Fate and removal of polycyclic musks, UV filters and biocides during wastewater treatment.

The fate of polycyclic musks (PCMs) (HHCB, AHTN, ADBI, AHDI, ATII, DPMI), UV filters (3-(4-methylbenzylidene) camphor, 4-MBC; octyl-methoxycinnamate, OMC; octocrylene, OC; octyl-triazone, OT) and biocides (permethrin, carbendazim) during wastewater treatment was studied on a full-scale plant. Average influent concentrations of OMC, HHCB, OC, AHTN, 4-MBC and OT were at 20070, 4420, 1680, 1430, 960 and 720 ng L(-1), respectively. The other PCMs, permethrin and carbendazim ranged between < limits of quantification and 670 ng L(-1). Concentrations in the water line decreased significantly for most compounds. Removal rates for PCMs ranged from 72% to 86%, for UV filters from 92% to >99% and were at 92% and 37% for permethrin and carbendazim, respectively. Removal during wastewater treatment was mainly driven by sorption onto solids and biodegradation. For anaerobic sludge digestion, elimination of PCMs, OMC and the biocides was observed.

Effects of insect growth regulators on the nontarget soil arthropod Folsomia candida (Collembola).

The aim of this study was to assess the effect of several insect growth regulators (IGRs) on the nontarget soil arthropod Folsomia candida (Collembola). The survival and reproduction rates of F. candida were evaluated after 28 days of exposure to six IGRs (methoprene, fenoxycarb, precocene II, tebufenozide, hexaflumuron and teflubenzuron) and to one herbicide (diuron) in artificial soil. The differences in the sensitivity of F. candida to these different substances are high. The chitin synthesis inhibitors teflubenzuron and hexaflumuron were the most toxic compounds with an EC50 of 0.05 mg/kg (dry weight) for teflubenzuron and an EC50 of 0.6mg/kg for hexaflumuron. Teflubenzuron is toxic for F. candida at concentrations that are probably close to environmental levels of this insecticide. Inhibition of reproduction is strongly related to adult survival for the juvenile hormone agonist methoprene and for the antijuvenile hormone precocene II, with an EC50 of 173 mg/kg and a LC50 of 178mg/kg for methoprene and an EC50 of 15 mg/kg and a LC50 of 26 mg/kg for precocene II. Fenoxycarb, another juvenile hormone analog, showed a dose-response curve for mortality different from that of methoprene; at concentrations such as 3052 mg/kg no effect on adult survival was observed. However, the EC50 value of 113mg/kg is of the same order of magnitude as that obtained for methoprene. A test with compressed soil contaminated with fenoxycarb was conducted to observe parameters such as numbers of eggs laid and juveniles hatched. No differences were observed between these two endpoints for fenoxycarb. An EC50 of 109 mg/kg was obtained for the ecdysone agonist tebufenozide. The herbicide diuron showed a relatively high toxicity for F. candida with an EC50 of 20 mg/kg. Our results show that some of the tested IGRs can have effects on Collembola at environmentally relevant concentrations (toxicity/exposure ratios < 5 for teflubenzuron, hexaflumuron, and diuron).

Occurrence of several acidic drugs in sewage treatment plants in Switzerland and risk assessment.

The occurrence and fate of five acidic drugs (Mefenamic acid, Ibuprofen, Ketoprofen, Diclofenac and Clofibric acid) were analysed in three sewage treatment plants (STP) over 4-7 consecutive days. The results point out that the five substances were persistent in wastewater effluents after municipal wastewater treatment. At the most, half of Mefenamic acid was eliminated. Ibuprofen was well removed (80%) by one sewage treatment plant. The removal of Ibuprofen is dependent on the residence time of wastewater in the STPs. A long raining period induce an important decrease of removal of Ibuprofen and Ketoprofen. Removal rates showed a great variability according to sewage treatment plants and types of treatments (e.g. biological, physico-chemical). The concentrations of Ibuprofen, Mefenamic acid and Diclofenac were relatively high in the effluents (150-2000 ng/l), showing a potential contamination of surface water. An environmental risk assessment is presented. Mefenamic acid seems to present a risk for the aquatic environment, with a ratio PEC/PNEC higher than one.

Considerations about the enantioselective transformation of polycyclic musks in wastewater, treated wastewater and sewage sludge and analysis of their fate in a sequencing batch reactor plant.

The present work consists of two distinct parts: in the first part enantioselective GC was used to separate the different enantiomeric/diastereomeric polycyclic musks, PCMs (HHCB, AHTN, AHDI, ATII and DPMI) including the main transformation product of HHCB, HHCB-lactone, in wastewater and sewage sludge. After optimization all PCMs were resolved on a cyclodextrin containing Rt-BDEXcst capillary GC column. Enantiomeric ratios of PCMs in a technical mixture were determined and compared to those obtained from enantioselective separation of wastewater and sewage sludge samples. In general, enantiomeric ratios were similar for most materials in influent, effluent and stabilized sewage sludge. However, the ratios for HHCB, AHDI and particularly ATII suggest some stereospecific removal of these compounds. In the second part, a field study was conducted on a wastewater treatment plant comprising a sequencing batch reactor. Concentrations of HHCB, AHTN, ADBI, AHDI, ATII, DPMI and HHCB-lactone were determined by non-enantioselective GC in daily samples of influent, effluent and activated sludge during one week. Mean concentrations in influent were 6900 and 1520 ng/l for HHCB and AHTN, respectively. The other PCMs exhibited contents 200 ng/l. Mean percent removal was between 61% (AHDI) and 87% (HHCB) resulting in mean effluent concentrations below 860 ng/l. HHCB-lactone concentration increased during wastewater treatment with a mean in the influent of 430 ng/l and in the effluent of 900 ng/l, respectively, indicating a degradation of HHCB.

