A spectroscopic study of the bromination of the endocrine disruptor ethynylestradiol

Bromination of ethynylestradiol (EE2) was studied using fluorescence and conventional and stopped-flow absorbance spectroscopy. EE2 transformations in the presence of bromine were determined to proceed through sequential reactions. The first step is very rapid and results in the formation of a brominated cyclohexadienone that is susceptible to reduction but in oxidative conditions it undergoes a transformation into monobromo-EE2 in a first-order OH- -accelerated reaction. The transformation from monobromo-EE2 to dibromo-EE2 follows a similar mechanism. The rates of reactions of bromine-substituted EE2 species are orders of magnitude lower than that of the parent compound indicating that these species can persist in conditions typical for water treatment operations.     

The mobility of thiobencarb and fipronil in two flooded rice-growing soils

The mobility of the rice pesticides thiobencarb (S-[(4-chlorophenyl) methyl] diethylcarbamothioate) and fipronil ([5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]pyrazole) were investigated in the glasshouse under flooded conditions using two Australian rice-growing soils. When using leakage rates of 10 mm day(-1), less than 20% of applied thiobencarb and fipronil remained in the water column after 10 days due to rapid transfer to the soil phase. Up to 70% and 65% of the applied thiobencarb and fipronil, respectively, were recovered from the 0-1 cm layer of soils. Only 5-7% of each pesticide was recovered from the 1-2 cm layer, and less than 2% was recovered from each 1 cm layer in the 2-10 cm region of the soils. Analysis of the water leaking from the base of the soil cores showed between 5-10% of the applied thiobencarb and between 10-20% of the applied fipronil leaching from the soil cores. The high levels of pesticide in the effluent was attributed to preferential flow of pesticide-laden water via soil macropores resulting from the wetting and drying process, worm holes and root channels.     

Role of protein, amino acids, and enzyme activity on odor production from anaerobically digested and dewatered biosolids.

The main objective of this research was to test the hypothesis that bioavailable protein and, more specifically, the sulfur-containing amino acids within the protein, can be degraded by proteolytic enzymes to produce odor-causing compounds--mainly volatile sulfur compounds (VSCs)--during biosolids storage. To achieve these objectives, samples of digester effluent and cake solids were collected at 11 different wastewater treatment plants in North America, and the samples were analyzed for protein and amino acid content and general protein-degrading enzyme activity. At the same time, cake samples were stored using headspace bottles, the concentration of VSCs were measured using gas chromatography, and olfactometry measurements were made by a trained odor panel. The results showed that the bound cake protein content and methionine content was well-correlated with VSC production and the detection threshold measured by the odor panel.     

Simulating Unstressed Crop Development and Growth Using the Unified Plant Growth Model (UPGM)

Since initial development of the EPIC model in 1989, the EPIC plant growth component has been incorporated into other erosion and crop management models (e.g., WEPS, WEPP, SWAT, ALMANAC, and GPFARM) and subsequently modified to meet research objectives of the model developers. This has resulted in different versions of the same base plant growth component. The objectives of this study are the following: (1) describe the standalone Unified Plant Growth Model (UPGM), initially derived from the WEPS plant growth model, to be used for merging enhancements from other EPIC-based plant growth models; and (2) describe and evaluate new phenology, seedling emergence, and canopy height sub-models derived from the Phenology Modular Modeling System (PhenologyMMS V1.2) and incorporated into UPGM. A 6-year (2005–2010) irrigated maize (Zea mays L.) study from northeast Colorado was used to calibrate and evaluate UPGM running both the original (i.e., based on WEPS) and new phenology, seedling emergence, and canopy height sub-models. Model statistics indicated the new sub-models usually resulted in better simulation results than the original sub-models. For example when comparing original and new sub-models, respectively, for predicting canopy height, the root mean square error (RMSE) was 53.7 and 40.7 cm, index of agreement (d) was 0.84 and 0.92, relative error (RE) was 26.0 and ?1.26 %, and normalized objective function (NOF) was 0.47 and 0.33. The new sub-models predict leaf number (old sub-models do not), with mean values for 4 years of 2.43 leaves (RMSE), 0.78 (d), 18.38 % (RE), and 0.27 (NOF). Simulating grain yield, final above ground biomass, and harvest index showed little difference when running the original or new sub-models. Both the new phenology and seedling emergence sub-models respond to varying water deficits, increasing the robustness of UPGM for more diverse environmental conditions. Future research will continue working to incorporate existing enhancements from other EPIC-based plant growth models to unify them into one model such as multispecies competition and N cycling.     

