Composition and yields of secondary organic aerosol formed from OH radical-initiated reactions of linear alkenes in the presence of NOx: Modeling and measurements

The products and mechanism of secondary organic aerosol (SOA) formation from the OH radical-initiated reactions of linear alkenes in the presence of NO_x were investigated in an environmental chamber. The SOA consisted primarily of products formed through reactions initiated by OH radical addition to the CC double bond, including β-hydroxynitrates and dihydroxynitrates, as well as cyclic hemiacetals, dihydrofurans, and dimers formed from particle-phase reactions of dihydroxycarbonyls. 1,4-Hydroxynitrates formed through reactions initiated by H-atom abstraction also appeared to contribute. Product yields and OH radical and alkoxy radical rate constants taken from the literature or calculated using structure–reactivity methods were used to develop a quantitative chemical mechanism for these reactions. SOA yields were then calculated using this mechanism with gas-particle partitioning theory and estimated product vapor pressures for comparison with measured values. Calculated and measured SOA yields agreed very well at high carbon numbers when semi-volatile products were primarily in the particle phase, but diverged with decreasing carbon number to a degree that depended on the model treatment of dihydroxycarbonyls, which appeared to undergo reversible reactions in the particle phase. The results indicate that the chemical mechanism developed here provides an accurate representation of the gas-phase chemistry, but the utility of the SOA model depends on the partitioning regime. The results also demonstrate some of the advantages of studying simple aerosol-forming reactions in which the majority of products can be identified and quantified, in this case leading to insights into both gas- and particle-phase chemistry.     

A comparison of fine particle and aerosol strong acidity at the interface zone (1540 m) and within (452 m) the planetary boundary layer of the Great Gulf and Presidential-Dry River Class I Wildernesses on the Presidential Range,New Hampshire USA

Mount Washington, NH in the White Mountain National Forest, is flanked to the north-northeast and south by two Class I Wilderness areas, the Great Gulf and Presidential Range-Dry River Wildernesses, respectively. The Clean Air Act protects Class I Area natural resource values from air pollution. Aerosol sulfate, a fine particulate component that is often transported long distances, is a known contributor to visibility degradation and acidic deposition. We examined summertime fine particulate aerosol mass and sulfate, strong acidity and ammonium concentrations from 1988 to 2007 on Mount Washington at two elevations, 452 and 1540 m (msl). The former site is often within, and the latter at the interface of, the planetary boundary layer. Comparisons of sampling interval durations (10 and 24 h) and site vs. site are made. We also examine the extent to which aerosol sulfate is neutralized.Ten hour (daytime) compared to 24 h samples have higher mass and aerosol sulfate concentrations, however paired samples are well correlated. Fine mass concentrations compared between the 452 m and 1540 m sites (standard temperature and pressure corrected) show a weak positive linear relationship with the later being approximately 32% lower. We attribute the lack of a strong correlation to the facts that the 1540 m site is commonly at the interface of and even above the regional planetary boundary layer in summer and that it can intercept different air masses relative to the 452 m site. Sulfate is ～18% lower at the higher elevation site, but comprises a greater percentage of total fine mass; 42% compared to 37% for the high and low elevation site, respectively. Aerosol strong acidity was found to increase with increasing sulfate concentrations at both sites. Further the ratio of hydrogen to sulfate ion was greater in 24 h than 10 h samples at the higher elevation site likely due to overnight transport of fresh acidic aerosols.     

