Uptake, Elimination and Effects of Cosmetic Microbeads on the Freshwater Gastropod Biomphalaria glabrata.

The presence of plastic cosmetic microbeads in the environment due to their extensive use in society and inevitable dispersal into wastewater is concerning. Therefore, it is vital to understand the processes of microplastic uptake and elimination by aquatic organisms, and to further assess their potential to cause harmful effects and wider impacts. We therefore investigated the short-term (48-h) and long-term (21-d) uptake, elimination, and effects of exposure to polyethylene microbeads (a mixture of fragments and spheres extracted from commercially available facial scrubs) on the freshwater snail, Biomphalaria glabrata. We found fast uptake in the short-term (75 µg/g/h) and the long-term (6.94 µg/g/h) in B. glabrata exposed to 800 particles/200-mL and 80 particles/200-mL, respectively. Irregular fragments were more easily ingested and egested compared to spheres (ANOVA, p < 0.05) in both 48-h and 21-d exposures. The mean size of the fragments in B. glabrata tissues (413 ± 16 µm) after 48-h exposure was significantly larger than that of the standard sample (369 ± 26 µm) (ANOVA, F3,20 = 3.339, p = 0.033), suggesting that aggregation in the gut may occur. Floating feces containing microbeads were observed in the long-term exposure, which could alter the fate, behavior, and bioavailability of egested microbeads. No significant effects on survival and growth were shown within 48-h or 21-d exposure periods. Thus, further studies on the specific features of microplastics (e.g., their shape and size) influencing uptake and elimination, as well as toxic molecular mechanisms, should be explored in future ecotoxicological studies.

A Comparison of Different Approaches for Characterizing Microplastics in Selected Personal Care Products.

Any uncertainty in determining numbers of microplastics in the environment may be a barrier to assessing their impact and may stem from various aspects of methodologies used to quantify them. We undertook a comparison of approaches to quantify and characterize microplastics in 4 personal care products. The aim was not only to determine how many particles were present but to assess any differences due to the methods used. Counting of extracted microplastics was undertaken using particle size analysis, light microscopy, and imaging flow cytometry. Micro-Fourier transform infrared spectroscopy (µ-FTIR) was used to characterize the particles in each product. The mean size distribution of microplastics differed depending on the method employed, and it was apparent that imaging flow cytometry was affected by high background noise that may require staining of plastics to overcome. The application of µ-FTIR confirmed polyethylene as the microplastic in each product. Methodological challenges encountered in the study and the literature have highlighted the need for standardization of methods for determining microplastics. Environ Toxicol Chem 2022;41:880-887. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Progesterone potentially degrades to potent androgens in surface waters.

Progesterone is a natural hormone, excreted in higher concentrations than estrogens, and has been detected in the aqueous environment. As with other compounds, it is transformed during wastewater treatment processes and in the environment. However, minor modifications to the structure may result in transformation products which still exhibit biological activity, so understanding what transformation products are formed is of importance. The current study was undertaken to identify putative transformation products resulting from spiking river water with progesterone in a laboratory-based degradation study and hence to follow the metabolic breakdown pathways. On the basis of literature reports and predictions from the EAWAG Biocatalysis/biodegradation database, target putative transformation products were initially monitored under unit resolution mass spectrometry. The identity of these transformation products was confirmed by using accurate-mass quadrupole time-of-flight. The study results highlight that transformation of progesterone can potentially create other classes of steroids, some of which may still be potent, and possess other types of biological activity.

An approach for prioritizing "down-the-drain" chemicals used in the household.

Many chemicals are present in cleaning and personal care products, which after use are washed down the drain and find their way into water bodies, where they may impact the environment. This study surveyed individuals to determine what products were used most in the home, in an attempt to prioritize which compounds may be of most concern. The survey resulted in the identification of 14 categories of products consisting of 315 specific brands. The survey estimated that individuals each discharge almost 33 L of products per year down the drain. Dishwashing liquids and hand wash gels, which accounted for 40% of this volume, were selected for identification of specific ingredients. Ingredients were classified as surfactants, preservatives, fragrances or miscellaneous, with hand wash gels having a wider range of ingredients than dishwashing liquids. A review of the literature suggested that preservatives, which are designed to be toxic, and fragrances, where data on toxicity are limited, should be prioritized. The approach undertaken has successfully estimated use and provisionally identified some classes of chemicals which may be of most concern when used in cleaning and personal care products.

A new role for carbonic anhydrase 2 in the response of fish to copper and osmotic stress: implications for multi-stressor studies.

