Mass balance analysis of triclosan, diethyltoluamide, crotamiton and carbamazepine in sewage treatment plants.

The behavior of antibacterial triclosan, insect-repellent diethyltoluamide (DEET), anticonvulsant carbamazepine, and antipruritic crotamiton was investigated at two sewage treatment plants (STPs) to clarify their complete mass balance. Twenty-four-hour flow-proportional composite samples were collected from the influent and effluent of primary and final sedimentation tanks, a biofiltration tank and disinfection tanks. Sludge samples (i.e., activated and excess sludge) and samples of the return flow from the sludge treatment process were collected in the same manner. The analytes in both the dissolved and particulate phases were individually determined by a gas chromatograph equipped with mass spectrometer. Triclosan was dominantly detected in the particulate phase especially in the early stage of treatment (up to 83%) and was efficiently removed (over 90%) in STPs, mainly by sorption to sewage sludge. Limited removal was observed for DEET (55+/-24%), while no significant removal was demonstrated for crotamiton or carbamazepine. The solid-water distribution coefficients (K(d), n=4) for triclosan (log K(d): 3.7-5.1), DEET (1.3-1.9) and crotamiton (1.1-1.6) in the sludge samples are also determined in this study. These findings indicate the limitations of current sewage treatment techniques for the removal of these water-soluble drugs (i.e. DEET, carbamazepine, and crotamiton).

Occurrence of nonylphenol, nonylphenol ethoxylate surfactants and nonylphenol carboxylic acids in wastewater in Japan.

Nonylphenol (NP) is known to be a byproduct of nonylphenol ethoxylates (NPnEO) which are used as detergents in industry. It is important that not only NP but also NPnEO and their related substances are analysed when behaviour of NP in the wastewater treatment process is surveyed. NPnEO are biodegraded to shorter ethoxylate (EO) chain NPnEO or nonylphenol carboxylates (NPnEC) under aerobic conditions, and then biodegraded to NP under anaerobic conditions. NP is one of the suspected endocrine disruptors (ED). Moreover, shorter EO chain NPnEO has greater toxicity than longer EO chain NPnEO. We conducted a field survey of NP and its related substances in 20 wastewater treatment plants (WWTP). The concentrations (median) of NP and its related substances in the WWTPs' influent ranged from 0.1 to 8.3 microg/L, showing NP concentration as the same level as those previously reported. The reduction of the long EO chain NPnEO in the WWTPs was almost complete, while the removal efficiency for the short EO chain NPnEO was less significant than the long EO chain NPnEO, suggesting that the degradation rate of the short EO chain NPnEO was lower than that of the long EO chain NPnEO in the wastewater treatment

Effects of antibacterial agents, levofloxacin and clarithromycin, on aquatic organisms.

Contamination of surface waters by pharmaceutical chemicals is an emerging environmental problem. This study evaluated the toxic effects of the antibacterial agents levofloxacin (LVFX) and clarithromycin (CAM), which are widely used in Japan, on aquatic organisms. Ecotoxicity tests using a bacterium, alga and crustacean were conducted. Microtox test using a marine fluorescent bacterium showed that LVFX and CAM have no acute toxicity to the bacterium. From the results of the Daphnia immobilisation test, LVFX and CAM did not show acute toxicity to the crustacean. Meanwhile, an algal growth inhibition test revealed that LVFX and CAM have high toxicity to the microalga. The phytotoxicity of CAM was about 100-fold higher than that of LVFX from a comparison of EC50 (median effective concentration) value. From the Daphnia reproduction test, LVFX and CAM also showed chronic toxicity to the crustacean. Concentrations of LVFX and CAM in the aquatic environment were compared with PNEC (predicted no effect concentration) to evaluate the ecological risk. As a result, the ecological risk of LVFX is considered to be low, but that of CAM is higher, suggesting that CAM discharged into an aquatic environment after therapeutic use may affect organisms in the aquatic environment.

Fate of oestrogenic compounds and identification of oestrogenicity in a wastewater treatment process.

Understanding of the fate of oestrogen and oestrogenic compounds is important in improving the removal efficiency for oestrogens in wastewater treatment plants (WWTPs). In this study an attempt was made to clarify the fate of oestrogen, oestrogen sulphates, and oestrogenic compounds (synthetic oestrogen, nonylphenol and its relatives) by an instrumental analysis, and the fate of oestrogenicity by an in vitro assay. The investigation was conducted in an activated sludge WWTP in winter and summer, focusing on identification of the primary substances that induce oestrogenicity. Wastewater samples were analysed by employing the silica-gel fractionation technique in conjunction with two-step column chromatography. The results revealed that, in winter, the WWTP efficiencies for the removal of nitrogen and oestrogens decreased and the oestrone level increased with the progress of the treatment. Oestrone and oestrogenic substances are likely to circulate between the aeration tank and the final sedimentation tank. In summer, however, these compounds were effectively removed in the WWTP. The results of the column chromatography coupled with the bioassay suggested that E1 and E2 are the predominant contributors to the oestrogenicity in the influent, return sludge and effluent of the WWTP. The measurement by the instrumental analysis supported these findings.

