Organic acids and selected nitrogen species for ABLE-3

The NASA Global Tropospheric Experiment (GTE) executed airborne science missions aboard the NASA Wallops Electra (NA429) in the North American high latitude (greater than 45 deg North) atmosphere during Jul. to Aug. 1988 and Jul. to Aug. 1990. These missions were part of GTE's Atmospheric Boundary Layer Experiment (ABLE). The 1988 mission , ABLE-3A, examined the ecosystems of Alaska as a source and/or sink for important tropospheric gases and particles, and gained new information on the chemical composition of the Arctic atmosphere during the summertime. During 1990 the second high latitude mission, ABLE-3B, focused on the Hudson Bay Lowland and Labrador regions of Canada. Both of these missions provided benchmark data sets on atmosphere biosphere exchange and atmospheric chemistry over largely uninhabited regions of North America. In support of the GTE/ABLE-3A and -3B field missions, the University of New Hampshire flew instrumentation aboard the Wallops Electra research aircraft to provide measurements of the trace gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) acid. In addition, measurements were conducted to determine the major water soluble ionic composition of the atmospheric aerosol. For ABLE-3B, groundbased measurements of the acidic trace gases were also performed from the NASA micrometerological tower situated at Schefferville, Laborador. These measurements were aimed at assessing dry deposition of acidic gases to the taiga ecosystem in the Laborador region of Canada

Measurements of nitric acid, carboxylic acids, and selected aerosol species for the NASA/GTE Pacific Mission - West (PEM-WEST)

The research investigation funded through this grant to the University of New Hampshire was performed during a major field expedition conducted by the NASA Tropospheric Chemistry Program. The NASA Global Tropospheric Experiment (GTE) executed an airborne science mission (PEM-WEST A) aboard the NASA Ames DC-8 over the Pacific Ocean during Sep./Oct. 1981. The atmosphere over the central Pacific Ocean is the only major region in the Northern Hemisphere that is relatively free from direct anthropogenic influence. Thus, this environment is ideally suited to study the natural biogeochemical cycles of carbon, nitrogen, ozone, sulfur, and aerosols without serious confounding problems related to anthropogenic emissions. Asian sources account for about 17 percent of the global budgets of nitrogen oxides (NO(x)) and sulfur dioxide (SO2). The Pacific Rim region therefore provides the opportunity to study the anthropogenic impact on natural atmospheric chemical cycles. The PEM-WEST A flights were focused on contrasting the chemistry of 'clean' air over the central Pacific with anthropogenically impacted air advected off the Asian continent. The principal objectives of PEM-WEST A were to investigate the atmospheric chemistry of ozone (O3) and its precursors, and to study important aspects of the atmospheric sulfur cycle over the western Pacific Ocean. Measurements conducted by the University of New Hampshire contributed directly to both of these objectives. Subsequent PEM-WEST field missions are planned by GTE in the mid-1990's to contrast atmospheric chemistry documented during PEM-WEST A with other time periods. This report presents preliminary findings from the PEM-WEST A field mission. Data interpretation is currently ongoing with the goal of manuscript submission of scientific results to a special issue of the Journal of Geophysical Research-Atmospheres in Feb. 1994. The reader is strongly encouraged to review this suite of profession articles to appreciate the overall scientific findings and benefits of the PEM-WEST A field mission

Wetlands: A potentially significant source of atmospheric methyl bromide and methyl chloride

Tropospheric methyl bromide (CH3Br) and methyl chloride (CH3Cl) are significant sources of ozone (O3) destroying halogens to the stratosphere. Their O3 depletion potential (ODP) can be determined from atmospheric lifetimes and therefore their atmospheric budgets, both of which are out of balance with known sink terms larger than identified sources. We have discovered a new source of CH3Br and CH3Cl emissions to the atmosphere at two wetland sites in the Northeastern United States. We have reason to believe that these compounds are biologically produced in situ. Our measurements indicate that the global annual flux of CH3Br and CH3Cl from wetlands could be as high as 4.6 Gg yr−1 Of CH3Br and 48 Gg yr−1 of CH3Cl. These are preliminary estimates based on measurements made during the end of the 1998 growing season, a time period of decreased emissions of other trace gases such as methane (CH4)

