Probing the sensitivity of gaseous Br2 production from the oxidation of aqueous bromide-containing aerosols and atmospheric implications

This paper presents a global sensitivity and uncertainty analysis of the bromine chemistry included in the Model of Aqueous, Gaseous and Interfacial Chemistry (MAGIC) in dark and photolytic conditions. Uncertainty ranges are established for input parameters (e.g. chemical rate constants, Henry's law constants, etc.) and are used in conjunction with Latin hypercube sampling and multiple linear regression to conduct a sensitivity analysis that determines the correlation between each input parameter and model output. The contribution of each input parameter to the uncertainty in the model output is calculated by combining results of the sensitivity analysis with input parameters' uncertainty ranges. Model runs are compared using the predicted concentrations of molecular bromine since Br_2(g) has been shown in previous studies to be generated via an interface reaction between O_3(g) and Br_(surface)^? during dark conditions [Hunt et al., 2004]. Formation of molecular bromine from the reaction of ozone with deliquesced NaBr aerosol: evidence for interface chemistry. Journal of Physical Chemistry A 108, 11559–11572]. This study also examines the influence of an interface reaction between OH_(g) and Br_(surface)^? in the production of Br_2(g) under photolytic conditions where OH_(g) is present in significant concentrations. Results indicate that the interface reaction between O_3(g) and Br_(surface)^? is significant and is most responsible for the uncertainty in MAGICs ability to calculate precisely Br_2(g) under dark conditions. However, under photolytic conditions the majority of Br_2(g) is produced from a complex mechanism involving gas-phase chemistry, aqueous-phase chemistry, and mass transport.     

SOA from methylglyoxal in clouds and wet aerosols: Measurement and prediction of key products

Aqueous OH radical oxidation of methylglyoxal in clouds and wet aerosols is a potentially important global and regional source of secondary organic aerosol (SOA). We quantify organic acid products of the aqueous reaction of methylglyoxal (30–3000 μM) and OH radical (approx. 4 × 10^?12 M), model their formation in the reaction vessel and investigate how the starting concentrations of precursors and the presence of acidic sulfate (0–840 μM) affect product formation. Predicted products were observed. The predicted temporal evolution of oxalic acid, pyruvic acid and total organic carbon matched observations at cloud relevant concentrations (30 μM), validating this methylglyoxal cloud chemistry, which is currently being implemented in some atmospheric models of SOA formation. The addition of sulfuric acid at cloud relevant concentrations had little effect on oxalic acid yields. At higher concentrations (3000 μM), predictions deviate from observations. Larger carboxylic acids (≥C₄) and other high molecular weight products become increasingly important as concentration increases, suggesting that small carboxylic acids are the major products in clouds while larger carboxylic acids and oligomers are important products in wet aerosols.     

Pollution influences on atmospheric composition and chemistry at high northern latitudes: Boreal and California forest fire emissions

We analyze detailed atmospheric gas/aerosol composition data acquired during the 2008 NASA ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) airborne campaign performed at high northern latitudes in spring (ARCTAS-A) and summer (ARCTAS-B) and in California in summer (ARCTAS-CARB). Biomass burning influences were widespread throughout the ARCTAS campaign. MODIS data from 2000 to 2009 indicated that 2008 had the second largest fire counts over Siberia and a more normal Canadian boreal forest fire season. Near surface arctic air in spring contained strong anthropogenic signatures indicated by high sulfate. In both spring and summer most of the pollution plumes transported to the Arctic region were from Europe and Asia and were present in the mid to upper troposphere and contained a mix of forest fire and urban influences. The gas/aerosol composition of the high latitude troposphere was strongly perturbed at all altitudes in both spring and summer. The reactive nitrogen budget was balanced with PAN as the dominant component. Mean ozone concentrations in the high latitude troposphere were only minimally perturbed (<5 ppb), although many individual pollution plumes sampled in the mid to upper troposphere, and mixed with urban influences, contained elevated ozone (ΔO₃/ΔCO = 0.11 ± 0.09 v/v). Emission and optical characteristics of boreal and California wild fires were quantified and found to be broadly comparable. Greenhouse gas emission estimates derived from ARCTAS-CARB data for the South Coast Air Basin of California show good agreement with state inventories for CO₂ and N₂O but indicate substantially larger emissions of CH₄. Simulations by multiple models of transport and chemistry were found to be broadly consistent with observations with a tendency towards under prediction at high latitudes.     

