Toxic cyanobacterial breakthrough and accumulation in a drinking water plant: a monitoring and treatment challenge.

The detection of cyanobacteria and their associated toxins has intensified in recent years in both drinking water sources and the raw water of drinking water treatment plants (DWTPs). The objectives of this study were to: 1) estimate the breakthrough and accumulation of toxic cyanobacteria in water, scums and sludge inside a DWTP, and 2) to determine whether chlorination can be an efficient barrier to the prevention of cyanotoxin breakthrough in drinking water. In a full scale DWTP, the fate of cyanobacteria and their associated toxins was studied after the addition of coagulant and powdered activated carbon, post clarification, within the clarifier sludge bed, after filtration and final chlorination. Elevated cyanobacterial cell numbers (4.7 × 10(6)cells/mL) and total microcystins concentrations (up to 10 mg/L) accumulated in the clarifiers of the treatment plant. Breakthrough of cells and toxins in filtered water was observed. Also, a total microcystins concentration of 2.47 µg/L was measured in chlorinated drinking water. Cyanobacterial cells and toxins from environmental bloom samples were more resistant to chlorination than results obtained using laboratory cultured cells and dissolved standard toxins.

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters.

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L(-1). These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.

Perfluorooctane sulfonate toxicity, isomer-specific accumulation, and maternal transfer in zebrafish (Danio rerio) and rainbow trout (Oncorhynchus mykiss).

Perfluorooctane sulfonate (PFOS; C(8)F(17)SO(3) (-)) bioaccumulation and toxicity have been demonstrated in both aquatic and terrestrial organisms. The majority of investigations have examined total PFOS concentrations in wildlife and in toxicity testing, but isomer-specific monitoring studies are less common, and no laboratory-based study of PFOS isomer accumulation in fish has been reported. The present study examined accumulation and maternal transfer of PFOS isomers in zebrafish and tissue-specific accumulation of PFOS isomers in trout parr. A median lethal dose (LC50) of 22.2 and 2.5 mg/L was calculated for adult zebrafish and trout parr, respectively. A two-week PFOS exposure resulted in tissue-specific PFOS accumulation in trout, with maximum concentrations identified in the liver tissue (>50 microg/g). Prior exposure to PFOS as alevin did not affect the accumulation of PFOS in tissues later in life. In both species, accumulation of branched PFOS isomers generally occurred to a lesser extent than linear PFOS, which may explain the relative deficiency of branched PFOS isomers in some aquatic species in the field. Analysis of exposed trout tissues indicated that isomer discrimination may occur at the level of elimination or uptake and elimination processes in the kidney or gill, respectively. When zebrafish underwent a reproductive cycle in the presence of PFOS, approximately 10% (wt) of the adult PFOS body burden was transferred to the developing embryos, resulting in a higher total PFOS concentration in eggs (116 +/- 13.3 microg/g) than in the parent fish (72.1 +/- 7.6 microg/g). The isomer profile in eggs was not significantly different from that of adults, suggesting that the maternal transfer of branched and linear PFOS isomers in fish is largely nonisomer specific.

Loadings, trends, comparisons, and fate of achiral and chiral pharmaceuticals in wastewaters from urban tertiary and rural aerated lagoon treatments.

A comparison of time-weighted average pharmaceutical concentrations, loadings and enantiomer fractions (EFs) was made among treated wastewater from one rural aerated lagoon and from two urban tertiary wastewater treatment plants (WWTPs) in Alberta, Canada. Passive samplers were deployed directly in treated effluent for nearly continuous monitoring of temporal trends between July 2007 and April 2008. In aerated lagoon effluent, concentrations of some drugs changed over time, with some higher concentrations in winter likely due to reduced attenuation from lower temperatures (e.g., less microbially mediated biotransformation) and reduced photolysis from ice cover over lagoons; however, concentrations of some drugs (e.g. antibiotics) may also be influenced by changing use patterns over the year. Winter loadings to receiving waters for the sum of all drugs were 700 and 400 g/day from the two urban plants, compared with 4 g/day from the rural plant. Per capita loadings were similar amongst all plants. This result indicates that measured loadings, weighted by population served by WWTPs, are a good predictor of other effluent concentrations, even among different treatment types. Temporal changes in chiral drug EFs were observed in the effluent of aerated lagoons, and some differences in EF were found among WWTPs. This result suggests that there may be some variation of microbial biotransformation of drugs in WWTPs among plants and treatment types, and that the latter may be a good predictor of EF for some, but not all drugs.