Atmospheric Mercury

Mercury is a serious environmental toxin that is distributed globally by large-scale atmospheric circulations. The chapters in this book cover measurements of speciated atmospheric mercury, regional modeling, continental-scale distributions across the U.S. and Canada, large-scale distributions in the free troposphere, and changes in wet deposition across the U.S. The diverse topics give snap-shots of current research areas in atmospheric mercury and some insight into policy issues in Europe. Together, the work demonstrates the complexity of atmospheric mercury and provides aspects on measuring and modeling it. Much work is needed in the future to unravel the chemical forms of oxidized atmospheric mercury and how it is intertwined in global cycling of mercury. The complexities of this work are extremely challenging for emerging atmospheric chemists

Deviations from ozone photostationary state during the International Consortium for Atmospheric Research on Transport and Transformation 2004 campaign: Use of measurements and photochemical modeling to assess potential causes

Nitric oxide (NO) and nitrogen dioxide (NO2) were monitored at the University of New Hampshire Atmospheric Observing Station at Thompson Farm (TF) during the ICARTT campaign of summer 2004. Simultaneous measurement of ozone (O3), temperature, and the photolysis rate of NO2 (jNO2) allow for assessment of the O3 photostationary state (Leighton ratio, Φ). Leighton ratios that are significantly greater than unity indicate that peroxy radicals (PO2), halogen monoxides, nitrate radicals, or some unidentified species convert NO to NO2 in excess of the reaction between NO and O3. Deviations from photostationary state occurred regularly at TF (1.0 ≤ Φ ≤ 5.9), particularly during times of low NOx (NOx = NO + NO2). Such deviations were not controlled by dynamics, as indicated by regressions between Φ and several meteorological parameters. Correlation with jNO2 was moderate, indicating that sunlight probably controls nonlinear processes that affect Φ values. Formation of PO2 likely is dominated by oxidation of biogenic hydrocarbons, particularly isoprene, the emission of which is driven by photosynthetically active radiation. Halogen atoms are believed to form via photolysis of halogenated methane compounds. Nitrate radicals are believed to be insignificant. Higher Φ values are associated with lower mixing ratios of isoprene and chloroiodomethane and lower ratios of NOx to total active nitrogen, indicating that photochemical aging may very well lead to increased Φ values. PO2 levels calculated using a zero‐dimensional model constrained by measurements from TF can account for 71% of the observed deviations on average. The remainder is assumed to be associated with halogen atoms, most likely iodine, with necessary mixing ratios up to 0.6 or 1.2 pptv, for chlorine and iodine, respectively

An estimate of the uptake of atmospheric methyl bromide by agricultural soils

Published estimates of removal of atmospheric methyl bromide (CH3Br) by agricultural soils are 2.7 Gg yr−1 (Gg = 109 g) [Shorter et al., 1995] and 65.8 Gg yr−1 [Serça et al., 1998]. The Serça et al. estimate, if correct, would suggest that the current value for total removal of atmospheric CH3Br by all sinks of 206 Gg yr−1 (based on Shorter et al., 1995) would be 30% too low. We have calculated a new rate of global agricultural soil uptake of atmospheric CH3Br from a larger sampling of cultivated soils collected from 40 sites located in the United States, Costa Rica, and Germany. First order reaction rates were measured during static laboratory incubations. These data were combined with uptake measurements we reported earlier based on field and laboratory experiments [Shorter et al. 1995]. Tropical (10.2°–10.4°N) and northern (45°–61°N) soils averaged lower reaction rate constants than temperate soils probably due to differing physical and chemical characteristics as well as microbial populations. Our revised global estimate for the uptake of ambient CH3Br by cultivated soils is 7.47±0.63 Gg yr−1, almost three times the value that we reported in 1995

Transport of sulfur dioxide from the Asian Pacific Rim to the North Pacific troposphere

