Windsor, Ontario exposure assessment study: design and methods validation of personal, indoor, and outdoor air pollution monitoring

The Windsor, Ontario Exposure Assessment Study evaluated the contribution of ambient air pollutants to personal and indoor exposures of adults and asthmatic children living in Windsor, Ontario, Canada. In addition, the role of personal, indoor, and outdoor air pollution exposures upon asthmatic children's respiratory health was assessed. Several active and passive sampling methods were applied, or adapted, for personal, indoor, and outdoor residential monitoring of nitrogen dioxide, volatile organic compounds, particulate matter (PM; PM < or = 2.5 microm [PM2.5] and < or = 10 microm [PM10] in aerodynamic diameter), elemental carbon, ultrafine particles, ozone, air exchange rates, allergens in settled dust, and particulate-associated metals. Participants completed five consecutive days of monitoring during the winter and summer of 2005 and 2006. During 2006, in addition to undertaking the air pollution measurements, asthmatic children completed respiratory health measurements (including peak flow meter tests and exhaled breath condensate) and tracked respiratory symptoms in a diary. Extensive quality assurance and quality control steps were implemented, including the collocation of instruments at the National Air Pollution Surveillance site operated by Environment Canada and at the Michigan Department of Environmental Quality site in Allen Park, Detroit, MI. During field sampling, duplicate and blank samples were also completed and these data are reported. In total, 50 adults and 51 asthmatic children were recruited to participate, resulting in 922 participant days of data. When comparing the methods used in the study with standard reference methods, field blanks were low and bias was acceptable, with most methods being within 20% of reference methods. Duplicates were typically within less than 10% of each other, indicating that study results can be used with confidence. This paper covers study design, recruitment, methodology, time activity diary, surveys, and quality assurance and control results for the different methods used.     

Evaluation of wetland methyl mercury export as a function of experimental manipulations

Mercury associated with natural enrichment, historic mining, and ore processing is a contaminant of concern in watersheds of the western USA. In this region, water is a highly managed resource and wetlands, known to be important sites of methyl mercury production, are often an integral component of watersheds. This study applied controlled manipulations of four replicated experimental wetland designs with different water and soil mercury concentrations to determine the potential impacts on methyl mercury export. Wetlands were manipulated by drying and wetting, changing hydraulic retention time, and adding sulfate and nitrate to influent waters. In a summer drying and wetting manipulation, an immediate increase in total methyl mercury release was observed with rewetting, however, concentrations decreased quickly. Drying all wetlands over the winter and rewetting in the spring resulted in high net methyl mercury output relative to that observed before drying. Net methyl mercury output was not influenced by changes in hydraulic retention time from 4 to 8 h or to 30 min, or by increasing the nitrate concentration from 0.1 to 10 mg L(-1). The addition of sulfate to the inlet waters of two mesocosms to increase concentrations from approximately 100 to 250 mg L(-1) did not result in a clear effect on methyl mercury output, most likely due to sulfate concentrations being higher than optimal for methyl mercury production. Despite the lack of response to sulfate amendments, the change in sulfate concentration between the inlet and outlet of the mesocosms and temperature were the parameters best correlated with methyl mercury outputs.     

Designing reverse-flow packed bed reactors for stable treatment of volatile organic compounds

Reverse-flow packed bed reactors can be used to treat gaseous pollutants from chemical plants. This article describes the design and operation of a modified reverse-flow reactor (MRFR) which has a recuperator on each end of the reactor and a reaction zone in the middle. The recuperators have low thermal dispersion and the reaction zone has a high thermal dispersion, obtained by placing metal inserts into the bed, parallel with the gas flow. Performance of the MRFR during extended lean and rich conditions is determined with analytical analysis and compares well with numerical simulations of CO oxidation; however, the theory is expected to be useful for any reaction kinetics. A major advantage of this MRFR design is an extended time for the reactor to extinguish during lean conditions. This work also describes MRFR performance with internal reactor cooling, which can be used as a control mechanism to maintain reactor temperature for proper removal of volatile organic compounds.     

Riparian vegetation dynamics and evapotranspiration in the riparian corridor in the delta of the Colorado River, Mexico

Like other great desert rivers, the Colorado River in the United States and Mexico is highly regulated to provide water for human use. No water is officially allotted to support the natural ecosystems in the delta of the river in Mexico. However, precipitation is inherently variable in this watershed, and from 1981-2004, 15% of the mean annual flow of the Lower Colorado River has entered the riparian corridor below the last diversion point for water in Mexico. These flows include flood releases from US dams and much smaller administrative spills released back to the river from irrigators in the US and Mexico. These flows have germinated new cohorts of native cottonwood and willow trees and have established an active aquatic ecosystem in the riparian corridor in Mexico. We used ground and remote-sensing methods to determine the composition and fractional cover of the vegetation in the riparian corridor, its annual water consumption, and the sources of water that support the ecosystem. The study covered the period 2000-2004, a flood year followed by 4 dry years. The riparian corridor occupies 30,000ha between flood control levees in Mexico. Annual evapotranspiration (ET), estimated by Moderate Resolution Imaging Spectrometer (MODIS) satellite imagery calibrated against moisture flux tower data, was about 1.1myr(-1) and was fairly constant throughout the study period despite a paucity of surface flows 2001-2004. Total ET averaged 3.4x10(8)m(3)yr(-1), about 15% of Colorado River water entering Mexico from the US Surface flows could have played only a small part in supporting these high ET losses. We conclude that the riparian ET is supported mainly by the shallow regional aquifer, derived from agricultural return flows, that approaches the surface in the riparian zone. Nevertheless, surface flows are important in germinating cohorts of native trees, in washing salts from the soil and aquifer, and in providing aquatic habitat, thereby enriching the habitat value of the riparian corridor for birds and other wildlife. Conservation and water management strategies to enhance the delta habitats are discussed in light of the findings.     