Occurrence of levofloxacin, clarithromycin and azithromycin in wastewater treatment plant in Japan.

Residual pharmaceutical products in sewage and other water environments have recently become a serious social problem in advanced countries. Among these pharmaceutical products, antibiotics have attracted special attention due to their serious impact on the ecosystem and connections to the emergence of drug-resistant bacteria. Our research intended to develop a new method to analyse the three antibiotics estimated to be released out of the body in large amounts in Japan; levofloxacin (LVFX), clarithromycin (CAM) and azithromycin (AZM), and survey the state of pollution in the sewerage. The concentrations of the water-phase antibiotics LVFX, CAM and AZM were measured in each process of activated sludge process in six wastewater treatment plants. Liquid chromatography tandem mass spectrometry (LC/MS/MS) was used to analyse solutions of the antibiotics after pretreatment with a solid phase extraction. The limits of quantification and the average recoveries for these antibiotics in the influent were 1.2 to 29 ng/L and 46 to 93%, respectively. In the influent, LVFX, CAM and AZM were detected at concentrations of 552, 647 and 260 ng/L, respectively, while their removal efficiencies were 42, 43 and 49%, respectively. Although the CAM and AZM concentrations decreased as the treatment progressed, it was shown that the LVFX concentration increased in activated sludge reactors in some cases. Despite differences in octanol-water partition coefficients among LVFX, CAM and AZM, their removal efficiency showed no major difference. This indicates that this removal phenomenon cannot be explained by simple adsorption by the activated sludge.

Development of on-site fish exposure system placed in water quality monitoring stations along a river.

Estrogen-like substances have been suspected to cause feminization of wild fish in rivers in Japan. To elucidate the influence of estrogen-like substances on fish in river, we have started to develop the on-site continuous fish exposure system using medaka Oryzias latipes that were placed in water quality monitoring stations along a river. Adult male medaka were exposed to the river water in a glass exposure tank placed in the monitoring stations. Flow rate of water and water temperature were controlled at 30 L/hour and 26 degrees C respectively, and a light: dark cycle was maintained 16:8 hours. A commercial diet free from phytoestrogens was fed 4 times in a day using automatic feeder. After 2-week exposure, hepatic vitellogenin concentration of each male medaka was measured. The exposure tests were repeatedly performed at both the upstream and the downstream of sewage treatment plants along the River Tama which is a representative urbanized river in Japan. At the control site Haijimabashi monitoring station, vitellogenin was not detected in male medaka. On the other hand, at the Ishihara monitoring station which is the most downstream in this test area, every male medaka were produced vitellogenin in the test performed in the spring of 2004. As the results of the water quality analysis, it could be inferred that the estrone derived from effluents of sewage treatment plants caused the feminization of male medaka. The reason why the concentrations of the estrone and the estrogenic activity using DNA recombinant yeast varied in proportion to the electric conductivity of river water measured at the water quality monitoring station. Furthermore, after continuous 2-week exposure, the vitellogenin production of male medaka was reduced similar to the decrease of the concentrations of the estrone and the estrogenic activity of river water.

Analysis and occurrence of estrogen in wastewater in Japan.

This paper describes an analytical procedure for free estrogens and their conjugates in domestic wastewater. The procedure demonstrated in this study is innovative in terms of levels of detection and quantification of the following substances: estrone (E1); 17beta-estradiol (E2); 17alpha-ethynylestradiol (EE2); estriol (E3); estrone-3-sulfate (E1-S); beta-estradiol 3-sulfate (E2-S); estriol 3-sulfate (E3-S); estrone beta-D-glucuronide (E1-G); beta-estradiol 17-(beta-D)-glucuronide (E2-G); estriol 3-(beta-D)-glucuronide (E3-G); beta-estradiol 3-sulfate 17-glucuronide (E2-SandG); and estradiol 3,17-disulfate (E2-diS). The detection limits of this method ranged from 0.1 to 1.4 ng/l. The recovery efficiencies of the estrogens in the analysis from influent and effluent of the secondary settling tank in a wastewater treatment plant (WWTP) were higher than 94% for the free estrogens, but were less than 50% for the conjugated estrogens. The field study using this method was conducted at twenty WWTPs in Japan. The median concentrations of the estrogens ranged from ND to as high as >100 ng/l. In the influent and secondary effluent samples, the concentrations of E1, E2 and E3 were the same levels as those previously reported. We found that the conjugated estrogens exist at higher concentrations in the influent and the secondary effluent than in the other studies, and that the concentrations of the conjugated estrogens were higher than those of the free estrogens.