Concentrations of estradiol, estrone, and ethinylestradiol were measured in the water column (daily for 28 or 14 days) and in the bed sediment (weekly over the same period) of the River Nene and the River Lea, U.K., upstream and downstream of sewage treatment works (STW). The concentrations of the three steroids in the STW effluents were also measured. Estrone was detected at the highest concentration and in almost all samples from the three STW effluents, concentrations ranging from <0.4 to 12.2 ng/L. Estradiol was also detected frequently (<0.4-4.3 ng/L), but ethinylestradiol was detected infrequently (<0.4-3.4 ng/L). Positive detections were only found for estrone in the sediment, and these seemed to be unrelated to the water column concentrations. Levels of estrone were clearly raised above background levels in the rivers as a result of the STW discharges. Levels of estradiol and ethinylestradiol were too close to their detection limits to assess the STW impact. River water estrone concentration declined downstream at a rate that was in excess of that due to dilution. The most likely cause of this decline is a combination of sorption and biodegradation equivalent to a first-order decay half-life of 2.5 days for the River Nene and 0.5 days for the River Lea.

In this study a number of analytical procedures are described to determine pharmaceuticals and personal care products (PPCPs) and their metabolites during sewage treatment. The work shows that PPCPs occur in sewage influent and are removed by various wastewater treatment processes. PPCPs include a wide range of chemicals such as prescription drugs as well as diagnostic agents, fragrances, sun-screen agents, and various other compounds commonly present in household items (e.g. detergents, cleaners, toothpastes etc.). During this study a number of PPCPs including painkillers (aspirin, ibuprofen), cholesterol control medication (clofibric acid), antibacterial agents (triclosan), musks (including galaxolide and tonalide), X-ray contrast media (diatrizoate), cancer treatment drugs (cyclophosphamide) and anti-depressant drugs (fluvoxamine) were investigated. Analysis was carried out using a number of techniques. Samples were extracted using solid phase extraction or liquid-liquid extraction and the extracts analysed using capillary gas chromatography-mass spectrometry (GC-MS) with selected ion monitoring or liquid chromatography mass spectrometry (LC-MS) or LC-MS-MS. The results obtained show that aspirin, clolibric acid, diatrozate, fluvoxamine and cyclophosphamide were not detected in any of the crude sewage or sewage effluent samples above the limit of detection of the applied methods. Ibuprofen was detected in all crude sewage samples as well as in all effluent samples with one exception. Removal of ibuprofen by the different STWs was generally between 80-100%, with the exception of one STW where removal was poor (14.4 to 44%). Triclosan was also detected in all crude sewage samples and in all sewage effluent samples. The highest concentration of triclosan detected was 3100 ng l(-1). A high removal efficiency was observed in effluent samples taken on two occasions (average removal 95.6%). The concentrations of musks detected in the crude sewage were generally low except for galaxolide and tonalide. The results from STW effluent samples showed significant removal of galaxolide (70-83% removal) except at one STW (STW 1) where removal was low (57% and 39%). Similar removal efficiencies for tonalide were achieved at these STWs (73-96%) except at STW 1 where removal was poor (53%).

No abstract

17α-ethinylestradiol (EE2), a synthetic oestrogen in oral contraceptives, is one of many pharmaceuticals found in inland waterways worldwide as a result of human consumption and excretion into wastewater treatment systems. At low parts per trillion (ppt), EE2 induces feminisation of male fish, diminishing reproductive success and causing fish population collapse. Intended water quality standards for EE2 set a much needed global precedent. Ozone and activated carbon provide effective wastewater treatments, but their energy intensities and capital/operating costs are formidable barriers to adoption. Here we describe the technical and environmental performance of a fast- developing contender for mitigation of EE2 contamination of wastewater based upon small- molecule, full-functional peroxidase enzyme replicas called “TAML activators”. From neutral to basic pH, TAML activators with H2O2 efficiently degrade EE2 in pure lab water, municipal effluents and EE2-spiked synthetic urine. TAML/H2O2 treatment curtails estrogenicity in vitro and substantially diminishes fish feminization in vivo. Our results provide a starting point for a future process in which tens of thousands of tonnes of wastewater could be treated per kilogram of catalyst. We suggest TAML/H2O2 is a worthy candidate for exploration as an environmentally compatible, versatile, method for removing EE2 and other pharmaceuticals from municipal wastewaters.

