Craig D. Adams

Oxidation and Biodegradability Enhancement of 1,4-Dioxane using Hydrogen Peroxide and Ozone

Ozone in combination with hydrogen peroxide has been shown to effectly oxidize 1,4-dioxane in synthetic solutions representing groundwater or industrial wastewater to more readily biodegradable oxidation products that could be treated using conventional biological treatment. Bicarbonate alkalinity and competition by 1,3-dioxolane and 2-methyl-1,4-dioxolane were found to increase the oxidant dosages required for 1,4-dioxane oxidation. The results of this study suggest that anaerobic pretreatment prior to advanced oxidation may be a viable means of reducing the ozone and hydrogen peroxide dosages required for biodegradability enhancement

Simultaneous determination of sulfonamides, tetracyclines and tiamulin in swine wastewater by solid-phase extraction and liquid chromatography-mass spectrometry.

Little is known about the contamination level of antibiotics in swine wastewater in China. The highly complex matrix of swine wastewater, which generally has a chemical oxygen demand (COD) concentration as high as 15,000 mg/L, makes it difficult to detect antibiotics at trace levels. In this work, a highly selective and sensitive analytical method was developed for simultaneous determination of three classes of commonly used veterinary antibiotics including five sulfonamides, three tetracyclines and one macrolide in swine wastewater using solid-phase extraction (SPE) and liquid chromatography-mass spectrometry (LC-MS). The method detection limits (MDL) in the swine wastewater were determined to be between 5 and 91 ng/L, depending on specific antibiotics. Except sulfamethizole, all the other eight antibiotics were detected in the swine wastewaters collected from three concentrated swine feeding plants located in the Beijing (China) area, showing a concentration range of 0.62-32.67 microg/L. These results reveal the representative concentration levels of selected antibiotics in the swine wastewaters of Beijing area.

Effects of Ionic Strength, Temperature, and pH on Degradation of Selected Antibiotics

Aqueous degradation rates, which include hydrolysis and epimerization, for chlortetracycline (CTC), oxytetracycline (OTC), tetracycline (TET), lincomycin (LNC), sulfachlorpyridazine (SCP), sulfadimethoxine (SDM), sulfathiazole (STZ), trimethoprim (TRM), and tylosin A (TYL) were studied as a function of ionic strength (0.0015, 0.050, or 0.084 mg/L as Na(2)HPO(4)), temperature (7, 22, and 35 degrees C), and pH (2, 5, 7, 9, and 11). Multiple linear regression revealed that ionic strength did not significantly affect (alpha = 0.05) degradation rates for all compounds, but temperature and pH affected rates for CTC, OTC, and TET significantly (alpha = 0.05). Degradation also was observed for TYL at pH 2 and 11. No significant degradation was observed for LNC, SCP, SDM, STZ, TRM, and TYL (pH 5, 7, and 9) under study conditions. Pseudo first-order rate constants, half-lives, and Arrhenius coefficients were calculated where appropriate. In general, hydrolysis rates for CTC, OTC, and TET increased as pH and temperature increased following Arrhenius relationships. Known degradation products were used to confirm that degradation had occurred, but these products were not quantified. Half-lives ranged from less than 6 h up to 9.7 wk for the tetracyclines and for TYL (pH 2 and 11), but no degradation of LIN, the sulfonamides, or TRM was observed during the study period. These results indicate that tetracyclines and TYL at pH 2 and 11 are prone to pH-mediated transformation and hydrolysis in some cases, but not the sulfonamides, LIN nor TRM are inclined to degrade under study conditions. This indicates that with the exception of CTC, OTC, and TET, pH-mediated reactions such as hydrolysis and epimerization are not likely removal mechanisms in surface water, anaerobic swine lagoons, wastewater, and ground water.

