Enantiomeric separation of metolachlor and its metabolites using LC-MS and CZE

The stereoisomers of metolachlor and its two polar metabolites [ethane sulfonic acid (ESA) and oxanilic acid (OXA)] were separated using liquid chromatography-mass spectrometry (LC-MS) and capillary zone electrophoresis (CZE), respectively. The separation of metolachlor enantiomers was achieved using a LC-MS equipped with a chiral stationary phase based on cellulose tris(3,5-dimethylphenyl carbamate) and an atmospheric pressure chemical ionization source operated under positive ion mode. The enantiomers of ESA and OXA were separated using CZE with gamma-cyclodextrin (gamma-CD) as chiral selector. Various CZE conditions were investigated to achieve the best resolution of the ESA and OXA enantiomers. The optimum background CZE electrolyte was found to consist of borate buffer (pH=9) containing 20% methanol (v/v) and 2.5% gamma-CD (w/v). Maximum resolution of ESA and OXA enantiomers was achieved using a capillary temperature of 15 degrees C and applied voltage of 30 kV. The applicability of the LC-MS and CZE methods was demonstrated successfully on the enantiomeric analysis of metolachlor and its metabolites in samples from a soil and water degradation study that was set up to probe the stereoselectivity of metolachlor biodegradation. These techniques allow the enantiomeric ratios of the target analytes to be followed over time during the degradation process and thus will prove useful in determining the role of chirality in pesticide degradation and metabolite formation.     

Spatial distribution of pesticides,organochlorine compounds,PBDEs, and metals in surface marine sediments from Cartagena Bay,Colombia

Environmental Science and Pollution Research - Cartagena Bay is an estuarine system located in the Caribbean Sea (Colombia, South America), that receives fresh water from Canal del Dique, which is...     

Effect of sequencing batch reactor operation on presence and concentration of tetracycline-resistant organisms.

The effect of sequencing batch reactor operation on presence and concentration of tetracycline-resistant organisms was studied as a function of organic loading rate (OLR) and solids retention time (SRT), with and without supplemented influent tetracycline. These effects were evaluated using bacterial counts, bacterial production, system growth rate, and percent resistance. These evaluation parameters were applied to both intermediate resistant and resistant heterotrophs, enterics, and lactose fermenters. Tetracycline intermediate resistant and resistant bacteria are defined as the survival of colonies on agar with 5 and 20 mg/L tetracycline, respectively. Based on these studies, increases in influent tetracycline concentration and OLR resulted in amplification of tetracycline resistance. Decreases in SRT also resulted in amplification of tetracycline resistance.     

Free and conjugated estrogen exports in surface-runoff from poultry litter-amended soil

Land application of animal manures such as poultry litter is a common practice, especially in states with surplus manure. Past studies have shown that animal manure may contain estrogens, which are classified as endocrine-disrupting chemicals and may pose a threat to aquatic and wildlife species. We evaluated the concentrations of estrogens in surface runoff from experimental plots (5 x 12 m each) receiving raw and pelletized poultry litter. We evaluated the free (estrone, E1; 17beta-estradiol, E2beta; estriol, E3) and conjugate forms (glucuronides and sulfates) of estrogens, which differ in their toxicity. Sampling was performed for 10 natural storm events over a 4-mo period (April-July 2008). Estrogen concentrations were screened using enzyme-linked immunosorbent assay (ELISA), followed by quantification using liquid chromatography with tandem mass spectrometry (LC/MS/MS). Concentrations of estrogens from ELISA were much higher than the LC/MS/MS values, indicating crossreactivity with organic compounds. Exports of estrogens were much lower from soils amended with pelletized poultry litter than the raw form of the litter. No-tillage management practice also resulted in a lower export of estrogens with surface runoff compared with reduced tillage. The concentrations and exports of conjugate forms of estrogens were much higher than the free forms for some treatments, indicating that the conjugate forms should be considered for a comprehensive assessment of the threat posed by estrogens.     

Determination of potential sources of PCBs and PBDEs in sediments of the Niagara River

Sediments from Niagara River, an important waterway connecting two of the Great Lakes (Lake Erie to Lake Ontario), were analyzed for 14 congeners of polychlorinated biphenyls (PCBs) and 9 congeners of polybrominated diphenyl ethers (PBDEs) using accelerated solvent extraction and gas chromatography/mass spectrometry. Total concentrations of PCBs ranged from 1.7 to 124.6 ng/g were PCBs 138 and 153 were found in all samples. All sites but one showed PBDE in sediments with total concentrations as high as 148 ng/g, suggesting that PBDE is becoming an important class of POP. A land-use and coverage map was used to trace potential localized sources of PCB and PBDE contamination. Results indicate that the highest levels of PCBs and PBDEs were found in sediments collected from areas closest to the discharge locations of municipal wastewater treatment plants (WWTP) and local industries. This is the first study that suggests the importance of WWTP discharges as a potential source of PBDE contamination in the Great Lakes.     

