Environmental release of oseltamivir from a Norwegian sewage treatment plant during the 2009 influenza A (H1N1) pandemic.

During the 2009 influenza type A(H1N1) pandemic, the antiviral drug oseltamivir (OP, Tamiflu®) was extensively used for treatment and prophylaxis after recommendation from World Health Organisation (WHO). Previous studies have indicated that the pharmaceutically active metabolite of OP, oseltamivir carboxylate (OC), is not readily degraded in sewage treatment plants (STPs) and therefore will be released into receiving waters in elevated concentrations during a pandemic outbreak of influenza. A method for analyzing OP and OC in wastewater by UPLC-TOF has been developed and validated. This analytical method has been used to study the release of OP and OC from a sewage treatment plant outside Oslo, Norway during the 2009 pandemic. Daily flow-proportional influent and effluent samples from 11 weeks covering the main wave of the influenza pandemic were analyzed, and the observed trend in OP and OC concentrations closely followed the trend in percentage of medical consultations caused by influenza-like illness. Concentrations in wastewater influent were in the range of 5-529 ng/L and 28-1213 ng/L for OP and OC, respectively. Concentration data from the 54 influent/effluent sample sets suggest STP removal in the range of -0.8% to 8% for OP and -14% to 0.6% for OC. Statistical analysis of the data sets was inconclusive in determining a removal rate different from 0.

Assessing inter-laboratory comparability and limits of determination for the analysis of cyclic volatile methyl siloxanes in whole Rainbow Trout (Oncorhynchus mykiss).

Cyclic volatile methyl siloxanes (cVMS) are high volume production chemicals used in a wide range of industrial and consumer products. Three cVMS compounds (D4, D5, and D6) have and are undergoing environmental risk evaluations in several countries and have been proposed for legal regulation in Canada. As interest in monitoring concentrations of these chemicals in the environment increase, there is a need to evaluate the analytical procedures for cVMS in biological matrices in order to assess the quality of data produced. The purpose of this study was to determine laboratory testing performance for measuring residues of D4, D5, and D6 in a standard set of fish homogenate samples and to estimate limits of determination for each substance. The samples sent to each laboratory consisted of homogenized whole body tissues of hatchery raised rainbow trout which were fed food fortified with D4, D5, and D6 (dosed) and trout that were fed standard food rations (control). The participants analyzed each sample using their analytical method of choice using their own standards and procedures for quantification and quality control. With a few exceptions, participating laboratories generated comparable results for D4, D5, and D6 in both the dosed and control samples having z-scores between 2 and -2. Method detection limits for the whole fish matrix were on average 2.4 ng g(-1) ww for D4, 2.3 ng g(-1) ww for D5, and 1.8 ng g(-1) ww for D6.

Plasma concentrations of parabens in postmenopausal women and self-reported use of personal care products: the NOWAC postgenome study.

Parabens are used extensively in personal care products; however, their estrogenic properties have raised concern over risks to human health. High levels of total parabens, mainly as conjugates, have been reported in human plasma/serum, with limited data on native parabens. Our objective was to assess and link plasma concentrations of native common parabens to self-reported use of personal care products in women from the general population. The information was obtained from an extensive questionnaire on diet and lifestyle previously answered by the women in the NOWAC study. Plasma samples from 332 individuals were extracted and cleaned up by automated solid phase extraction and analyzed by ultra high performance liquid chromatography time-of-flight mass spectrometry. Native methyl paraben dominated and was detected in 63% of the samples, with a median level of 9.4 ng/ml. Ethyl paraben (median < 3 ng/ml) and propyl paraben (median < 2 ng/ml) were detected in 22 and 29%, respectively. Butyl and benzyl parabens were not detected. For the first time, elevated levels of native parabens are reported in women from the general population. The concentrations were significantly associated with the use of skin lotions, indicating that frequent (daily or more) use maintain elevated concentrations despite the parabens short half-lives. These findings clearly emphasize the need to study potential health effects in the general population.

Volatile siloxanes in the European arctic: assessment of sources and spatial distribution.

The purpose of this study was to investigate presence and potential accumulation of cyclic volatile methyl siloxanes (cVMS) in the Arctic environment. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were analyzed in sediment, zooplankton, Atlantic cod (Gadus morhua), shorthorn sculpin (Myxocephalus scorpius), and bearded seal (Erignathus barbatus) collected from the Svalbard archipelago within the European Arctic in July 2009. Highest levels were found for D5 in fish collected from Adventfjorden, with average concentrations of 176 and 531 ng/g lipid in Atlantic cod and shorthorn sculpin, respectively. Decreasing concentration of D5 in sediment collected away from waste water outlet in Adventfjorden indicates that the local settlement of Longyearbyen is a point source to the local aquatic environment. Median biota sediment accumulation factors (BSAFs) calculated for D5 in Adventfjorden were 2.1 and 1.5 for Atlantic cod and shorthorn sculpin, respectively. Biota concentrations of D5 were lower or below detection limits in remote and sparsely populated regions (Kongsfjorden and Liefdefjorden) compared to Adventfjorden. The levels of cVMS were found to be low or below detection limits in bearded seal blubber and indicate a low risk for cVMS accumulation within mammals. Accumulation of cVMS in fish appears to be influenced by local exposure from human settlements within the Arctic.

Diurnal variations in the occurrence and the fate of hormones and antibiotics in activated sludge wastewater treatment in Oslo, Norway.