Interactions between sewage sludge-amended soil and earthworms—comparison between <Emphasis Type="Italic">Eisenia fetida</Emphasis> and <Emphasis Type="Italic">Eisenia andrei</Emphasis> composting species

Vermicomposting is an eco-friendly technology, where earthworms are introduced in the waste, inter alia sewage sludge, to cooperate with microorganisms and enhance decomposition of organic matter. The main aims of the present study was to determine the influence of two different earthworm species, Eisenia fetida and Eisenia andrei, on the changes of selected metallic trace elements content in substratum during vermicomposting process using three different sewage sludge mainly differentiated by their metal contents. Final vermicompost has shown a slight reduction in Cd, Cu, Ni, and Pb, while the Zn concentration tends to increase. Accumulation of particular heavy metals in earthworms’ bodies was assessed. Both species revealed high tendency to accumulate Cd and Zn, but not Cu, Ni, and Pb, but E. andrei has higher capabilities to accumulate some metals. Riboflavin content, which content varies depending on metal pollution in several earthworms species, was measured supravitaly in extruded coelomocytes. Riboflavin content decreased slightly during the first 6 weeks of exposure and subsequently restored till the end of the 9-week experiment. Selected agronomic parameters have also been measured in the final product (vermicompost) to assess the influence of earthworms on substratum.     

Novel insights in Al-MCM-41 precursor as adsorbent for regulated haloacetic acids and nitrate from water

High concentration of NO ₃ ^? in groundwater has raised concern over possible contamination of drinking water supplies. In addition, the formation of haloacetic acids (HAAs) as by-products during disinfection with chlorine-based agents is still a relevant issue, since HAAs pose serious health hazard. In this work, we investigated the affinity of a precursor of Al-MCM-41 (a mesostructured hexagonal aluminosilicate containing the template surfactant) towards nitrate and HAAs, for its possible application in the removal of these pollutants from natural and drinking waters. Additionally, adsorption kinetics and isotherms were studied. The adsorbent was synthesized using cetyltrimethylammonium bromide as surfactant and characterized by physico?Cchemical techniques. Simulated drinking water was spiked with the EPA-regulated HAAs (monochloroacetic (MCAA), monobromoacetic (MBAA), dichloroacetic (DCAA), dibromoacetic (DBAA), and trichloroacetic (TCAA) acids) and placed in contact with the adsorbent. The effect of matrix composition was studied. Adsorption kinetic studies were performed testing three kinetics models. For the adsorption studies, three adsorption isotherm approaches have been tested to experimental data. The pollutant recoveries were evaluated by suppressed ion chromatography. The affinity of the adsorbent was TCAA = DBAA = DCAA > MBAA > MCAA with DCAA, DBAA, and TCAA completely removed. A removal as high as 77?% was achieved for 13?mg/L nitrate. The adsorption isotherms of NO ₃ ^? and monochloroacetic acid can be modeled by the Freundlich equation, while their adsorption kinetics follow a pseudo-second-order rate mechanism. The adsorbent exhibited high affinity towards HAAs in simulated drinking water even at relevant matrix concentrations, suggesting its potential application for water remediation technologies.     