Searching for evidence of acid-catalyzed enhancement of secondary organic aerosol formation using ambient aerosol data

Laboratory experiments suggest that strong acids promote formation of enhanced levels of secondary organic aerosol (SOA), and organic aerosols may contribute to the health impacts of fine PM. We report results from examining hourly speciated fine particle data for evidence of ambient aerosol acidity-catalyzed SOA formation, as indicated by larger increases in the concentrations of organic aerosol mass occurring on days and in locations where more acidic aerosol (lower NH₄⁺/SO₄⁼ molar ratios) exists. Data sets from the southeastern U.S. were examined for which hourly acidity of PM_2.5 aerosols could be estimated, and for which hourly organic carbon (OC) content had been measured simultaneously. Within-day organic aerosol changes during selected periods were statistically related to concurrent aerosol acidity levels estimated from nitrate-corrected ammonium-to-sulfate ratios. Data from the Look Rock, TN, TVA/IMPROVE site for mid-July to mid-August 2004 showed average compositions frequently as acidic as NH₄HSO₄, however, no apparent increases in OC levels with increasing aerosol acidity were observed, even when [OC] changes were compared with time-delayed aerosol acidity estimates. SEARCH network data (2003–2004) for rural Centreville, AL (CTR) and Yorkville, GA (YRK) sites were also examined. Warm-season acidity levels were higher at CTR than at YRK, and daytime levels exceeded those at night at both sites. At the YRK site no consistent positive correlations were found between changes in OC or TC levels and aerosol acidity, even with time lags up to 6 h. Aerosol acidity at this site, however, is relatively low due to nearby agricultural sources of NH₃. In contrast, during selected periods from April to October 2004, at CTR, 6-h lagged OC changes were weakly correlated with daytime, nitrate-corrected NH₄⁺/SO₄⁼ molar ratios, but distinguishing this apparent relationship from meteorological effects on measured OC levels is challenging.     

Rights and Conflicts in the Management of Fisheries in the Lower Songkhram River Basin,Northeast Thailand

A complex, pre-existing local property rights system, characterized by overlap and conflict, comprises the local basis for managing inland fisheries in communities of the Lower Songkhram River Basin (LSRB) of Northeastern Thailand. The components, conflicts and changes of the system are analyzed for fourteen communities, focusing on the auction system for barrages, an illegal and destructive, yet tolerated, fishery. These rights, adapted to gear type, seasonality, and habitat of the LSRB fisheries, are a critical social resource and proven management system that should be legitimized. Recommendations are made for both improving general inland fisheries policy and reforming the barrage fishery.     

Flood Effects on an Alaskan Stream Restoration Project: The Value of Long‐Term Monitoring1

Densmore, Roseann V. and Kenneth F. Karle, 2009. Flood Effects on an Alaskan Stream Restoration Project: The Value of Long‐Term Monitoring. Journal of the American Water Resources Association (JAWRA) 45(6):1424‐1433. Abstract: On a nationwide basis, few stream restoration projects have long‐term programs in place to monitor the effects of floods on channel and floodplain configuration and floodplain vegetation, but long‐term and event‐based monitoring is required to measure the effects of these stochastic events and to use the knowledge for adaptive management and the design of future projects. This paper describes a long‐term monitoring effort (15 years) on a stream restoration project in Glen Creek in Denali National Park and Preserve in Alaska. The stream channel and floodplain of Glen Creek had been severely degraded over a period of 80 years by placer mining for gold, which left many reaches with unstable and incised streambeds without functioning vegetated floodplains. The objectives of the original project, initiated in 1991, were to develop and test methods for the hydraulic design of channel and floodplain morphology and for floodplain stabilization and riparian habitat recovery, and to conduct research and monitoring to provide information for future projects in similar degraded watersheds. Monitoring methods included surveyed stream cross‐sections, vegetation plots, and aerial, ground, and satellite photos. In this paper we address the immediate and outlying effects of a 25‐year flood on the stream and floodplain geometry and riparian vegetation. The long‐term monitoring revealed that significant channel widening occurred following the flood, likely caused by excessive upstream sediment loading and the fairly slow development of floodplain vegetation in this climate. Our results illustrated design flaws, particularly in regard to identification and analysis of sediment sources and the dominant processes of channel adjustment.     