Concentrations and specific loads of polycyclic musks in sewage sludge originating from a monitoring network in Switzerland.

Polycyclic musks (HHCB, AHTN, ADBI, AHDI, ATII) and a metabolite of HHCB (HHCB-lactone) were analyzed in sewage sludge samples within the framework of a monitoring network in Switzerland. Mean values in stabilised sludge from 16 wastewater treatment plants were 20.3 mg/kg d.m. for HHCB, 7.3 mg/kg d.m. for AHTN and 1.8 mg/kg d.m. for HHCB-lactone, respectively. Contents of ADBI, AHDI and ATII were between 0.1 and 1.8 g/kg d.m. The results show that polycyclic musks origin mainly from private households and that loads from craft industry, industry and atmospheric deposition are negligible. The technology of wastewater treatment and sludge processing seems to be of minor importance for degradation processes of polycyclic musks. The calculated input in wastewater of polycyclic musks is lower by a factor of 5-7 than the estimates based on use volumes. This discrepancy might be explained by degradation processes, other emission pathways than wastewater or inappropriate estimation of production volumes.

Degradation in soil and water and ecotoxicity of rimsulfuron and its metabolites.

The degradation and ecotoxicity of sulfonylurea herbicide rimsulfuron and its major metabolites were examined in batch samples of an alluvial sandy loam and in freshwater. An HPLC-DAD method was adapted to simultaneously identify and quantify rimsulfuron and its metabolites, which was successfully validated by GC-MS analysis. In aqueous solutions, pure rimsulfuron was rapidly hydrolyzed into metabolite 1 (N-(4,6-dimethoxypyrimidin-2-yl)-N-(3-(ethylsulfonyl)-2-pyridinylurea)), which itself was transformed into the more stable metabolite 2 (N-((3-(ethylsulfonyl)-2-pyridinyl)-4,6-dimethoxy-2-pyrimidineamine)), with half-life (t(1/2)) values of 2 and 2.5 days, respectively. Hydrolysis was instantaneous under alkaline conditions (pH = 10). In aqueous suspensions of the alluvial soil (pH = 8), formulated rimsulfuron had a half-life of 7 days, whereas that of metabolite 1 was similar to that in water (about 3.5 days). The degradation of the two major metabolites was also studied in soil suspensions with the pure compounds at concentrations ranging from 1 to 10 mg l(-1). The half-life of metabolite 1 ranged from 3.9 to 5 days, close to the previous values. Metabolite 2 was more persistent and its degradation is strongly dependent on the initial concentration (C0): half-life values ranged from 8.1 to 55 days at 2-10 mg l(-1), respectively. These values are higher than those determined from the kinetics of metabolite 1 transformation into metabolite 2 (t(1/2) = 8-19 days). The ecotoxicity of the three chemicals was evaluated through their effect on Daphnia magna and Vibrio fischeri (Microtox bioassay). No effect was observed on D. magna with 24 and 48 h acute toxicity tests. Similarly, no toxic effect was observed with the Microtox test for the three chemicals in the range of concentrations tested that included the field application dose. Thus, being of low persistence and lacking acute toxicity, these chemicals present a low environmental risk. However, chronic effects should be studied in order to confirm the safety of rimsulfuron and its major metabolites.

Estrogenic activity assessment of environmental chemicals using in vitro assays: identification of two new estrogenic compounds.

Environmental chemicals with estrogenic activities have been suggested to be associated with deleterious effects in animals and humans. To characterize estrogenic chemicals and their mechanisms of action, we established in vitro and cell culture assays that detect human estrogen receptor [alpha] (hER[alpha])-mediated estrogenicity. First, we assayed chemicals to determine their ability to modulate direct interaction between the hER[alpha] and the steroid receptor coactivator-1 (SRC-1) and in a competition binding assay to displace 17ss-estradiol (E(2)). Second, we tested the chemicals for estrogen-associated transcriptional activity in the yeast estrogen screen and in the estrogen-responsive MCF-7 human breast cancer cell line. The chemicals investigated in this study were o,p'-DDT (racemic mixture and enantiomers), nonylphenol mixture (NPm), and two poorly analyzed compounds in the environment, namely, tris-4-(chlorophenyl)methane (Tris-H) and tris-4-(chlorophenyl)methanol (Tris-OH). In both yeast and MCF-7 cells, we determined estrogenic activity via the estrogen receptor (ER) for o,p'-DDT, NPm, and for the very first time, Tris-H and Tris-OH. However, unlike estrogens, none of these xenobiotics seemed to be able to induce ER/SRC-1 interactions, most likely because the conformation of the activated receptor would not allow direct contacts with this coactivator. However, these compounds were able to inhibit [(3)H]-E(2) binding to hER, which reveals a direct interaction with the receptor. In conclusion, the test compounds are estrogen mimics, but their molecular mechanism of action appears to be different from that of the natural hormone as revealed by the receptor/coactivator interaction analysis.