Application of a benthic observed/expected-type model for assessing Central Appalachian streams influenced by regional stressors in West Virginia and Kentucky

Stream bioassessments rely on taxonomic composition at sites compared with natural, reference conditions. We developed and tested an observed/expected (O/E) predictive model of taxonomic completeness and an index of compositional dissimilarity (BC index) for Central Appalachian streams using combined macroinvertebrate datasets from riffle habitats in West Virginia (WV) and Kentucky (KY). A total of 102 reference sites were used to calibrate the O/E model, which was then applied to assess over 1,200 sites sampled over a 10-year period. Using an all subsets discriminant function analysis (DFA) procedure, we tested combinations of 14 predictor variables that produced DF and O/E models of varying performance. We selected the most precise model using a probability of capture at >0.5 (O/E _0.5, SD?=?0.159); this model was constructed with only three simple predictor variables—Julian day, latitude, and whether a site was in ecoregion 69a. We evaluated O/E and BC indices between reference and test sites and compared their response to regional stressors, including coal mining, residential development, and acid deposition. The Central Appalachian O/E and BC indices both showed excellent discriminatory power and were significantly correlated to a variety of regional stressors; in some instances, the BC index was slightly more sensitive and responsive than the O/E _0.5 model. These indices can be used to supplement existing bioassessment tools crucial to detecting and diagnosing stream impacts in the Central Appalachian region of WV and KY.     

Comparison of precipitation chemistry measurements obtained by the Canadian Air and Precipitation Monitoring Network and National Atmospheric Deposition Program for the period 1995–2004

Precipitation chemistry and depth measurements obtained by the Canadian Air and Precipitation Monitoring Network (CAPMoN) and the US National Atmospheric Deposition Program/National Trends Network (NADP/NTN) were compared for the 10-year period 1995–2004. Colocated sets of CAPMoN and NADP instrumentation, consisting of precipitation collectors and rain gages, were operated simultaneously per standard protocols for each network at Sutton, Ontario and Frelighsburg, Ontario, Canada and at State College, PA, USA. CAPMoN samples were collected daily, and NADP samples were collected weekly, and samples were analyzed exclusively by each network’s laboratory for pH, H^?+?, Ca^2?+?, Mg^2?+?, Na^?+?, K^?+?, $\text{NH}_{4}^{+}$ , Cl^???, $\text{NO}_{3}^{-}$ , and $\text{SO}_{4}^{2-}$ . Weekly and annual precipitation-weighted mean concentrations for each network were compared. This study is a follow-up to an earlier internetwork comparison for the period 1986–1993, published by Alain Sirois, Robert Vet, and Dennis Lamb in 2000. Median weekly internetwork differences for 1995–2004 data were the same to slightly lower than for data for the previous study period (1986–1993) for all analytes except $\text{NO}_{3}^{-}$ , $\text{SO}_{4}^{2-}$ , and sample depth. A 1994 NADP sampling protocol change and a 1998 change in the types of filters used to process NADP samples reversed the previously identified negative bias in NADP data for hydrogen-ion and sodium concentrations. Statistically significant biases (α = 0.10) for sodium and hydrogen-ion concentrations observed in the 1986–1993 data were not significant for 1995–2004. Weekly CAPMoN measurements generally are higher than weekly NADP measurements due to differences in sample filtration and field instrumentation, not sample evaporation, contamination, or analytical laboratory differences.     