The NASA Pacific Exploratory Mission over the Western Pacific Ocean (PEM-West B) field experiment provided an opportunity to study sulfur dioxide (SO2) in the troposphere over the western Pacific Ocean from the tropics to 60°N during February–March 1993. The large suite of chemical and physical measurements yielded a complex matrix in which to understand the distribution of sulfur dioxide over the western Pacific region. In contrast to the late summer period of Pacific Exploratory Mission-West A (PEM-West A) (1991) over this same area, SO2showed little increase with altitude, and concentrations were much lower in the free troposphere than during the PEM-West B period. Volcanic impacts on the upper troposphere were again found as a result of deep convection in the tropics. Extensive emission of SO2 from the Pacific Rim land masses were primarily observed in the lower well-mixed part of the boundary layer but also in the upper part of the boundary layer. Analyses of the SO2 data with aerosol sulfate, beryllium-7, and lead-210 indicated that SO2 contributed to half or more of the observed total oxidized sulfur (SO2 plus aerosol sulfate) in free tropospheric air. The combined data set suggests that SO2 above 8.5 km is transported from the surface but with aerosol sulfate being removed more effectively than SO2. Cloud processing and rain appeared to be responsible for lower SO2 levels between 3 and 8.5 km than above or below this region

Coastal water source of short‐lived halocarbons in New England

Short‐lived halocarbon tracers were used to investigate marine influences on air quality in a coastal region of New England. Atmospheric measurements made at the University of New Hampshire\u27s Observing Station at Thompson Farm (TF) in Durham, New Hampshire, indicate that relatively large amounts of halocarbons are emitted from local estuarine and coastal oceanic regions. Bromine‐containing halocarbons of interest in this work include bromoform (CHBr3) and dibromomethane (CH2Br2). The mean mixing ratios of CHBr3 and CH2Br2 from 11 January to 5 March 2002 were 2.6 pptv and 1.6 pptv, and from 1 June to 31 August 2002 mean mixing ratios were 5.9 pptv and 1.4 pptv, respectively. The mean mixing ratio of CHBr3 was not only highest during summer, but both CHBr3 and CH2Br2 exhibited large variability in their atmospheric mixing ratios during this season. We attribute the greater variability to increased production combined with faster atmospheric removal rates. Other seasonal characteristics of CHBr3 and CH2Br2 in the atmosphere, as well as the impact of local meteorology on their distributions at this coastal site, are discussed. Tetrachloroethene (C2Cl4) and trichloroethene (C2HCl3) were used to identify time periods influenced by urban emissions. Additionally, measurements of CHBr3, CH2Br2, C2Cl4, methyl iodide (CH3I), and ethyl iodide (C2H5I) were made at TF and five sites throughout the nearby Great Bay estuarine area between 18 and 19 August 2003. These measurements were used to elucidate the effect of the tidal cycle on the distributions of these gases. The mean mixing ratios of CHBr3, CH2Br2, CH3I, and C2H5I were ∼82%, 46%, 14%, and 17% higher, respectively, near the coast compared to inland sites, providing evidence for a marine source of short‐lived halocarbons at TF. Correlation between the tidal cycle and atmospheric concentrations of marine tracers on the night of 18 August 2003 showed that the highest values for the brominated species occurred ∼2–3 hours after high tide. Emission fluxes of CHBr3, CH2Br2, CH3I, and C2H5I on this night were estimated to be 26 ± 57, 4.7 ± 5.4, 5.9 ± 4.6, and 0.065 ± 0.20 nmol m−2 h−1, respectively. Finally, the anthropogenic source strength of CHBr3 was calculated to determine its impact on atmospheric levels observed in this region. Although our results indicate that anthropogenic contributions could potentially range from 15 to 60% of the total dissolved CHBr3 in the Great Bay, based on the observed ratio of CH2Br2/CHBr3 and surface seawater measurements in the Gulf of Maine, it appears unlikely that anthropogenic activities are a significant source of CHBr3 in the region