Phase partitioning modeling of ethanol, isopropanol, and methanol with BTEX compounds in water

This study investigates the equilibrium phase partitioning behavior of ethanol, isopropanol, and methanol in a two-phase liquid-liquid system consisting of water and an individual BTEX (Benzene, Toluene, Ethylbenzene, and Xylenes) compound. A previously developed computer program is enhanced to generate ternary phase diagrams for analysis of each three-component cosolvent-nonaqueous phase liquid (NAPL)-water mixture combination. The required activity coefficients are estimated using the UNIFAC (Universal Quasichemical Functional group Activity Coefficient) model. The UNIFAC-derived ternary phase diagrams generally show good agreement against published experimental data, and similar phase partitioning behavior is observed for every BTEX compound in the presence of the same cosolvent. Furthermore, a set of laboratory experiments is conducted to determine the maximum single-phase water content for every mixture combination considered in this study where the volume composition of the cosolvent and the NAPL components is a blend of 85% alcohol and 15% BTEX compound. Comparison of experimentally-derived maximum single-phase water contents against UNIFAC-derived results shows good agreement for mixtures containing ethanol and methanol, but relatively poor agreement for mixtures containing isopropanol.     

Polycyclic aromatic hydrocarbons and their hydroxylated metabolites in fish bile and sediments from coastal waters of Colombia

Sediments and fish bile collected from the Atlantic coastal waters of Colombia were analyzed for 16 parent polycyclic aromatic hydrocarbons (PAHs), and 23 hydroxylated PAHs (OH-PAHs), respectively. Sediments contained overall mean SigmaPAH concentrations of 2090, 234 and 170 ng/g, dry wt, for Cartagena Bay, Caimanera Marsh, and Totumo Marsh, respectively. The mean concentration of the summed OH-PAHs in fish bile was 1250, 180 and 64.1 ng/g bile wt for Cartagena Bay, Caimanera Marsh, and Totumo Marsh, respectively. The results suggest that Cartagena Bay is heavily polluted by PAHs, and that exposure to high concentrations of PAHs together with other factors could contribute to the decreased health of fish living in this ecosystem. This is one of the first studies to describe the analysis of 23 individual OH-PAHs in fish bile, using authentic standards.     

Estimating the number of active and successful bald eagle nests:an application of the dual frame method

Monitoring the number of animals in a wildlife population is an important task. In this paper, we estimate the number of active and successful bald eagle nests in a specific region using dual frame sampling techniques. The dual frame method combines independent samples from an incomplete list frame and an area frame that is assumed to be complete. Hartley's screening estimator is used to combine sample information from both frames. This methodology will be useful for monitoring any wildlife population where the breeding individuals have highly visible nesting territories which tend to be stable over many years.     

Rhizoremediation of pentachlorophenol by Sphingobium chlorophenolicum ATCC 39723

Sphingobium chlorophenolicum is well known as a pentachlorophenol (PCP) degrader. The objective of this study was to evaluate PCP degradation in a loamy sandy soil artificially contaminated with PCP using phytoremediation and bioaugmentation. Measurements of PCP concentrations were carried out using high performance liquid chromatography analyses (HPLC). The toxic effect of PCP on plants was studied through the monitoring of weight plant and root length. The biodegradation of PCP by S. chlorophenolicum in soil was assessed with a bioluminescence assay of Escherichia coli HB101 pUCD607. Bacterial analyses were carried out by plating on Mineral Salt Medium (MSM) for S. chlorophenolicum, MSM for PCP-degrading/tolerant organisms and Trypticase Soy Broth Agar (TSBA) for heterotrophic organisms. The introduction of S. chlorophenolicum into soil with plants showed a faster degradation when compared to the non-inoculated soil. The monitoring of the plant growth showed a protective role of S. chlorophenolicum against the toxicity of PCP. The bioassay confirmed that initial toxicity was lowered while degradation progressed. There was a significant increase of organisms tested in the roots in comparison to those in the soil. This study showed that the presence of S. chlorophenolicum enhanced the PCP degradation in a loamy soil and also it had a protective role to prevent phytotoxic effects of PCP on plant growth. The combined use of bioaugmentation and plants suggests that the rhizosphere of certain plant species may be important for facilitating microbial degradation of pesticides in soil with important implications for using vegetation to stabilize and remediate surface soils.