the full suite of nonylphenolic moieties which this method can facilitate.

The significance of hazardous chemicals in wastewater treatment works effluents.

The advent of increasingly stringent and wider ranging European Union legislation relating to water and the environment has required regulators to assess compliance risk and to respond by formulating appropriate pollution control measures. To support this process the UK Water Industry has completed a national Chemicals Investigation Programme (CIP), to monitor over 160 wastewater treatment works (WwTWs) for 70 determinands. Final effluent concentrations of zinc, polynuclear aromatic hydrocarbons (fluoranthene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(g,h,i)perylene and indeno(1,2,3-cd)pyrene), "penta" congeners (BDEs) 47 and 99, tributyltin, triclosan, erythromycin, oxytetracycline, ibuprofen, propranolol, fluoxetine, diclofenac, 17ß-estradiol and 17α-ethinyl estradiol exceeded existing or proposed Environmental Quality Standards (EQSs) in over 50% of WwTWs. Dilution by receiving water might ensure compliance with EQSs for these chemicals, apart from the BDEs. However, in some cases there will be insufficient dilution to ensure compliance and additional management options may be required.

The fate of steroid estrogens: partitioning during wastewater treatment and onto river sediments.

The partitioning of steroid estrogens in wastewater treatment and receiving waters is likely to influence their discharge to, and persistence in, the environment. This study investigated the partitioning behaviour of steroid estrogens in both laboratory and field studies. Partitioning onto activated sludge from laboratory-scale Husmann units was rapid with equilibrium achieved after 1 h. Sorption isotherms and Kd values decreased in the order 17α-ethinyl estradiol>17α-estradiol>estrone>estriol without a sorption limit being achieved (1/n>1). Samples from a wastewater treatment works indicated no accumulation of steroid estrogens in solids from primary or secondary biological treatment, however, a range of steroid estrogens were identified in sediment samples from the River Thames. This would indicate that partitioning in the environment may play a role in the long-term fate of estrogens, with an indication that they will be recalcitrant in anaerobic conditions.

Fate of alkylphenolic compounds during activated sludge treatment: impact of loading and organic composition.

The impact of loading and organic composition on the fate of alkylphenolic compounds in the activated sludge plant (ASP) has been studied. Three ASP designs comprising carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification treatment were examined to demonstrate the impact of increasing levels of process complexity and to incorporate a spectrum of loading conditions. Based on mass balance, overall biodegradation efficiencies for nonylphenol ethoxylates (NPEOs), short chain carboxylates (NP(1-3)EC) and nonylphenol (NP) were 37%, 59%, and 27% for the carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification ASP, respectively. The presence of a rich community of ammonia oxidizing bacteria does not necessarily facilitate effective alkylphenolic compound degradation. However, a clear correlation between alkylphenolic compound loading and long chain ethoxylate compound biodegradation was determined at the three ASPs, indicating that at higher initial alkylphenolic compound concentrations (or load), greater ethoxylate biotransformation can occur. In addition, the impact of settled sewage organic composition on alkylphenolic compound removal was evaluated. A correlation between the ratio of chemical oxygen demand (COD) to alkylphenolic compound concentration and biomass activity was determined, demonstrating the inhibiting effect of bulk organic matter on alkylphenol polyethoxylate transformation activity. At all three ASPs the biodegradation pathway proposed involves the preferential biodegradation of the amphiphilic ethoxylated compounds, after which the preferential attack of the lipophilic akylphenol moiety occurs. The extent of ethoxylate biodegradation is driven by the initial alkylphenolic compound concentration and the proportion of COD constituted by the alkylphenol polyethoxylates (APEOs) and their metabolites relative to the bulk organic concentration of the sewage composed of proteins, acids, fats, and polysaccharides. Secondary effluents from this study are characterized by low bulk organic concentrations and comparatively high micropollutant concentrations. Based on the biodegradation mechanism proposed in this study, application of high rate tertiary biological treatment processes to secondary effluents characterized by low bulk organic concentrations and comparatively high APEO concentrations is predicted to provide a sustainable solution to micropollutant removal.

Removal of steroid estrogens in carbonaceous and nitrifying activated sludge processes.