We present an assessment of the dynamics in the influent concentration of hormones (estrone, estriol) and antibiotics (trimethoprim, sulfamethoxazole, tetracycline, ciprofloxacin) in the liquid phase including the efficiency of biological municipal wastewater treatment. The concentration of estradiol, 17-alpha-ethinylestradiol, doxycycline, oxytetracycline, demeclocycline, chlortetracycline, cefuroxime, cyclophosphamide, and ifosfamide were below the limit of detection in all of the sewage samples collected within this study. Two different types of diurnal variation pattern were identified in the influent mass loads of selected antibiotics and hormones that effectively correlate with daily drug administration patterns and with the expected maximum human hormone release, respectively. The occurrence of natural hormones and antimicrobials, administered every 12 hours, shows a daily trend of decreasing contaminant mass load, having the maximum values in the morning hours. The occurrence of antibiotics, typically administered every 8 hours, indicates a daily peak value in samples collected under the highest hydraulic loading. The efficiency of biological removal of both hormones and antibiotics is shown to be limited. Compared to the values obtained in the influent samples, increased concentrations are observed in the biologically treated effluent for trimethoprim, sulfamethoxazole and ciprofloxacin, mainly as a result of deconjugation processes. Ciprofloxacin is shown as the predominant antimicrobial compound in the effluent, and it is present at quantities approximately 10 fold greater than the total mass of the other of the compounds due to poor removal efficiency and alternating solid-liquid partitioning behaviour. Our results suggest that, to increase the micro-pollutant removal and the chemical dosing efficiency in enhanced tertiary treatment, significant benefits can be derived from the optimisation of reactor design and the development of control schemes that accounts for diurnal secondary effluent micro-pollutant and hydraulic loading patterns.

Impacts of competitive inhibition, parent compound formation and partitioning behavior on the removal of antibiotics in municipal wastewater treatment.

We present a process model that predicts the removal of the antibiotic micropollutants, sulfamethoxazole (SMX), tetracycline (TCY), and ciprofloxacin (CIP), in an activated sludge treatment system. A novel method was developed to solve the inverse problem of inferring process rate, sorption, and correction factor parameter values from batch experimental results obtained under aerobic and anoxic conditions. Instead of spiking the batch reactors with reference substances, measurements were made using the xenobiotic organic micropollutant content of preclarified municipal sewage. Parent compound formation and removal were observed, and the model developed using the simulation software West showed limited efficiency to describe the selected micropollutants profiles, when growth substrate removal occurs. The model structure was optimized by accounting for competitive inhibition by readily biodegradable substrates on the cometabolic micropollutant biotransformation processes. Our results suggest that, under anoxic conditions, hydrophobicity-independent mechanisms can significantly impact solid-liquid partitioning that our model takes into account by using the sorption coefficient as a lumped parameter. Forward dynamic simulations were carried out to evaluate the developed model and to confirm it for SMX using data obtained in a full-scale treatment plant. Evaluation of measured and simulation results suggest that, robust model prediction can be achieved by approximating the influent load of chemicals biodegrading via a given parent compound, e.g., human conjugates, as an antibiotic mass that is proportional to the parent compound load.

A new method for determination of halogenated flame retardants in human milk using solid-phase extraction.

A method has been developed for quantitation of a selection of halogenated flame retardants in human milk. The method has been validated for seven polybrominated diphenyl ethers (PBDEs), BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, and BDE-183, and the halogenated phenols 2,4,6-tribromophenol (TriBP), pentabromophenol (PeBP), tetrachlorobisphenol-A (TCBP-A), and tetrabromobisphenol-A (TBBP-A). The sample preparation includes solid-phase extraction using an N-vinylpyrrolidone-divinylbenzene copolymer with on-column lipid decomposition followed by additional cleanup on sulfuric acid-silica columns and methylation of the phenolic compounds. Separation and detection were performed by gas chromatography-electron capture mass spectrometry, using a 5% phenyl 95% dimethylpolysiloxane column. The method has been validated in the range of 1.8-180 pg/g milk for most of the halogenated flame retardants. The average absolute recoveries were from 49 to 83%, and the average recoveries with respect to internal standards were in the range of 53 to 121%. Estimated limits of detection were in the range of 0.3 to 1.0 pg/g milk using a sample size of 5 g for all compounds, except TCBP-A, for which the limit of detection was estimated to 6.7 pg/g milk.

Comparing electron ionization high-resolution and electron capture low-resolution mass spectrometric determination of polybrominated diphenyl ethers in plasma, serum and milk.

Gas chromatography coupled to low-resolution mass spectrometry with electron capture negative ionization as detection mode (GC-LRMS (ECNI)) has been compared to gas chromatography coupled to high-resolution mass spectrometry using electron ionization as detection mode (GC-HRMS (EI)) for determination of polybrominated diphenyl ethers (PBDEs) in biological samples. Extracts of 5.0 g plasma, serum and milk samples were analyzed using both methods. The GC-LRMS (ECNI) and GC-HRMS (EI) systems were found to be equally well suited for determination of PBDEs in the biological samples, as well as in standard solutions, with respect to response, detection limits and repeatability at the pg-level. The estimated limits of detection (LOD) in milk extracts ranged from 0.3-0.6 pg PBDE/g milk and 0.4-0.7 pg PBDE/g milk, for the GC-LRMS (ECNI) and GC-HRMS (EI) systems, respectively. The method repeatability including sample preparation was in the range 4.7-8.4% and 0.6-10% relative standard deviation (RSD) for the GC-LRMS (ECNI) and GC-HRMS (EI) systems, respectively.