Atlasi Daneshvar

Ozone oxidation of pharmaceuticals, endocrine disruptors and pesticides during drinking water treatment.

This study investigates the oxidation of pharmaceuticals, endocrine disrupting compounds and pesticides during ozonation applied in drinking water treatment. In the first step, second-order rate constants for the reactions of selected compounds with molecular ozone (k(O3)) were determined in bench-scale experiments at pH 8.10: caffeine (650+/-22M(-1)s(-1)), progesterone (601+/-9M(-1)s(-1)), medroxyprogesterone (558+/-9M(-1)s(-1)), norethindrone (2215+/-76M(-1)s(-1)) and levonorgestrel (1427+/-62M(-1)s(-1)). Compared to phenolic estrogens (estrone, 17beta-estradiol, estriol and 17alpha-ethinylestradiol), the selected progestogen endocrine disruptors reacted far slower with ozone. In the second part of the study, bench-scale experiments were conducted with surface waters spiked with 16 target compounds to assess their oxidative removal using ozone and determine if bench-scale results would accurately predict full-scale removal data. Overall, the data provided evidence that ozone is effective for removing trace organic contaminants from water with ozone doses typically applied in drinking water treatment. Ozonation removed over 80% of caffeine, pharmaceuticals and endocrine disruptors within the CT value of about 2 mg min L(-1). As expected, pesticides were found to be the most recalcitrant compounds to oxidize. Caffeine can be used as an indicator compound to gauge the efficacy of ozone treatment.

Seasonal variations in the occurrence and fate of basic and neutral pharmaceuticals in a Swedish river–lake system

The seasonal variations in the occurrence of carbamazepine, atenolol, metoprolol, sotalol, and acebutolol were studied at seven sites along River Fyris from December 2007 to December 2008. Samples were collected from the effluent of a waste water treatment plant (WWTP), at one upstream site, and five downstream sites of the WWTP. During one occasion in May 2008, water samples were collected at different locations and depths in the recipient lake. All analytes except of acebutolol were present in both the river and the lake at quantifiable amounts at all sampling occasions. Carbamazepine was found in similar concentrations (about 90 ng L(-1)) at all sampling sites and all studied depths (0.5-40 m) in the lake, indicating high environmental persistence of this compound. A clear seasonal pattern was observed for the natural attenuation of the beta-blockers in the river, with the highest attenuation occurring in summer and the lowest in winter. The loss of beta-blockers on a distance of 1320 m reached up to 75% during summer time but was insignificant during winter. The seasonal variations in the loss followed the seasonal variations in water temperature and chlorophyll a mass flow suggesting that biotransformation and adsorption are the main processes responsible for the loss of the studied pharmaceuticals in River Fyris downstream the WWTP.

Evaluating pharmaceuticals and caffeine as indicators of fecal contamination in drinking water sources of the Greater Montreal region.

We surveyed four different river systems in the Greater Montreal region, upstream and downstream of entry points of contamination, from April 2007 to January 2009. The studied compounds belong to three different groups: PPCPs (caffeine, carbamazepine, naproxen, gemfibrozil, and trimethoprim), hormones (progesterone, estrone, and estradiol), and triazine herbicides and their metabolites (atrazine, deethylatrazine, deisopropylatrazine, simazine, and cyanazine). In the system A, B, and C having low flow rate and high TOC, we observed the highest detection frequencies and mass flows of PPCPs compared to the other compounds, reflecting discharge of urban contaminations through WWTPs and CSOs. However, in River D, having high flow rate and low TOC, comparable frequency of detection of triazine and their by-products and PPCPs, reflecting cumulative loads of these compounds from the Great Lakes as well as persistency against natural attenuation processes. Considering large differences in the removal efficiencies of caffeine and carbamazepine, a high ratio of caffeine/carbamazepine might be an indicative of a greater proportion of raw sewage versus treated wastewater in surface waters. In addition, caffeine appeared to be a promising indicator of recent urban fecal contaminations, as shown by the significant correlation with FC (R(2)=0.45), while carbamazepine is a good indicator of cumulative persistence compounds.