A carbonaceous (heterotrophic) activated sludge process (ASP), nitrifying ASP and a nitrifying/denitrifying ASP have been studied to examine the role of process type in steroid estrogen removal. Biodegradation efficiencies for total steroid estrogens (Sigma(EST)) of 80 and 91% were recorded for the nitrifying/denitrifying ASP and nitrifying ASP respectively. Total estrogen biodegradation (Sigma(EST)) was only 51% at the carbonaceous ASP, however, the extent of biodegradation in the absence of nitrification clearly indicates the important role of heterotrophs in steroid estrogen removal. The low removal efficiency did not correlate with biomass activity for which the ASP(carbonaceous) recorded 80 microg kg(-1) biomass d(-1) compared to 61 and 15 microg kg(-1) biomass d(-1) at the ASP(nitrifying) and ASP(nitrifying/denitrifying) respectively. This finding was explained by a moderate correlation (r(2)=0.55) between total estrogen loading (Sigma(EST) mgm(-3)d(-1)) and biomass activity (microg Sigma(EST) degraded kg(-1) d(-1)) and has established the impact of loading on steroid estrogen removal at full-scale. At higher solids retention time (SRT), steroid estrogen biodegradation of>80% was observed, as has previously been reported. It is postulated that hydraulic retention time (HRT) is as important as SRT as this governs both reaction time and loading. This observation is based on the high specific estrogen activity determined at the ASP(carbonaceous) plant, the significance of estrogen loading and the positive linear correlation between SRT and HRT.

Modelling the long-term fate of mercury in a lowland tidal river. II. Calibration and comparison of two models with field data.

This study presents results of the application of two-one-dimensional/dynamic-deterministic models developed to evaluate and predict mercury contamination of a lowland river, the River Yare, Norfolk, UK. As a general indication of model performance, MODEL 1 produced a prediction of the overall mass balance of mercury in the River Yare that was 6% lower than an estimate, based on measurements, and 10% lower than the prediction provided by MODEL 2. The mercury surficial sediment concentrations calculated by MODEL 1 varied from 0.46 mg kg(-1) in 1995 (Reach 3) to 3.55 mg kg(-1) in 1986 (Reaches 6 and 7), whereas the minimum mercury concentration calculated by MODEL 2 was 0.42 mg kg(-1) in 1995 (Reach 3) and the maximum was 8.45 mg kg(-1) in 1986 (Reach 5). Average mercury concentrations experimentally measured in surficial sediments ranged from 0.47 mg kg(-1) in 1995 (Reach 3) to 8.10 mg kg(-1) in 1986 (Reach 6). MODEL 2 gave an excellent prediction of mercury in fish flesh compared with the results obtained from the actual analysis of fish flesh. Both models demonstrated good ability to simulate actual values determined for all compartments, water, surficial sediments, bottom sediments, and fish.

Modelling the long-term fate of mercury in a lowland tidal river. I. Description of two finite segment models.

Crucial determinants of the potential effects of mercury in aquatic ecosystems are the speciation, partitioning, and cycling of its various species. These processes are affected by site-specific factors, such as water chemistry, sediment transport, and hydrodynamics. This study presents two different approaches to the development of one-dimensional/dynamic-deterministic models for the evaluation and prediction of mercury contamination in a lowland tidal river, the River Yare (Norfolk, UK). The models described here were developed to encompass the entire river system and address the mass balance of mercury in a multicompartment system, including tidal reversal and saline limit. The models were focused on river systems, with the River Yare being used as a case study because previous modelling studies have been centred on lakes and wetlands whilst there is a paucity of information for rivers. Initial comparisons with actual measured water parameters (salinity and suspended solids) indicate that both models exhibit good agreement with the actual values.

The effectiveness of conventional trickling filter treatment plants at reducing concentrations of copper in wastewaters.

Eight different sewage treatment works were sampled in the North West of England. The effectiveness of the conventional treatment processes (primary sedimentation and biological trickling filters) as well as various tertiary treatment units in terms of both total and dissolved copper removal was evaluated. The removal of total copper across primary sedimentation averaged 53% and were relatively consistent at all sites, however, at three sites the removal of dissolved copper also occurred at this stage of treatment. Removal of total copper by the biological trickling filters averaged 49%, however, substantial dissolution of copper occurred at two sites, which highlighted the unpredictability of this treatment process in the removal of dissolved copper. Copper removal during tertiary treatment varied considerably even for the same treatment processes installed at different sites, primarily due to the variability of insoluble copper removal, with little effect on copper in the dissolved form being observed. The proportion of dissolved copper increased significantly during treatment, from an average of 22% in crude sewages to 55% in the final effluents. There may be the potential to optimise existing, conventional treatment processes (primary or biological treatment) to enhance dissolved copper removal, possibly reducing the requirement for installing any tertiary processes specifically for the removal of copper.

Influence of operating parameters on the biodegradation of steroid estrogens and nonylphenolic compounds during biological wastewater treatment processes.