Evaluating the vulnerability of surface waters to antibiotic contamination from varying wastewater treatment plant discharges

Effluents from three wastewater treatment plants with varying wastewater treatment technologies and design were analyzed for six antibiotics and caffeine on three sampling occasions. Sulfamethoxazole, trimethoprim, ciprofloxacin, tetracycline, and clindamycin were detected in the effluents at concentrations ranging from 0.090 to 6.0 microg/L. Caffeine was detected in all effluents at concentrations ranging from 0.19 to 9.9 microg/L. These findings indicate that several conventional wastewater management practices are not effective in the complete removal of antibiotics, and their discharges have a large potential to affect the aquatic environment. To evaluate the persistence of antibiotics coming from the wastewater discharges on the surrounding surface waters, samples were collected from the receiving streams at 10-, 20- and 100-m intervals. Ciprofloxacin, sulfamethoxazole, and clindamycin (0.043 to 0.076 microg/L) were found as far as 100 m from the discharge point, which indicates the persistence of these drugs in surface waters.     

Tetracycline as a selector for resistant bacteria in activated sludge

Tetracycline, one of the most widely used antibiotics, is excreted into wastewater after consumption by humans and animals. The focus of this research was to evaluate the fate of tetracycline resistant bacteria in the activated sludge process as a function of tetracycline loading. The studies were conducted with aerobic biological sequencing batch reactors (SBRs). When comparing 250 microgl(-1) tetracycline fed SBRs with parallel SBRs having a background influent wastewater tetracycline concentration of approximately 1 microgl(-1), tetracycline fed reactors were found to have increased concentrations and production rates of tetracycline resistant bacteria, higher net growth rates of resistant bacteria, and higher percentages of tetracycline resistant bacteria, which were amplified by increase in organic loading and growth rates.     

Dissolved Organic Carbon and Estrogen Transport in Surface Runoff From Agricultural Land Receiving Poultry Litter1

Dutta, Sudarshan, Shreeram Inamdar, Jerry Tso, Diana S. Aga, and J. Tom Sims, 2012. Dissolved Organic Carbon and Estrogen Transport in Surface Runoff from Agricultural Land Receiving Poultry Litter. Journal of the American Water Resources Association (JAWRA) 48(3): 558-569. DOI: 10.1111/j.1752-1688.2011.00634.x Abstract: Dissolved organic carbon (DOC) provides a reactive substrate for the transport of organic contaminants with runoff. Very few studies have investigated the export of DOC from agricultural land, especially those receiving manure applications. We investigated exports of DOC in surface runoff from agricultural fields receiving various treatments of poultry litter (raw vs. pelletized). In addition, we also investigated how estrogens in runoff were associated with DOC. Different forms of estrogens studied were: estrone, 17β-estradiol, estriol, and their conjugates. Experimental agricultural plots were 12 m × 5 m long and had reduced tillage and no-till management practices. The aromatic content of DOC was characterized using specific ultraviolet absorbance (SUVA). Flow-weighted concentrations of DOC and SUVA in surface runoff from plots with poultry litter were significantly (p ≤ 0.10) greater than the control (no litter) plots. Compared to pelletized poultry litter, reduced-tillage plots with raw litter yielded higher DOC concentrations and SUVA values. No significant differences (p ≥ 0.10) in DOC and SUVA were observed between litter treatments for plots with no-till. Total estrogen concentrations (including all forms) were positively and significantly (p ≤ 0.10) correlated with DOC. These results can help select and guide agricultural management practices that can reduce the exports of DOC and associated contaminant from agricultural land receiving manure applications.     

Occurrence of sulfonamide antimicrobials in private water wells in Washington County, Idaho, USA

Samples from six private wells formerly used as sources for drinking water by the residents of Washington County (Weiser, Idaho) were collected to assess the impact of a nearby confined animal feeding operation (CAFO) on the quality of the local groundwater. All six samples were found contaminated by two veterinary antimicrobials, sulfamethazine (at concentrations from 0.076 to 0.22 μg/l) and sulfadimethoxine (at concentrations from 0.046 to 0.068 μg/l). These groundwater samples also contained elevated concentrations of nitrate and ammonium. Three of the sampled wells have nitrate levels that exceeded the maximum contaminant level set by the US Environmental Protection Agency for drinking water, with nitrate concentration as high as 39.1 mg/l. All but one well showed nitrate, which instead contained ammonium at 1.22 mg/l. Analysis of the nitrate and ammonium in these samples by isotopic ratio mass spectrometry indicated δ¹⁵N characteristic of an animal or human waste source. Results from this study underscore the role of CAFO as an important source of antibiotic contamination of groundwater.     

Addressing the challenges of tetracycline analysis in soil: extraction, clean-up, and matrix effects in LC-MS

An optimized extraction and clean-up method for the analysis of chlortetracycline, doxycycline, oxytetracycline, and tetracycline antibiotics in soil is presented in this work. Soil extraction using different solvents was performed, but the use of a 50 : 50 (v/v) methanol : acetate buffer (pH 8) solvent mixture in a pressurized liquid extraction (PLE) system proved to give the best extraction efficiency and reproducibility. The effect of soil composition on the PLE extraction efficiency was also examined, and results indicated that recovery data for one soil is not necessarily consistent with other soil types containing different compositions of clay and organic matter content. The percent recoveries of the optimized PLE method varied between the soils and ranged from 22-99%, depending on soil type, and more specifically clay content. In addition, the extent of ionization suppression caused by co-extracted humic acids was examined in an ion trap mass spectrometer (MS), and a single quadrupole MS. It was found that under positive electrospray ionization, the single quadrupole MS was less susceptible to ionization suppression than the ion trap MS. Therefore, various sample clean-up procedures were evaluated to selectively reduce the amount of co-extracted humic acids in the soil extracts. The most effective clean-up was obtained from the use of StrataX sorbent in combination with a strong anion exchange cartridge.