Characterization of five passive sampling devices for monitoring of pesticides in water

Five different passive sampler devices were characterized under laboratory conditions for measurement of 124 legacy and current used pesticides in water. In addition, passive sampler derived time-weighted average (TWA) concentrations were compared to time-integrated active sampling in the field. Sampling rates (RS) and passive sampler-water partition coefficients (KPW) were calculated for individual pesticides using silicone rubber (SR), polar organic chemical integrative sampler (POCIS)-A, POCIS-B, Chemcatcher(®) SDB-RPS and Chemcatcher(®) C18. The median RS (Lday(-1)) decreased as follows: SR (0.86)>POCIS-B (0.22)>POCIS-A (0.18)>Chemcatcher(®) SDB-RPS (0.05)>Chemcatcher(®) C18 (0.02), while the median logKPW (Lkg(-1)) decreased as follows: POCIS-B (4.78)>POCIS-A (4.56)>Chemcatcher(®) SDB-RPS (3.17)>SR (3.14)>Chemcatcher(®)C18 (2.71). The uptake of the selected compounds depended on their physicochemical properties, i.e. SR showed a better uptake for more hydrophobic compounds (log octanol-water partition coefficient (KOW)>5.3), whereas POCIS-A, POCIS-B and Chemcatcher(®) SDB-RPS were more suitable for hydrophilic compounds (logKOW<0.70). Overall, the comparison between passive sampler and time-integrated active sampler concentrations showed a good agreement and the tested passive samplers were suitable for capturing compounds with a wide range of KOWs in water.

Characterization and Application of Passive Samplers for Monitoring of Pesticides in Water.

Five different water passive samplers were calibrated under laboratory conditions for measurement of 124 legacy and current used pesticides. This study provides a protocol for the passive sampler preparation, calibration, extraction method and instrumental analysis. Sampling rates (RS) and passive sampler-water partition coefficients (KPW) were calculated for silicone rubber, polar organic chemical integrative sampler POCIS-A, POCIS-B, SDB-RPS and C18 disk. The uptake of the selected compounds depended on their physicochemical properties, i.e., silicone rubber showed a better uptake for more hydrophobic compounds (log octanol-water partition coefficient (KOW) > 5.3), whereas POCIS-A, POCIS-B and SDB-RPS disk were more suitable for hydrophilic compounds (log KOW < 0.70).

Concentrations, fluxes and field calibration of passive water samplers for pesticides and hazard-based risk assessment

Three passive sampler types including Chemcatcher® C18, polar organic chemical integrative sampler-hydrophilic-lipophilic balance (POCIS-HLB) and silicone rubber (SR) based on polydimethylsiloxane (PDMS) were evaluated for 124 legacy and current used pesticides at two sampling locations in southern Sweden over a period of 6 weeks and compared to time-proportional composite active sampling. In addition, an in situ calibration was performed resulting in median in situ sampling rates (RS, L day-1) of 0.01 for Chemcatcher® C18, 0.03 for POCIS-HLB, and 0.18 for SR, and median in situ passive sampler-water partition coefficients (log KPW, L kg-1) of 2.76 for Chemcatcher® C18, 3.87 for POCIS-HLB, and 2.64 for SR. Deisopropylatrazine D5 showed to be suitable as a performance reference compound (PRC) for SR. There was a good agreement between the pesticide concentrations using passive and active sampling. However, the three passive samplers detected 38 pesticides (including 9 priority substances from the EU Water Framework Directive (WFD) and 2 pyrethriods) which were not detected by the active sampler. The most frequently detected pesticides with a detection frequency of >90% for both sites were atrazine, 2,6-dichlorobenzamide, bentazone, chloridazon, isoproturon, and propiconazole. The annual average environmental quality standard (AA-EQS) for inland surface waters of the EU WFD and the risk quotient (RQ) of 1 was exceeded on a number of occasions indicating potential risk for the aquatic environment.