Controversy of oral contraceptives and risk of rheumatoid arthritis: meta-analysis of conflicting studies and review of conflicting meta-analyses with special emphasis on analysis of heterogeneity.

The authors analyze the heterogeneity present in the combined results of past observational studies that investigated the association between oral contraceptive use and rheumatoid arthritis. The authors also evaluate discrepancies among meta-analyses that focus on the same relation. Of the 15 initially reviewed studies, 10 were selected for this meta-analysis, which also includes a qualitative summary of study characteristics and a critical appraisal of study quality. The authors used the direct method to combine the study results when there was no evidence of heterogeneity and the DerSimonian-Laird method when heterogeneity was present. Using a meta-regression to assess the sources of heterogeneity, the authors weighted summary estimates by sample size and undertook a sensitivity analysis. There was a strong indication of heterogeneity when combining all studies (x2 = 29.34, p = 0.00060) with the source of controls explaining most of the heterogeneity. The most important factor in explaining the differences among the overall summary estimates given by the meta-analyses is that different effect estimates had been selected for the same studies. There is no conclusive evidence of a protective effect of oral contraceptives on the risk of developing rheumatoid arthritis. Consensus is needed on how meta-analyses of observational studies should be conducted.

PIP: Epidemiologists extracted data from 10 different studies to conduct a meta-analysis in order to compare the differences among the case-control studies and cohort studies that examine the association between oral contraceptives (OCs) and rheumatoid arthritis. They also analyzed the differences among four meta-analyses that study the same association. The epidemiologists used the direct method to combine the findings of the 10 studies when heterogeneity was absent and the DerSimonian-Laird method when heterogeneity was present. They applied a meta-regression to assess the sources of heterogeneity. Specifically, the epidemiologists weighted summary estimates by sample size and conducted a sensitivity analysis. When all the studies were combined, heterogeneity was strong (p = 0.0006). The source of controls explained most of the heterogeneity. As for the meta-analyses, the most important factor in accounting for the differences among the overall summary estimates is that the researchers had selected different effect estimates for the same studies. It is still not clear whether or not OCs have a protective effect against developing rheumatoid arthritis. Epidemiologists need to reach a consensus on how they should conduct meta-analyses of observational studies.

Analysis of the association between chondrocalcinosis and osteoarthritis: a community based study.

OBJECTIVES: To analyse the association between chondrocalcinosis and osteoarthritis (OA) of the hands and knees in an unselected elderly rural population. METHODS: A community based cross sectional study was performed in individuals randomly selected from a previous epidemiological survey on the prevalence of chondrocalcinosis in people older than 60 years from Osona county, Catalonia, northeastern Spain. Radiological OA (grade 2 or more of Kellgren's classification) was evaluated in 26 individuals with chondrocalcinosis and in 104 controls. A total of 18 articular areas of both knees (medial and lateral tibiofemoral compartments) and hands (first, second and third metacarpophalangeal (MCP), first carpometacarpal, trapezium-scaphoid, radiocarpal and distal radioulnar joints) were studied. RESULTS: Radiological changes of OA in the knees were more common in subjects with chondrocalcinosis than in those without it, with an odds ratio adjusted for age and gender (aOR) of 4.3 (95% confidence interval (CI) 1.6 to 11.8, p = 0.005). OA was also more frequent in almost all areas of the hands in individuals with chondrocalcinosis, though the difference reached statistical significance only in the MCP joints (aOR 3.1; 95% CI 1.1 to 8.8; p = 0.033). However, taking into account the side and the different joint compartments analysed, the association between chondrocalcinosis and OA was significant only in the lateral tibiofemoral compartment and the left MCP joints. CONCLUSIONS: In an elderly population unselected for their rheumatic complaints, there was a real association between OA and chondrocalcinosis. This association was particularly relevant in the lateral tibiofemoral compartment of the knee and in the first three left MCP joints.

Soil contamination by some organic micropollutants related to sewage sludge spreading.

The aim of the present publication is to give some information on soil contamination by 4 different micropollutant classes due to sewage sludge spreading. The soil under research shows an accumulation of light molecular weight PAHs and PCBs, DEHP and 4-NP just after spreading, but one month later the concentration of these micropollutant groups fall to the concentration detected just before the sludge spreading. As far as the soil concentration is concerned, only PAHs and PCBs are precipitation dependent. Some test plots, enriched during 10 years with fertilisers, pig-dung or sewage sludges show only an increase of the PAH concentrations of the plots amended with sludges. In the same way, the sewage sludge is chiefly responsible for the increase of PCBs in the soils, but pig-dung seems to contain quantities of these micropollutants which have to be taken into consideration.