This study investigated operational factors influencing the removal of steroid estrogens and nonylphenolic compounds in two sewage treatment works, one a nitrifying/denitrifying activated sludge plant and the other a nitrifying/denitrifying activated sludge plant with phosphorus removal. Removal efficiencies of >90% for steroid estrogens and for longer chain nonylphenol ethoxylates (NP4-12EO) were observed at both works, which had equal sludge ages of 13 days. However, the biological activity in terms of milligrams of estrogen removed per day per tonne of biomass was found to be 50-60% more efficient in the nitrifying/denitrifying activated sludge works compared to the works which additionallyincorporated phosphorusremoval. A temperature reduction of 6 degrees C had no impact on the removal of free estrogens, but removal of the conjugated estrone-3-sulfate was reduced by 20%. The apparent biomass sorption (LogKp) values were greater in the nitrifying/denitrifying works than those in the nitrifying/denitrifying works with phosphorus removal for both steroid estrogens and honylphenolic compounds possibly indicating a different cell surface structure and therefore microbial population. The difference in biological activity (mg tonne(-1) d(-1)) identified in this study, of up to seven times, suggests thatthere is the potential for enhancing the removal of estrogens and nonylphenols if more detailed knowledge of the factors responsible for these differences can be identified and maximized, thus potentially improving the quality of receiving waters.

Fate of conjugated natural and synthetic steroid estrogens in crude sewage and activated sludge batch studies.

Steroids are excreted from the human body in the conjugated form but are present in sewage influent and effluent as the free steroid, the major source of estrogenic activity observed in water courses. The fate of sulfate and glucuronide conjugated steroid estrogens was investigated in batch studies using activated sludge grown on synthetic sewage in a laboratory-scale Husmann simulation and crude sewage from the field. A clear distinction between the fate of sulfate and glucuronide conjugates was observed in both matrices, with sulfated conjugates proving more recalcitrant and glucuronide deconjugation preferential in crude sewage. For each conjugate, the free steroid was observed in the biotic samples. The degree of free steroid formation was dependent on the conjugate moiety, favoring the glucuronide. Subsequent degradation of the free steroid (and sorption to the activated sludge solid phase) was evaluated. Deconjugation followed the first order reaction rate with rate constants for 17alpha-ethinylestradiol 3-glucuronide, estriol l6alpha-glucuronide, and estrone 3-glucuronide determined as 0.32, 0.24, and 0.35 h respectively. The activated sludge solid retention time over the range of 3-9 days had 74 to 94% of sulfate conjugates remaining after 8 h. In contrast, a correlation between increasing temperature and decreasing 17alpha-ethinylestradiol 3-glucuronide concentrations in the activated sludge observed no conjugate present in the AS following 8 h at 22 degrees C Based on these batch studies and literature excretion profiles, a hypothesis is presented on which steroids and what form (glucuronide, sulfate, or free) will likely enter the sewage treatment plant.

Testicular dysgenesis syndrome and the estrogen hypothesis: a quantitative meta-analysis: [review] / A síndrome da disgenesia testicular e a hipótese do estrogênio: uma meta-análise quantitativa: [revisão]

Sugeriu-se que anomalias do trato reprodutivo masculino como hipospádia e criptorquidismo, assim como o câncer de testículo, componham uma síndrome comum com diminuição da espermatogênese, e de etiologia comum, a interrupção do desenvolvimento gonadal na fase fetal, a síndrome de disgenesia testicular (SDT). O único levantamento quantitativo da relação entre exposição pré-natal a agentes estrogênicos e câncer de testículo data de mais de dez anos; outras revisões da relação entre compostos estrogênicos diferentes do potente estrogênio sintético dietilstilbestrol (DES) e SDT continuam inconclusivas. Foi feita uma meta-análise quantitativa da relação entre SDT e exposição pré-natal a agentes estrogênicos. A inclusão na análise baseou-se em critérios mecanísticos e foi explorada a plausibilidade de um modo de ação mediada pelo receptor estrogênico-α (REα). Incluíram-se oito estudos sobre a etiologia das hipospádias e/ou criptorquidismo não identificados em revisões sistemáticas anteriores. Mais quatro estudos sobre estrogênios sintéticos resultaram em uma estimativa estatisticamente significativa para câncer de testículo. Os resultados das análises dos subconjuntos apontam à existência de fontes não identificadas de heterogeneidade entre estudos ou populações estudadas.