Effects of Ozonation on the Biodegradability of Substituted Phenols

Abstract The aerobic biodegradability of unoxidised and ozonated chloro-, nitro-, and amino-phenols was investigated using batch bioassays with unacclimated biomass. Chloro- and nitro-phenols exhibited biorecalcitrant behavior at 200 mg/liter as COD, yet were more readily degraded at 30 mg/liter as COD. Ozonation of chloro- and nitro-phenols significantly enhanced their biodegradability. While unoxidized aminophenols were readily degradable, ozonation significantly decreased their biodegradability. Quantitative structure activity relationships (QSARs) using Hammett constants were developed for biodegradability of unoxidized substituted phenols. For the eight substituted phenols studied, ozonation significantly decreased the Microtox toxicity of each, with EC50 values increasing from 0.7 to 1.6 orders-of-magnitude.

Investigation of Pharmaceuticals in Missouri Natural and Drinking Water Using High Performance Liquid Chromatography-Tandem Mass Spectrometry

A comprehensive method has been developed and validated in two different water matrices for the analysis of 16 pharmaceutical compounds using solid phase extraction (SPE) of water samples, followed by liquid chromatography coupled with tandem mass spectrometry. These 16 compounds include antibiotics, hormones, analgesics, stimulants, antiepileptics, and X-ray contrast media. Method detection limits (MDLs) that were determined in both reagent water and municipal tap water ranged from 0.1 to 9.9 ng/L. Recoveries for most of the compounds were comparable to those obtained using U.S. EPA methods. Treated and untreated water samples were collected from 31 different water treatment facilities across Missouri, in both winter and summer seasons, and analyzed to assess the 16 pharmaceutical compounds. The results showed that the highest pharmaceutical concentrations in untreated water were caffeine, ibuprofen, and acetaminophen, at concentrations of 224, 77.2, and 70 ng/L, respectively. Concentrations of pharmaceuticals were generally higher during the winter months, as compared to those in the summer due, presumably, to smaller water quantities in the winter, even though pharmaceutical loadings into the receiving waters were similar for both seasons.

Determination of endocrine-disrupting chemicals in the liquid and solid phases of activated sludge by solid phase extraction and gas chromatography-mass spectrometry

The highly complex matrix of activated sludge in sewage treatment plants (STPs) makes it difficult to detect endocrine-disrupting chemicals (EDCs) which are usually present at low concentration levels. To date, no literature has reported the concentrations of steroid estrogens in activated sludge in China and very limited data are available worldwide. In this work, a highly selective and sensitive analytical method was developed for simultaneous determination of two classes of EDCs, including estrone (E1), 17beta-estradiol (E2), estriol (E3), 17 alpha-ethynylestradiol (EE2), 4-nonylphenol (NP) and bisphenol A (BPA), in the liquid and solid phases of activated sludge. The procedures for sample preparation, extracts derivatization, and gas chromatography-mass spectrometry (GC-MS) quantification were all optimized to effectively determine target EDCs while minimizing matrix interference. The developed method showed good calibration linearity, recovery, precision, and a low limit of quantification (LOQ) for all selected EDCs in both liquid and solid phases of activated sludge. It was successfully applied to determine the concentrations of EDCs in activated sludge samples from two STPs located in Beijing and Shanghai of China, respectively.

Inhibition of microbial metabolism in anaerobic lagoons by selected sulfonamides, tetracyclines, lincomycin, and tylosin tartrate

Antibiotics are used to maintain healthy livestock and to promote weight gain in concentrated animal feed operations. Antibiotics rarely are metabolized completely by livestock and, thus, are often present in livestock waste and in waste-treatment lagoons. The introduction of antibiotics into anaerobic lagoons commonly used for swine waste treatment has the potential for negative impacts on lagoon performance, which relies on a consortium of microbes ranging from fermentative microorganisms to methanogens. To address this concern, the effects of eight common veterinary antibiotics on anaerobic activity were studied. Anaerobic microcosms, prepared from freshly collected lagoon slurries, were amended with individual antibiotics at 10 mg/L for the initial screening study and at 1, 5, and 25 mg/L for the dose-response study. Monitored metabolic indicators included hydrogen, methane, and volatile fatty acid concentrations as well as chemical oxygen demand. The selected antibiotics significantly inhibited methane production relative to unamended controls, thus indicating that antibiotics at concentrations commonly found in swine lagoons can negatively impact anaerobic metabolism. Additionally, historical antibiotic usage seems to be a potential factor in affecting methane production. Specifically, less inhibition of methane production was noted in samples taken from the lagoon with a history of multiple-antibiotic use.