The majority of ecotoxicological studies are performed under stable and optimal conditions, whereas in reality the complexity of the natural environment faces organisms with multiple stressors of different type and origin, which can activate pathways of response often difficult to interpret. In particular, aquatic organisms living in estuarine zones already impacted by metal contamination can be exposed to more severe salinity variations under a forecasted scenario of global change. In this context, the present study aimed to investigate the effect of copper exposure on the response of fish to osmotic stress by mimicking in laboratory conditions the salinity changes occurring in natural estuaries. We hypothesized that copper-exposed individuals are more sensitive to osmotic stresses, as copper affects their osmoregulatory system by acting on a number of osmotic effector proteins, among which the isoform two of the enzyme carbonic anhydrase (CA2) was identified as a novel factor linking the physiological responses to both copper and osmotic stress. To test this hypothesis, two in vivo studies were performed using the euryhaline fish sheepshead minnow (Cyprinodon variegatus) as test species and applying different rates of salinity transition as a controlled way of dosing osmotic stress. Measured endpoints included plasma ions concentrations and gene expression of CA2 and the α1a-subunit of the enzyme Na+/K+ ATPase. Results showed that plasma ions concentrations changed after the salinity transition, but notably the magnitude of change was greater in the copper-exposed groups, suggesting a sensitizing effect of copper on the responses to osmotic stress. Gene expression results demonstrated that CA2 is affected by copper at the transcriptional level and that this enzyme might play a role in the observed combined effects of copper and osmotic stress on ion homeostasis.

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 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.

Challenges for the development of a biotic ligand model predicting copper toxicity in estuaries and seas.

An effort is ongoing to develop a biotic ligand model (BLM) that predicts copper (Cu) toxicity in estuarine and marine environments. At present, the BLM accounts for the effects of water chemistry on Cu speciation, but it does not consider the influence of water chemistry on the physiology of the organisms. We discuss how chemistry affects Cu toxicity not only by controlling its speciation, but also by affecting the osmoregulatory physiology of the organism, which varies according to salinity. In an attempt to understand the mechanisms of Cu toxicity and predict its impacts, we explore the hypothesis that the common factor linking the main toxic effects of Cu is the enzyme carbonic anhydrase (CA), because it is a Cu target with multiple functions and salinity-dependent expression and activity. According to this hypothesis, the site of action of Cu in marine fish may be not only the gill, but also the intestine, because in this tissue CA plays an important role in ion transport and water adsorption. Therefore, the BLM of Cu toxicity to marine fish should also consider the intestine as a biotic ligand. Finally, we underline the need to incorporate the osmotic gradient into the BLM calculations to account for the influence of physiology on Cu toxicity.

From dishwasher to tap? Xenobiotic substances benzotriazole and tolyltriazole in the environment.

There is increasing evidence that the use of chemicals frequently results in widespread environmental contamination with little understanding of the toxicological implications. Benzotriazoles are used in, among other applications, dishwashing formulations for home use, and are a class of chemicals recently reported to be present in European waters. This study demonstrates their presence in UK wastewaters, rivers, and drinking water. It also estimates that their use as silver polishing agents in dishwasher tablets and powders may account for a significant proportion of inputs to wastewaters. The lack of a complete set of good quality (eco)toxicological data on possible chronic effects of these high use chemicals should caution against using them in a manner which may have contributed to such widespread environmental contamination.

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.

Hazard and risk assessment for indirect potable reuse schemes: An approach for use in developing Water Safety Plans.

This paper describes research undertaken to develop an approach for facilitating an initial hazard assessment and risk characterisation for a proposed indirect potable reuse scheme, as part of the water safety plan recommended by the World Health Organization. The process involved a description and evaluation of the catchment, which was the sewerage system supplying the sewage treatment works that would provide the effluent to supply the pilot scale indirect potable reuse water treatment plant. Hazards, sources and barriers throughout the proposed system were identified and evaluated. An initial assessment of the possible hazards, highlighted chemical hazards as predominating, and assessment of risks, using a heat map as output, categorised most hazards as medium or high risk. However, this outcome has been influenced by a precautionary approach which assigned a high likelihood to the occurrence of hazards where no data was available on their occurrence in the system. As more data becomes available, and the waster safety plan develops, it is anticipated that the risk heat map will become more specific. Additionally, high quality targets, to drinking water standards, have been set, although water from the potable reuse plant will be discharged to receiving waters where it will undergo natural attenuation prior to further treatment to potable standards before distribution. The assessment has demonstrated the usefulness of the approach where data is initially limited, in generating a heat map allowing for prioritisation of hazards to a practical level.

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.

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.

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.