Evidence of degradation of polybrominated biphenyls in soil samples from michigan

Abstract

Soil samples obtained from the former polybrominated biphenyls (PBB) manufacturing site in Michigan were analyzed by gas chromatography and gas chromatography with mass spectrometric detection. The results indicate significant degradation of the PBB residue in the soil sample. The soil sample with the highest concentration of PBB has the greatest degree of degradation. Principal degradation products include 2,3’,4,4’,5‐pentabromo‐biphenyl, 2,2’,4,4’,5‐pencabromobiphenyl and two unidentified tetrabromobiphenyls.

The degradation pattern observed supports a photochemical decomposition mechanism. These degraded residues may be more toxic than the original Firemaster residues. The implications of the results are discussed.     

Evaluation of a Watershed Model for Estimating Daily Flow Using Limited Flow Measurements1

Abstract: The Soil and Water Assessment Tool (SWAT) model was evaluated for estimation of continuous daily flow based on limited flow measurements in the Upper Oyster Creek (UOC) watershed. SWAT was calibrated against limited measured flow data and then validated. The Nash‐Sutcliffe model Efficiency (NSE) and mean relative error values of daily flow estimations were 0.66 and 15% for calibration, and 0.56 and 4% for validation, respectively. Also, further evaluation of the model’s estimation of flow at multiple locations was conducted with parametric paired t‐test and nonparametric sign test at a 95% confidence level. Among the five main stem stations, four stations were statistically shown to have good agreement between predicted and measured flows. SWAT underestimated the flow of the fifth main stem station possibly because of the existence of complex flood control measures near to the station. SWAT estimated the daily flow at one tributary station well, but with relatively large errors for the other two tributaries. The spatial pattern of predicted flows matched the measured ones well. Overall, it was concluded from the graphical comparisons and statistical analyses of the model results that SWAT was capable of reproducing continuous daily flows based on limited flow data as is the case in the UOC watershed.     

Effects of repeated exposure to malathion on growth, food consumption, and locomotor performance of the western fence lizard (Sceloporus occidentalis)

Effects of repeated pollutant exposure on growth, locomotor performance, and behavior have rarely been evaluated in reptiles. We administered three doses of malathion (2.0, 20, or 100mg/kg body weight) to western fence lizards (Sceloporus occidentalis) over an 81day period. Eight and 23% mortality occurred at 20 and 100mg/kg (p=0.079) and 85% of lizards in the 100mg/kg group exhibited clinical symptoms of poisoning. Growth, food consumption, body condition index, and terrestrial locomotor performance were not significantly influenced by malathion. However, arboreal sprint velocity was significantly reduced in lizards receiving 100mg/kg. Fifty percent of lizards in the 100mg/kg group also refused to sprint in the arboreal setting (p=0.085). Based on these results, arboreal locomotor performance was the most sensitive metric of exposure we evaluated. Further study of compounds such as malathion is warranted due to highly variable application rates and exposure scenarios.     

Spatial distribution of metals within the liver acinus and their perturbation by PCB126

Animal studies show that exposure to the environmental pollutant 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) causes alterations in hepatic metals as measured in acid-digested volume-adjusted tissue. These studies lack the detail of the spatial distribution within the liver. Here we use X-ray fluorescence microscopy (XFM) to assess the spatial distribution of trace elements within liver tissue. Liver samples from male Sprague Dawley rats, treated either with vehicle or PCB126, were formalin fixed and paraffin embedded. Serial sections were prepared for traditional H&E staining or placed on silicon nitride windows for XFM. With XFM, metal gradients between the portal triad and the central vein were seen, especially with copper and iron. These gradients change with exposure to PCB126, even reverse. This is the first report of how micronutrients vary spatially within the liver and how they change in response to toxicant exposure. In addition, high concentrations of zinc clusters were discovered in the extracellular space. PCB126 treatment did not affect their presence, but did alter their elemental makeup suggesting a more general biological function. Further work is needed to properly evaluate the gradients and their alterations as well as classify the zinc clusters to determine their role in liver function and zinc homeostasis.     

Effects of Nighttime Chemistry upon the Transport of Ozone and Ozone Precursors

It has been recognized for several years that ozone in rural areas can exceed the National Ambient Air Quality Standard (NAAQS) for photochemical oxidant whirh was 0.08 ppm for one hour, not to be exceeded more than once per year. During the summer of 1973, the NAAQS was exceeded from 15 to 37% of the time at four rural monitoring sites in Maryland, Pennsylvania, Ohio, and West Virginia.¹ This is a greater violation rate than is found in many urban areas. Dimitriades and Altshuller² have enumerated four possible sources for this rural ozone: (a) transport from urban areas, (b) local photochemical generation from urban ozone precursors, (c) local photochemical generation from precursors of rural origin which may be man-made or natural, and (d) injection of stratospheric ozone into the rural area. This paper considers the chemistry pertinent to the first two of these possible sources of rural ozone, namely the long distance (overnight) transport of ozone and ozone precursors.     

Improving Baghouse Performance at the Monticello Generating Station

At the Monticello station, operated by the Texas Utilities Generating Company, lignite coal obtained locally in Titus and Hopkins Counties fuels each of the three units. Units 1 and 2 are identical 575-MW Combustion Engineering (CE) boilers, each of which discharges its effluent to a 36- compartment shake/deflate cleaned baghouse paralleled with four electrostatic precipitators (ESP). Unit 3 is a larger boiler and is followed by an ESP and a scrubber. The Unit 1 and 2 baghouses were designed to clean 80 percent of the flue gas. Since startup, these baghouses have regularly experienced flange-to-flange pressure drops in excess of 10 in. H₂O, with large opacity spikes caused by ash bleeding through the bags after compartment cleanings. Because of higher-than-expected pressure drop, the baghouses receive only about 45-50 percent of the flue gas. Analysis has shown the Monticello lignite ash significantly differs from most other coal ashes. Testing has shown that the Monticello ash is not filtered effectively by many "standard" bag materials. However, this testing indicates that there are fabrics that show promise of eliminating the ash bleedthrough with little pressure drop penalty. Testing has also shown that injection of low concentrations (10-15 ppm) of ammonia (NH₃) into the flue gas significantly decreases ash bleedthrough, so that with NH₃ injection "standard" bag materials may perform adequately. Currently, fullcompartment testing of four fabrics, with and without NH₃ injection, is under way at the Unit 1 baghouse. The research conducted at the Monticello station is reviewed in this paper and the encouraging results from the full-compartment tests are presented.     

Quality assured measurements of animal building emissions: gas concentrations

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), methane (CH4), nonmethane hydrocarbons (NMHC), particulate matter <10 microm in diameter, and total suspended particulate from swine and poultry production buildings in the United States. This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with > or =10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH3, H2S, CO2, CH4, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.