Modeling Nitrate-Nitrogen Load Reduction Strategies for the Des Moines River,Iowa Using SWAT

The Des Moines River that drains a watershed of 16,175 km² in portions of Iowa and Minnesota is impaired for nitrate-nitrogen (nitrate) due to concentrations that exceed regulatory limits for public water supplies. The Soil Water Assessment Tool (SWAT) model was used to model streamflow and nitrate loads and evaluate a suite of basin-wide changes and targeting configurations to potentially reduce nitrate loads in the river. The SWAT model comprised 173 subbasins and 2,516 hydrologic response units and included point and nonpoint nitrogen sources. The model was calibrated for an 11-year period and three basin-wide and four targeting strategies were evaluated. Results indicated that nonpoint sources accounted for 95% of the total nitrate export. Reduction in fertilizer applications from 170 to 50 kg/ha achieved the 38% reduction in nitrate loads, exceeding the 34% reduction required. In terms of targeting, the most efficient load reductions occurred when fertilizer applications were reduced in subbasins nearest the watershed outlet. The greatest load reduction for the area of land treated was associated with reducing loads from 55 subbasins with the highest nitrate loads, achieving a 14% reduction in nitrate loads achieved by reducing applications on 30% of the land area. SWAT model results provide much needed guidance on how to begin implementing load reduction strategies most efficiently in the Des Moines River watershed.     

Characterizing long-term hydrologic-response and sediment-transport for the R-5 catchment

Recently there have been several calls to establish long-term data collection networks to monitor near-surface hydrologic response and landscape evolution. The focus of this paper is a long-term dataset from the International Hydrologic Decade (1965-1974). The small upland catchment, known as R-5, located near Chickasha, Olahoma, has been the subject of considerable attention within the event-based hydrologic modeling community for more than 30 yr. Here, for the first time, 8 yr of continuous near-surface hydrologic-response and sediment-transport data are analyzed to show trends in the catchment's long-term behavior. The datasets include precipitation, temperature, solar radiation, soil-water content, infiltration, water discharge, and sediment discharge. Potential and actual evapotranspiration rates were estimated and used to calculate an average annual water balance for the catchment. Findings include, for example, that rainfall intensity rarely exceeds the threshold for Horton-type runoff, soil-water content is both spatially and temporally variable, and the water and sediment discharge rates are positively correlated. The R-5 data provide a unique opportunity to test (and refine) process-based models of continuous hydrologic response and sediment transport at the catchment scale for applications in the emerging fields of hydroecology and hydrogeomorphology.     

Phosphorus and nitrogen sorption to soils in the presence of poultry litter-derived dissolved organic matter

Two environmental aspects associated with land application of poultry litter that have not been comprehensively evaluated are (i) the competition of dissolved organic matter (DOM) and P for soil sorption sites, and (ii) the sorption of dissolved organic nitrogen (DON) relative to inorganic nitrogen species (e.g., NO(3)(-) and NH(4)(+)) and dissolved organic carbon (DOC). The competition between DOM and P for sorption sites has often been assumed to increase the amount of P available for plant growth; however, elevating DOM concentrations may also increase P available for transport to water resources. Batch sorption experiments were conducted to (i) evaluate soil properties governing P sorption to benchmark soils of Southwestern Missouri, (ii) elucidate the impact of poultry litter-derived DOM on P sorption, and (iii) investigate DON retention relative to inorganic N species and DOC. Soils were reacted for 24 h with inorganic P (0-60 mg L(-1)) in the presence and absence of DOM (145 mg C L(-1)) using a background electrolyte solution comparable to DOM extracts (I = 10.8 mmol L(-1); pH 7.7). Soil P sorption was positively correlated with metal oxide (r(2) = 0.70) and clay content (r(2) = 0.79) and negatively correlated with Bray-1 extractable P (r(2) = 0.79). Poultry litter-derived DOM had no significant negative impact on P sorption. Dissolved organic nitrogen was preferentially removed from solution relative to (NO(3)(-)-N + NO(2)(-)-N), NH(4)(+)-N, and DOC. This research indicates that poultry litter-derived DOM is not likely to enhance inorganic P transport which contradicts the assumption that DOM released from organic wastes increases plant-available P when organic amendments and fertilizer P are co-applied. Additionally, this work demonstrates the need to further evaluate the fate and transport of DON in agroecosystem soils receiving poultry litter applications.     

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.     

Degradation and metabolite formation of 17beta-estradiol-3-sulphate in New Zealand pasture soils

Estrogens-sulphates such as 17beta-estradiol-3-sulphate and estrone-3-sulphate are excreted by livestock in the urine. These conjugates are precursors to the free counterparts 17beta-estradiol and estrone, which are endocrine disrupting chemicals. In this study microcosm laboratory experiments were conducted in three pasture soils from New Zealand to study the aerobic degradation and metabolite formation kinetics of 17beta-estradiol-3-sulphate at three different incubation temperatures. The degradation of 17beta-estradiol-3-sulphate followed a first-order kinetic and the temperature dependence of the rate constants was sufficiently described by the Arrhenius equation. Degradation was different between the three investigated soils and the rate constants across the soils were significantly correlated to the arylsulphatase activity at 7.5 and 15 degrees C. Estrone-3-sulphate and 17beta-estradiol were identified as primary metabolites and estrone as a secondary metabolite. Results suggest arylsulphatase activity originating from soil microbial biomass is the main driver for the degradation of 17beta-estradiol-3-sulphate.