Comparison of photochemical behavior of various humic substances in water: II. Photosensitized oxygenations

The photochemical oxygenation of 2,5-dimethylfuran (DMF) in water was studied under a variety of reaction conditions employing various humic substances as photosensitizers. As predicted by theory, the reactions at low DMF concentrations were first order with respect to DMF, and the reaction rate constants were directly proportional to the average light intensity and to the concentration of humic substance. The rate of oxygenation photosensitized by the humic matter from a river was independent of hydrogen ion activity in the pH 5 to 9 range. Wavelength studies indicate that oxygenations photosensitized by humic substances are induced by ultraviolet and blue radiation. Rate constants computed for this photosensitized reaction in sunlight were in close agreement with experimental values. Calculations also show that the ratio of the sunlight rate constants to total visible solar irradiance (400 to 700 nm) is approximately constant. Therefore, it may be possible to calibrate rate constants for photosensitized reactions in terms of commonly measured units of visible light intensity such as foot candles.     

Quality-assured measurements of animal building emissions: particulate matter concentrations

Federally funded, multistate field studies were initiated in 2002 to measure emissions of particulate matter (PM) < 10 microm (PM10) and total suspended particulate (TSP), ammonia, hydrogen sulfide, carbon dioxide, methane, nonmethane hydrocarbons, and odor from swine and poultry production buildings in the United States. This paper describes the use of a continuous PM analyzer based on the tapered element oscillating microbalance (TEOM). In these studies, the TEOM was used to measure PM emissions at identical locations in paired barns. Measuring PM concentrations in swine and poultry barns, compared with measuring PM in ambient air, required more frequent maintenance of the TEOM. External screens were used to prevent rapid plugging of the insect screen in the PM10 preseparator inlet. Minute means of mass concentrations exhibited a sinusoidal pattern that followed the variation of relative humidity, indicating that mass concentration measurements were affected by water vapor condensation onto and evaporation of moisture from the TEOM filter. Filter loading increased the humidity effect, most likely because of increased water vapor adsorption capacity of added PM. In a single layer barn study, collocated TEOMs, equipped with TSP and PM10 inlets, corresponded well when placed near the inlets of exhaust fans in a layer barn. Initial data showed that average daily mean concentrations of TSP, PM10, and PM2.5 concentrations at a layer barn were 1440 +/- 182 microg/m3 (n = 2), 553 +/- 79 microg/m3 (n = 4), and 33 +/- 75 microg/m3 (n = 1), respectively. The daily mean TSP concentration (n = 1) of a swine barn sprinkled with soybean oil was 67% lower than an untreated swine barn, which had a daily mean TSP concentration of 1143 +/- 619 microg/m3. The daily mean ambient TSP concentration (n = 1) near the swine barns was 25 +/- 8 microg/m3. Concentrations of PM inside the swine barns were correlated to pig activity.     

Tourism impacts of Three Mile Island and other adverse events: Implications for Lincoln County and other rural counties bisected by radioactive wastes intended for Yucca Mountain

Whether the proposed Yucca Mountain nuclear waste repository system will adversely impact tourism in southern Nevada is an open question of particular importance to visitor-oriented rural counties bisected by planned waste transportatin corridors (highway or rail). As part of one such county's repository impact assessment program, tourism implications of Three Mile Island (TMI) and other major hazard events have beem revisited to inform ongoing county-wide socioeconomic assessments and contingency planning efforts. This paper summarizes key research implications of such research as applied to Lincoln County, Nevada. Implications for other rural counties are discussed in light of the research findings.     

Comparison of photochemical behavior of various humic substances in water: I. Sunlight induced reactions of aquatic pollutants photosensitized by humic substances

Humic substances are shown to photosensitize transformations of several types of synthethic chemicals that do not photoreact when exposed to sunlight in distilled water. In most cases, photoproducts were the same in colored natural waters and in solutions of soil-derived humic substances, including those obtained commercially. Kinetic studies in sunlight indicated that the efficiencies of the reactions photosensitized by humic substances of various origins were the same within a factor of 2.     

Chemistry of methylmercurials in aqueous solution

The kinetics of acid cleavage of dimethylmercury (DMM) was studied in aqueous solution. At 25°C and pH 5, DMM has an acidolysis half-life of about 33 years. Cleavage of dimethylmercury by mercuric species is pH-dependent and is slow at the concentrations of mercuric species in solution in the aquatic environment. Dimethylmercury and methylmercuric ion do not undergo sunlight photodegradation. The evaporative loss of dimethylmercury from water can be compared with oxygen diffusion based on the ratio of transfer constants.