Marine macrophytes as effective lead biosorbents

Several species of seagrass and marine macrophytes were investigated for their biosorption performance in the removal of lead from aqueous solution. The effect of pH on the equilibrium of the seagrass Cymodocea nodosa as a biosorbent also was studied. It was found that increasing pH increased lead biosorption, with a maximum uptake of approximately 140 mg/g in the range pH 3.3 to 5. Equilibrium data at different pH levels were successfully fitted to competitive equilibrium models. In addition, the seaweeds belonging to different phyla (i.e., Chlorophyta, Heterokontophyta, and Rhodophyta) were studied for the effect of their structure on equilibrium at a constant pH 5. The brown algae (Heterokontophyta) showed the highest potential for lead sorption, with a maximum uptake of 220 mg/g for C. compressa and 140 mg/g for S. lomentaria. The green algae (Chlorophyta) showed lead uptake in the range 40 to 90 mg/g, and the red algae (Rhodophyta) was least effective, with uptake in the range 10 to 40 mg/g.     

Imidacloprid movement in soils and impacts on soil microarthropods in southern Appalachian eastern hemlock stands

Imidacloprid is a systemic insecticide effective in controlling the exotic pest (hemlock woolly adelgid) in eastern hemlock () trees. Concerns over imidacloprid impacts on nontarget species have limited its application in southern Appalachian ecosystems. We quantified the movement and adsorption of imidacloprid in forest soils after soil injection in two sites at Coweeta Hydrologic Laboratory in western North Carolina. Soils differed in profile depth, total carbon and nitrogen content, and effective cation exchange capacity. We injected imidacloprid 5 cm into mineral soil, 1.5 m from infested trees, using a Kioritz soil injector. We tracked the horizontal and vertical movement of imidacloprid by collecting soil solution and soil samples at 1 m, 2 m, and at the drip line from each tree periodically for 1 yr. Soil solution was collected 20 cm below the surface and just above the saprolite, and acetonitrile-extractable imidacloprid was determined through the profile. Soil solution and extractable imidacloprid concentrations were determined by high-performance liquid chromatography. Soil solution and extractable imidacloprid concentrations were greater in the site with greater soil organic matter. Imidacloprid moved vertically and horizontally in both sites; concentrations generally declined downward in the soil profile, but preferential flow paths allowed rapid vertical movement. Horizontal movement was limited, and imidacloprid did not move to the tree drip line. We found a negative relationship between adsorbed imidacloprid concentrations and soil microarthropod populations largely in the low-organic-matter site; however, population counts were similar to other studies at Coweeta.     

Annual Average Radon Concentrations in California Residences

A study was conducted to determine the annual average radon concentrations in California residences, to determine the approximate fraction of the California population regularly exposed to radon concentrations of 4 pCI/l or greater, and to the extent possible, to identify regions of differing risk for high radon concentrations within the state. Annual average indoor radon concentrations were measured with passive (alpha track) samplers sent by mail and deployed by home occupants, who also completed questionnaires on building and occupant characteristics. For the 310 residences surveyed, concentrations ranged from 0.10 to 16 pCI/l, with a geometric mean of whole-house (bedroom and living room) average concentrations of 0.85 pCI/l and a geometric standard deviation of 1.91. A total of 88,000 California residences (0.8 percent) were estimated to have radon concentrations exceeding 4 pCI/l. When the state was divided into six zones based on geology, significant differences in geometric mean radon concentrations were found between several of the zones. Zones with high geometric means were the Sierra Nevada mountains, the valleys east of the Sierra Nevada, the central valley (especially the southern portion), and Ventura and Santa Barbara Counties. Zones with low geometric means included most coastal counties and the portion of the state from Los Angeles and San Bernardino Counties south.     

The Use of Stable Isotopes to Differentiate Specific Source Markers for MTBE

The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the i 13 C values were observed although the samples had isotopically distinct i -D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.     

Transport of ammonium perfluorooctanoate in environmental media near a fluoropolymer manufacturing facility

In order to understand better the pathways for transport of ammonium perfluorooctanoate (APFO) from a point source, a focused investigation of environmental media (water and soil) near a fluoropolymer manufacturing facility (Site) was undertaken. Methods were developed and validated at 2 microg kg(-1) [the limit of quantitation (LOQ)] in soil, and at 50 ng l(-1) in water. Environmental media were sampled from a public water supply well field located north of the Site, across a river. The data suggest that APFO air emissions from the Site are transported to the well field, deposited onto the soil, and then migrate downward with precipitation into the underlying aquifer.