Male reproductive tract abnormalities such as hypospadias and cryptorchidism, and testicular cancer have been proposed to comprise a common syndrome together with impaired spermatogenesis with a common etiology resulting from the disruption of gonadal development during fetal life, the testicular dysgenesis syndrome (TDS). The only quantitative summary estimate of the link between prenatal exposure to estrogenic agents and testicular cancer was published over 10 years ago; other reviews of the link between estrogenic compounds, other than the potent pharmaceutical estrogen diethylstilbestrol (DES), and TDS end points have remained inconclusive. We conducted a quantitative meta-analysis of the association between the end points related to TDS and prenatal exposure to estrogenic agents. Inclusion in this analysis was based on mechanistic criteria, and the plausibility of an estrogen receptor (ER)-α-mediated mode of action was specifically explored. Eight studies were included, investigating the etiology of hypospadias and/or cryptorchidism that had not been identified in previous systematic reviews. Four additional studies of pharmaceutical estrogens yielded a statistically significant updated summary estimate for testicular cancer. Results of the subset analyses point to the existence of unidentified sources of heterogeneity between studies or within the study population.

Testicular dysgenesis syndrome and the estrogen hypothesis: a quantitative meta-analysis.

Male reproductive tract abnormalities such as hypospadias and cryptorchidism, and testicular cancer have been proposed to comprise a common syndrome together with impaired spermatogenesis with a common etiology resulting from the disruption of gonadal development during fetal life, the testicular dysgenesis syndrome (TDS). The only quantitative summary estimate of the link between prenatal exposure to estrogenic agents and testicular cancer was published over 10 years ago; other reviews of the link between estrogenic compounds, other than the potent pharmaceutical estrogen diethylstilbestrol (DES), and TDS end points have remained inconclusive. We conducted a quantitative meta-analysis of the association between the end points related to TDS and prenatal exposure to estrogenic agents. Inclusion in this analysis was based on mechanistic criteria, and the plausibility of an estrogen receptor (ER)-alpha-mediated mode of action was specifically explored. Eight studies were included, investigating the etiology of hypospadias and/or cryptorchidism that had not been identified in previous systematic reviews. Four additional studies of pharmaceutical estrogens yielded a statistically significant updated summary estimate for testicular cancer. Results of the subset analyses point to the existence of unidentified sources of heterogeneity between studies or within the study population.

A sensitive and robust method for the determination of alkylphenol polyethoxylates and their carboxylic acids and their transformation in a trickling filter wastewater treatment plant.

This paper presents a method for the determination of alkylphenols, alkylphenol polyethoxylates (APEO) and alkylphenol ethoxycarboxylates (APEC) in the aqueous and particulate phase of wastewater samples. Quantification was achieved by liquid chromatography-tandem mass spectrometry. The sensitivity of the method is demonstrated by low detection limits, in the dissolved phase 1.2-9.6ngl(-1) for alkylphenol, AP1-3EO and APEC and 0.1-4.1ngl(-1) for longer chain alkylphenol polyethoxylates. The method detection limit for particulate phase samples ranged from 6 to 60ngg(-1) for AP, AP1-3EO and APEC; with the longer chain APEO being from 0.5 to 20ngg(-1). Matrix effects were noted in complex matrix rich samples. There was a distinct change in the distribution of alkylphenol ethoxylates during biological treatment of the wastewater, with the major biotransformation products observed being carboxylated derivatives at concentrations of up to 1768ngl(-1). Shorter chain APEO were present in higher proportions in the suspended solids, due to their higher affinity to particulate matter compared to the long-chain oligomers.

Testicular dysgenesis syndrome and the estrogen hypothesis: a quantitative meta-analysis.

BACKGROUND: Male reproductive tract abnormalities such as hypospadias and cryptorchidism, and testicular cancer have been proposed to comprise a common syndrome together with impaired spermatogenesis with a common etiology resulting from the disruption of gonadal development during fetal life, the testicular dysgenesis syndrome (TDS). The hypothesis that in utero exposure to estrogenic agents could induce these disorders was first proposed in 1993. The only quantitative summary estimate of the association between prenatal exposure to estrogenic agents and testicular cancer was published over 10 years ago, and other systematic reviews of the association between estrogenic compounds, other than the potent pharmaceutical estrogen diethylstilbestrol (DES), and TDS end points have remained inconclusive. OBJECTIVES: We conducted a quantitative meta-analysis of the association between the end points related to TDS and prenatal exposure to estrogenic agents. Inclusion in this analysis was based on mechanistic criteria, and the plausibility of an estrogen receptor (ER)-alpha-mediated mode of action was specifically explored. RESULTS: We included in this meta-analysis eight studies investigating the etiology of hypospadias and/or cryptorchidism that had not been identified in previous systematic reviews. Four additional studies of pharmaceutical estrogens yielded a statistically significant updated summary estimate for testicular cancer. CONCLUSIONS: The doubling of the risk ratios for all three end points investigated after DES exposure is consistent with a shared etiology and the TDS hypothesis but does not constitute evidence of an estrogenic mode of action. Results of the subset analyses point to the existence of unidentified sources of heterogeneity between studies or within the study population.