Lead, Zinc, Copper, and Cadmium in Fish and Sediments from the Big River and Flat River Creek of Missouri's Old Lead Belt

The Old Lead Belt of Missouri was a major lead-producing region for over a century. Several large tailings piles and other industrial wastes remain behind, though mining operations in the region ceased in 1972. Samples of stream sediments and fish were collected from established sites on the Big River and Flat River Creek over a 3-year period from 1998 to 2000 to evaluate ongoing remediation efforts and determine the current impact of residual mining wastes. Benthic sediments and fish taken in the vicinity of inactive industrial sites were found to contain elevated concentrations of Pb, Zn, Cu, and Cd. Concentrations of Pb and Zn in fillets of suckers and sunfish, as well as in whole bodies of sunfish, correlate well with metal concentrations observed in surficial sediments. The results of analyses provide valuable quantitative information regarding specific sources, current levels of contamination, potential risk to public health, and will allow more accurate assessment of continuing remediation efforts.

Oxidation Kinetics of Two Pesticides in Natural Waters by Ozonation and Ozone Combined with Hydrogen Peroxide

The oxidation of bromoxynil and trifluralin was investigated using ozone (O(3)) and O(3) combined with hydrogen peroxide (H(2)O(2)) in natural waters using batch reactors. The results indicated that these pesticides could not be completely degraded during ozonation, achieving degradation levels lower than 50%. An enhancement of the level of degradation was observed using O(3)/H(2)O(2) process. A biphasic behaviour of O(3) was also observed. Depending on the experimental conditions, the rate constant for O(3) decomposition was estimated to be between 7.4 × 10(-4) s(-1) to 5.8 × 10(-2) s(-1), and 3.2 × 10(-3) s(-1) to 4.2 × 10(-2) s(-1) for bromoxynil and trifluralin samples, respectively. Acute toxicity analysis performed using Microtox(®) showed a decrease in the toxic effects of the samples on the luminescent bacteria during the first few minutes of treatment, followed by an increase of the toxic effects at the end of the reaction for both pesticides. The quantification of oxidation by-products generated during treatment was also addressed. The total molar balances of the degradation by-products versus the initial pesticide concentrations ranged from 60 to 103% under different experimental conditions.

Oxidative removal of selected endocrine-disruptors and pharmaceuticals in drinking water treatment systems, and identification of degradation products of triclosan

The potential occurrences of endocrine-disrupting compounds (EDCs), as well as pharmaceuticals, are considered to be emerging environmental problems due to their persistence and continuous input into the aquatic ecosystem, even at only trace concentrations. This study systematically investigated the oxidative removal of eight specially selected ECDs and pharmaceuticals by comparing their relative reactivity as a function of different oxidative treatment processes (i.e., free chlorine, ozone, monochloramine, and permanganate) under various pH conditions. For the oxidative removal study, EDC and pharmaceutical standards were spiked into both deionized water and natural water, followed by treatment using common oxidants at typical water treatment concentrations. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used for identification and quantification. The removal efficiency of the EDCs and pharmaceuticals varied significantly between oxidation processes. Free chlorine, permanganate, and ozone treatments were all highly effective at the elimination of triclosan and estrone, while they were not effective for removing ibuprofen, iopromide, and clofibric acid. Monochloramine (at a dose of 3mg/L) was mostly ineffective in eliminating any of the selected EDCs and pharmaceuticals under the tested conditions. pH also played an important role in the removal efficiency of the EDCs and pharmaceuticals during free chlorine, permanganate, and ozone treatments. Additionally, the study identified the oxidation products of triclosan by permanganate, and 2,4-dichlorophenol was identified as the major oxidation product of triclosan by permanganate in drinking water system treatment. Furthermore, 2,4-dichlorophenol was further degradated to 4,5-dichloro-2-(2,4-dichlorophenoxy)phenol and/or 5,6-dichloro-2-(2,4-dichlorophenoxy)phenol. The kinetics for this reaction indicated that the reaction was first order in the drinking water system.