No abstract

Despite the recent focus on nitrogenous disinfection byproducts in drinking water, there is limited occurrence data available for many species. This paper analyses the occurrence of seven haloacetonitriles, three haloacetamides, eight halonitromethanes and cyanogen chloride in 20 English drinking water supply systems. It is the first survey of its type to compare bromine substitution factors (BSFs) between the haloacetamides and haloacetonitriles. Concentrations of the dihalogenated haloacetonitriles and haloacetamides were well correlated. Although median concentrations of these two groups were lower in chloraminated than chlorinated surface waters, median BSFs for both in chloraminated samples were approximately double those in chlorinated samples, which is significant because of the higher reported toxicity of the brominated species. Furthermore, median BSFs were moderately higher for the dihalogenated haloacetamides than for the haloacetonitriles. This indicates that, while the dihalogenated haloacetamides were primarily generated from hydrolysis of the corresponding haloacetonitriles, secondary formation pathways also contributed. Median halonitromethane concentrations were remarkably unchanging for the different types of disinfectants and source waters: 0.1 μg · mgTOC(-1) in all cases. Cyanogen chloride only occurred in a limited number of samples, yet when present its concentrations were higher than the other N-DBPs. Concentrations of cyanogen chloride and the sum of the halonitromethanes were not correlated with any other DBPs.

TAML activators enable homogeneous oxidation catalysis where the catalyst and substrate (S) are ultradilute (pM-low μM) and the oxidant is very dilute (high nM-low mM). Water contamination by exceptionally persistent micropollutants (MPs), including metaldehyde (Met), provides an ideal space for determining the characteristics and utilitarian limits of this ultradilute catalysis. The low MP concentrations decrease throughout catalysis with S oxidation (k) and catalyst inactivation (k) competing for the active catalyst. The percentage of substrate converted (%Cvn) can be increased by discovering methods to increase k/k. Here we show that NaClO extends catalyst lifetime to increase the Met turnover number (TON) 3-fold compared with HO, highlighting the importance of oxidant choice as a design tool in TAML systems. Met oxidation studies (pH 7, DO, 0.01 M phosphate, 25 °C) monitored by H NMR spectroscopy show benign acetic acid as the only significant product. Analysis of TAML/NaClO treated Met solutions employing successive identical catalyst doses revealed that the processes can be modeled by the recently published relationship between the initial and final [S] (S and S, respectively), the initial [catalyst] (Fe) and k/k. Consequently, this study establishes that ΔS is proportional to S and that the %Cvn is conserved across all catalyst doses in multicatalyst-dose processes because the rate of the k process depends on [S] while that of the k process does not. A general tool for determining the Fe required to effect a desired %Cvn is presented. Examination of the dependence of TON on k/k and Fe at a fixed S indicates that for any TAML process employing Fe < 1 × 10 M, small catalyst doses are not more efficient than one large dose.

Steroid estrogens are thought to be the major cause of feminization (intersex) in wild fish. Widely used wastewater treatment technologies are not effective at removing these contaminants to concentrations thought to be required to protect aquatic wildlife. A number of advanced treatment processes have been proposed to reduce the concentrations of estrogens entering the environment. Before investment is made in such processes, it is imperative that we compare their efficacy in terms of removal of steroid estrogens and their feminizing effects with other treatment options. This study assessed both steroid removal and intersex induction in adult and early life stage fish (roach, Rutilus rutilus). Roach were exposed directly to either secondary (activated sludge process (ASP)), tertiary (sand filtrated (SF)), or advanced (chlorine dioxide (ClO(2)), granular activated charcoal (GAC)) treated effluents for six months. Surprisingly, both the advanced GAC and tertiary SF treatments (but not the ClO(2) treatment) significantly removed the intersex induction associated with the ASP effluent; this was not predicted by the steroid estrogen measurements, which were higher in the tertiary SF than either the GAC or the ClO(2). Therefore our study highlights the importance of using both biological and chemical analysis when assessing new treatment technologies.