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 (R² = 0.45), while carbamazepine is a good indicator of cumulative persistence compounds.     

The evaluation of electrical energy per order (E(Eo)) for photooxidative decolorization of four textile dye solutions by the kinetic model

Photooxidative decolorization of four textile dyestuffs, C.I. Acid Orange 7 (AO7), C.I. Acid Orange 8 (AO8), C.I. Acid Orange 52 (AO52) and C.I. Acid Blue 74 (AB74), by UV/H2O2 was investigated in a laboratory scale photoreactor equipped with a 15 W low pressure mercury vapour lamp. The decolorization of the dyes was found to follow pseudo-first-order kinetics, and hence the figure-of-merit electrical energy per order (E(Eo)) is appropriate for estimating the electrical energy efficiency. The E(Eo) values were found to depend on the concentration of H2O2, concentration and basic structure of the dye. This study shows that these textile dyes can be treated easily and effectively with the UV/H2O2 process with E(Eo) values between 0.4 and 5 kW h m-3 order-1, depending on the initial concentrations of dyes and H2O2. The kinetic model, based on the initial rates of degradation, provided good prediction of the E(Eo) values for a variety of conditions.     

Photocatalytic degradation of an organophosphorus pesticide phosalone in aqueous suspensions of titanium dioxide

The present work deals with photocatalytic degradation of an organophosphorus pesticide, phosalone, in water in the presence of TiO2 particles under UV light illumination (1000 W). The influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO2, irradiation time, stirring rate, and distance from UV source, on the photodegradation efficiency of phosalone was investigated. The degradation rate of phosalone was not high when the photolysis was carried out in the absence of TiO2 and it was negligible in the absence of UV light. The half-life (DT50) of a 20 ppm aqueous solution of phosalone was 15 min in optimized conditions. The plot of lnC (phosalone) vs. time was linear, suggesting first order reaction (K=0.0532 min(-1)). The half-life time of photomineralization in the concentration range of 7.5-20 ppm was 13.02 min. The efficiency of the method was also determined by measuring the reduction of Chemical Oxygen Demand (COD). During the mineralization under optimized conditions, COD decreased by more than 45% at irradiation time of 15 min. The photodegradation of phosalone was enhanced by addition of proper amount of hydrogen peroxide (150 ppm).     

Critical effect of hydrogen peroxide concentration in photochemical oxidative degradation of C.I. Acid Red 27 (AR27)

The photochemical decolorization of C.I. Acid Red 27 (AR27), an anionic monoazo dye, was studied in the UV/H2O2 process by using a batch reactor with a UV-C lamp emitting at 254 nm (30 W). The decolorization rate follows pseudo-first order kinetic with respect to the AR27 concentration. The results indicate that the apparent reaction rate constant in the UV/H2O2 process is a function of H2O2 concentration. In this work, a mathematical relation between the apparent reaction rate constant of the AR27 removal and used H2O2 was established. The applied amount of H2O2 was performed in two forms: (i) the light fraction absorbed by H2O2 in 254 nm, (ii) the initial concentration ratio of H2O2 to AR27. The results obtained from this mathematical model are in good agreement with experimental results.     

Neglected sources of pharmaceuticals in river water--footprints of a Reggae festival

Wastewater treatment plants (WWTPs) are commonly considered as the main source of pharmaceuticals in surface waters. Here, however, we show that an open-air festival, attracting approximately 10,000 visitors per year at the shores of River Fyris upstream of Uppsala WWTP, can temporarily result in a higher pharmaceutical input into the river water than the WWTP. Studying the influence of Uppsala Reggae festival on the occurrence of ten commonly used acidic and basic pharmaceuticals upstream, in the effluent, and downstream of the Uppsala WWTP, we found that occasional heavy rainfalls during the festival in 2008 severely increased the mass flows of all pharmaceuticals at the WWTP upstream site. Also, strong increases in ammonium (210-fold), nitrate (21-fold), and total nitrogen (21-fold) mass flows were observed. The pharmaceutical mass flows at the upstream site were up to 3.4 times higher than those observed in the WWTP effluent. In contrast, in 2009, the festival was not accompanied with rainfalls and no major additional input of pharmaceuticals and nitrogen was observed. The findings of this study give new insights into risk assessments and are relevant for monitoring programmes.     

Winter accumulation of acidic pharmaceuticals in a Swedish river

Purpose  

In this study, seasonal variations in the concentration profile of four analgesics and one lipid regulator were monitored on their way from a wastewater treatment plant (WWTP) effluent, along a river, and into a lake.     