Furazolidone residues in chicken and swine tissues after feeding trials

Abstract

Broiler chickens and swine fed furazolidone in their diet were sacrificed, and samples of liver, kidney, skin/fat and muscle were harvested and analyzed for furazolidone residue. Chickens fed 200 g of furazolidone/ton of feed were withdrawn from treatment 21, 14, 7, 5, 3, or 0 days before slaughter. Birds withdrawn from medication more than 5 days prior to slaughter had no residues in any of the tissues sampled. One of the 12 birds in each of the 5 day and 3 day withdrawal groups had detectable residues in the skin/fat. Seven of the 12 birds in the 0 day withdrawal group had residues of <2 ppb in skin/fat samples. Chickens fed 400 g furazolidone/ton of feed were withdrawn from treatment 0 days before slaughter. Residues of 0.7 to 3.5 ppb were found in the skin of these birds; residues were not found in other tissues. Swine were fed 300 g furazolidone/ton of feed for 2 weeks or 150 g/ton for 5 weeks. They were withdrawn from treatment 10, 7, 5, 3, or 0 days before slaughter. Tissue samples taken from these swine did not contain detectable furazolidone residues.     

Development and Evaluation of a Method to Determine Indicator Microorganisms in Air Emissions and Residue from Medical Waste Incinerators

To allow testing of microbial destruction in medical waste incinerators, methods were developed to determine indicator microorganisms (Bacillus Stearothermophilus spores) in incinerator air emissions and residue. The emission trapping train consisted of a water cooled glass probe and impingers containing a neutral phosphate buffer. In field tests, spores were injected directly into the probe, and results showed that approximately 60 percent of the spores were recovered. Spores were analyzed with adequate precision using a microbial membrane filter unit. Lab experiments indicated that spores were stable in neutral pH phosphate buffer for up to 20 days, and heat shocking samples (heating to 80°C for 20 minutes) reduced spore numbers in acidic or basic buffer. Laboratory tests also showed that 60 to 70 percent of spores initially added to ash were recovered up to 22 days after addition of the spores. In addition, lab tests showed that spores can be effectively recovered from residue test pipes spiked with indicator spores.     

Pilot-Scale Evaluation of an Incinerability Ranking System for Hazardous Organic Compounds

The U.S. Environmental Protection Agency’s (EPA) hazardous waste incinerator performance standards specify a minimum destruction and removal efficiency (DRE) for principal organic hazardous constituents (POHCs) designated in the incinerator waste feed. In the past, selection of appropriate POHCs for incinerator trial burns has been based largely on their heats of combustion. Attempting to improve upon this approach, the University of Dayton Research Institute (UDRI), under contract to the EPA Risk Reduction Engineering Laboratory, has developed a thermal stability-based ranking of compound "incinerability". The subject study was conducted to evaluate the laboratory-developed ranking system in a pilot-scale incinerator.

Mixtures of POHCs, spanning the ranking scale from most- to least-difficult to destroy (Class 1 to Class 7, respectively), were prepared and combined with a clay-based sorbent matrix. These mixtures were then fed into the rotary kiln incineration system at the U.S. EPA Incineration Research Facility (IRF). In a series of five tests, the following conditions were evaluated: baseline/ typical operation; thermal failure (quenching); mixing failure (overcharging); matrix failure (low feed H/CI ratio); and a worst-case combination of the three failure modes.

Under baseline conditions, mixing failure, and matrix failure, kiln-exit DREs for each compound were comparable from test to test. Operating conditions in these 3 modes appeared to be sufficient to effect considerable destruction (greater than 99.99 percent DRE) of all compounds. As a result, separation of the highest-ranked POHCs from the lowest-ranked POHCs according to observed DRE was not possible; a correlation between POHC ranking and DRE could not be confirmed.

A correlation between predicted and observed incinerability was more evident for the thermal failure and worst-case conditions. Kiln-exit DREs for the four POHCs predicted to be most stable (those in Classes 1 and 2) ranged from 99% to 99.99% under these conditions, and were generally lower than DREs for the POHCs predicted to be more easily destroyed. Statistically significant correlations above the 99 percent and 93 percent confidence intervals were identified for the thermal-failure and worst-case tests, respectively.