JEM spotlight: recent advances in analysis of pharmaceuticals in the aquatic environment.

Both ecosystem and human health rely on clean, abundant supplies of water, thus many classes of potential pollutants are regulated. In recent years, the possible risks associated with largely uncontrolled inputs of pharmaceuticals to rivers, lakes, groundwater, and coastal waters, mainly via wastewater, have been a focus of much research. During this time, our capacity to sequester, identify, and quantify pharmaceuticals in environmental matrices has improved. Devices have emerged to allow passive uptake of drugs to augment or replace laborious grab sampling. Advances in sample preparation have streamlined extraction procedures and removed interfering matrix components. New instrumental techniques have allowed faster, more accurate and sensitive detection of drugs in water samples. This review highlights all of these advances, from sample collection to instrumental analysis, which will continue to help us better understand the fate and effects of pharmaceuticals in aquatic systems.

Laboratory calibration and field deployment of the polar organic chemical integrative sampler for pharmaceuticals and personal care products in wastewater and surface water.

Aqueous sampling rates for 25 pharmaceuticals and personal care products (PPCPs) were determined on the commercially available passive Polar Organic Chemical Integrative Sampler (POCIS). To date, POCIS calibration has only been carried out for a handful of compounds. Uptake rates were 0.040 to 2.462 L/d under conditions of flowing water; quiescent conditions resulted in uptake rates between 0.016 and 0.223 L/d. The uptake of many PPCPs appears to be boundary-layer controlled, as indicated by higher sampling rates under flowing conditions. Sampling rates were corrected for analyte dissipation rates, and some correlations with octanol-water partition coefficients were noted. Field deployments of POCIS in wastewater effluent and surface waters had time-weighted average concentrations derived from laboratory calibrations that were consistent with regular grab samples. This work indicates that POCIS can be used as a quantitative tool for measuring PPCPs in the aquatic environment.

Stereoisomer analysis of wastewater-derived beta-blockers, selective serotonin re-uptake inhibitors, and salbutamol by high-performance liquid chromatography-tandem mass spectrometry.

A reversed-phase enantioselective liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) method was developed to measure enantiomer fractions (EF) and concentrations of pharmaceuticals in wastewater. Enantiomer resolution of six beta-blockers (atenolol, metoprolol, nadolol, pindolol, propranolol, and sotalol) along with two selective serotonin re-uptake inhibitors (citalopram, fluoxetine) and one beta(2)-agonist (salbutamol) was achieved with the Chirobiotic V stationary phase. Analyte recovery averaged 86% in influent and 78% in effluent with limits of detection ranging from 0.2 to 7.5 ng/L. These results represent an improvement in wastewater EF measurement for atenolol, metoprolol and propranolol as well as the first EF measurements of citalopram, fluoxetine, nadolol, pindolol, salbutamol and sotalol in wastewaters. Changes in EF through treatment indicate biologically mediated stereoselective processes were likely occurring during wastewater treatment.

Stereoisomer quantification of the beta-blocker drugs atenolol, metoprolol, and propranolol in wastewaters by chiral high-performance liquid chromatography-tandem mass spectrometry.

A chiral liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) method was developed and validated for measuring individual enantiomers of three beta-blocker drugs (atenolol, metoprolol, and propranolol) in wastewater treatment plant (WWTP) influents and effluents. Mean recoveries of the pharmaceuticals ranged from 67 to 106%, and the limits of detection of the analytes were 2-17 ng/L in wastewater effluents. The method was demonstrated by measuring, for the first time, the stereoisomer composition of target analytes in raw and treated wastewaters of two Canadian WWTPs. In these trials, racemic amounts of the three drugs were observed in influent of one wastewater treatment plant, but nonracemic amounts were observed in another. Effluents of the two plants contained nonracemic amounts of the drugs. These results indicate that biologically-mediated stereoselective processes that differ among WWTPs had occurred to eliminate individual enantiomers of the target analytes.