Photocatalytic degradation of the herbicide erioglaucine in the presence of nanosized titanium dioxide: comparison and modeling of reaction kinetics

The present work mainly deals with photocatalytic degradation of a herbicide, erioglaucine, in water in the presence of TiO2 nanoparticles (Degussa P-25) under ultraviolet (UV) light illumination (30 W). The degradation rate of erioglaucine was not so high when the photolysis was carried out in the absence of TiO2 and it was negligible in the absence of UV light. We have studied the influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO2, irradiation time and initial concentration of erioglaucine on the photodegradation efficiency of erioglaucine. A kinetic model is applied for the photocatalytic oxidation by the UV/TiO2 system. Experimental results indicated that the photocatalytic degradation process could be explained in terms of the Langmuir-Hinshelwood kinetic model. The values of the adsorption equilibrium constant, K, and the second order kinetic rate constant, k, were 0.116 ppm-1 and 0.984 ppm min-1, respectively. In this work, we also compared the reactivity between the commercial TiO2 Degussa P-25 and a rutile TiO2. The photocatalytic activities of both photocatalysts were tested using the herbicide solution. We have noticed that photodegradation efficiency was different between both of them. The higher photoactivity of Degussa P-25 compared to that of rutile TiO2 for the photodegradation of erioglaucine may be due to higher hydroxyl content, higher surface area, nano-size and crystallinity of the Degussa P-25. Our results also showed that the UV/TiO2 process with Degussa P-25 as photocatalyst was appropriate as the effective treatment method for removal of erioglaucine from a real wastewater. The electrical energy consumption per order of magnitude for photocatalytic degradation of erioglaucine was lower with Degussa P-25 than in the presence of rutile TiO2.     

On-line solid phase extraction and liquid chromatography/tandem mass spectrometry to quantify pharmaceuticals, pesticides and some metabolites in wastewaters, drinking, and surface waters

A simple on-line method was developed for the analysis of pharmaceuticals, pesticides and some metabolites in drinking, surface and wastewater samples. The technique is based on the use of on-line solid-phase extraction combined with liquid chromatography electrospray tandem mass spectrometry with positive electrospray ionization (LC-ESI(PI)-MS/MS). The injection of only 1 mL of filtered water sample is used with a total analysis time of 20 min, including the period required to flush the SPE cartridge with organic solvent and reconditioning the LC column. Method detection limits were in the range of 2 to 24 ng L(-1) for the compounds of interest, with recoveries from 87 to 110% in surface as well as wastewater samples. Matrix effects were observed for some compounds without exceeding more than 25%. All results displayed a good degree of reproducibility, with relative standard deviations (RSD) of less than 12% for all compounds. Moreover, at least 200 samples were analyzed without altering the performance of the pre-concentration column. This method was preferred over traditional off-line procedures because it minimizes tedious sample preparation, increases productivity and sample throughput. The analysis of various water and wastewater samples showed that caffeine, carbamazepine and atrazine could be detected in all the samples analysed and the selected compounds are always present in at least one of the sample types.     

Pasture diversification to combat climate change impacts on grazing dairy production

Among livestock systems, grazing is likely to be most impacted by climate change because of its dependency to feed quality and availability. In order to reduce the impact of climate change on grazing livestock systems, adaptation measures should be implemented. The goal of this study is to identify the best pasture composition for a representative grazing dairy farm in Michigan in order to reduce the impacts of climate change on production. In order to achieve the goal of this study, three objectives were sought: (1) identify the best pasture composition, (2) assess economic and resource use impacts of pasture compositions under future climate scenarios, and (3) evaluate the resiliency of pasture compositions. A representative farm was developed based on a livestock practices survey and incorporated into the Integrated Farm System Model (IFSM). For the pasture compositions, four cool-season grass species and two legumes were evaluated under both current and future climate scenarios. The effectiveness of adaptation measures based on economic and resource use criteria was evaluated. Overall, the pasture composition with 50% perennial ryegrass (Lolium multiflorum) and 50% red clover (Trifolium pratense) was identified as the best. In addition, the increase in precipitation and temperature of the most intensive climate scenario could significantly improve farm net return per cow (Bos taurus) and whole farm profit while no significant impact was observed on resource use criteria. Finally, the overall sensitivity assessment showed that the most resilient pasture composition under future climate scenarios was ryegrass with red clover and the least resilient was orchardgrass (Dactylis glomerata) with white clover (Trifolium repens).