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Organic macromolecules constitute a high percentage of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean ecodynamics model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed for labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of proteins, polysaccharides and refractory heteropolycondensates. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally well within an order of magnitude. Global distributions are further estimated for both fractional coverage of bubble films at the air–water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant patterns. These results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change.

Atmospheric measurements of bromoform (CHBr3) and dibromomethane (CH2Br2) were conducted at two sites, Thompson Farm (TF) in Durham, New Hampshire (summer 2002-2004), and Appledore Island (AI), Maine (summer 2004). Elevated mixing ratios of CHBr3 were frequently observed at both sites, with maxima of 37.9 parts per trillion by volume (pptv) and 47.4 pptv for TF and AI, respectively. Average mixing ratios of CHBr3 and CH2Br2 at TF for all three summers ranged from 5.3-6.3 and 1.3-2.3 pptv, respectively. The average mixing ratios of both gases were higher at AI during 2004, consistent with AI's proximity to sources of these bromocarbons. Strong negative vertical gradients in the atmosphere corroborated local sources of these gases at the surface. At AI, CHBr3 and CH2Br2 mixing ratios increased with wind speed via sea-to-air transfer from supersaturated coastal waters. Large enhancements of CHBr3 and CH2Br2 were observed at both sites from 10 to 14 August 2004, coinciding with the passage of Tropical Storm Bonnie. During this period, fluxes of CHBr3 and CH2Br3 were 52.4 ± 21.0 and 9.1 ± 3.1 nmol m-2 h-1, respectively. The average fluxes of CHBr3 and CH2Br2 during nonevent periods were 18.9 ± 12.3 and 2.6 ± 1.9 nmol m-2 h-1, respectively. Additionally, CHBr3 and CH2Br2 were used as marine tracers in case studies to (1) evaluate the impact of tropical storms on emissions and distributions of marine-derived gases in the coastal region and (2) characterize the transport of air masses during pollution episodes in the northeastern United States. Copyright 2008 by the American Geophysical Union.

Increasing atmospheric mixing ratios Of CO2 have already lowered surface ocean pH by 0.1 units compared to preindustrial values and pH is expected to decrease an additional 0.3 units by the end of this century. Pronounced physiological changes in some phytoplankton have been observed during previous CO2 perturbation experiments. Marine microorganisms are known to consume and produce climate-relevant organic gases. Concentrations of (CH3)2S (DMS) and CH2ClI were quantified during the Third Pelagic Ecosystem CO2 Enrichment Study. Positive feedbacks were observed between control mesocosms and those simulating future CO2. Dimethyl sulfide was 26% (±10%) greater than the controls in the 2× ambient CO2 treatments, and 18% (±10%) higher in the 3xCO2 mesocosms. For CHClI the 2×CO2 treatments were 46% (±4%) greater than the controls and the 3×CO2 mesocosms were 131% (±11%) higher. These processes may help contribute to the homeostasis of the planet. Copyright 2007 by the American Geophysical Union.

We have identified terrestrial sources of methyl iodide (CH3I) and assessed their importance in its atmospheric budget using a synthesis of field observations. Measurements include those from NASA DC-8 research flights over the United States and the North Atlantic, the AIRMAP long-term ground-observing network in New England, and a field campaign at Duke Forest, North Carolina. We found an average CH3I flux of ∼2,700 ng m-2 d-1 to the atmosphere from midlatitude vegetation and soils, a value similar in magnitude to previous estimates of the oceanic source strength. The large-scale aircraft measurements of vertical profiles over the continental U.S. showed CH3I-mixing ratios comparable to and greater than those observed over the North Atlantic. Overall, midlatitude terrestrial biomes appear to contribute 33 Gg yr-1 to the CH3I global budget. Copyright 2007 by the American Geophysical Union.

Atomic chlorine and bromine monoxide concentrations ([Cl] and [BrO]) and dimethyl sulfide (DMS) sea-air fluxes are estimated from data collected during a Lagrangian flight made near Christmas Island (2°N, 157°W) during August 1996 aboard the NASA P3-B aircraft. Intensive hydrocarbon sampling began in the surface layer (SL) one-half hour after sunrise and continued until ∼1300 local solar time. Our empirical model includes in situ observations of hydroxyl [HO] and precise measurements of ethane (C2H6) mixing ratios. Ethane was ∼40 pptv higher in the buffer layer (BuL) than in the SL, thus vertical exchange tended to replace any C2H6 that was photochemically removed in the SL. In spite of this, SL C2H6 mixing ratios decreased significantly during the flight. Using only the measured [HO] and estimated vertical mixing, our mass balance equation cannot explain all of the observed SL C2H6 loss. However, when an initial [Cl] of 8.4 (±2.0) × 104 Cl cm-3, decreasing to 5.7 (±2.0) × 104 Cl cm-3 at midday, is included, the observed and estimated C2H6 values are in excellent agreement. Using our [Cl], we estimate a DMS flux a factor of 2 higher than when HO is the only oxidant considered. This flux estimate, when compared to that derived by Lenschow et al. (1999), suggests that if the differences are real, we may be missing a loss term. Best agreement occurs when an average BrO mixing ratio of 1.3 (±1.3) pptv is included in our mass balance equation. Copyright 2005 by the American Geophysical Union.

Elevated concentrations of methyl bromide (CH3Br) were observed in the Arctic atmospheric boundary layer (BL) during periods of widespread BL ozone (O3) depletion episodes (ODEs: O3 mixing ratios < 20 × 10-9 or parts per billion by volume, ppbv) particularly during major ODEs (MODES: O3 < 4 ppbv). No other organic gases measured during TOPSE (Tropospheric Ozone Production about the Spring Equinox) exhibited anti-correlations with O3 during these ODEs. Methyl bromide has both natural and anthropogenic sources and contributes ∼ half of the bromine (Br) to the stratosphere, where it can catalytically destroy O3. Several known CH3Br sources are evaluated, but the current knowledge cannot explain the observed enhancements. If the mechanism is direct gasphase photochemical production, a significant portion of the unknown CH3Br source may be found.

Airborne whole air samples collected over the western Pacific in spring, 2001 showed depletion of tetrachloroethene (C2Cl4) in every upper tropospheric (UT) air parcel that had interacted with large areas of cirrus less than three days upwind. The amount of C2Cl4 depletion showed a negative correlation with time since the interaction, consistent with the C2Cl4-depleted air parcels mixing with the ambient air as they moved downwind of the cirrus. Ethane and C2Cl4 both react relatively quickly with atomic chlorine (Cl) but ethane was not significantly depleted in these same air parcels, indicating that the C2Cl4 depletion cannot be attributed to Cl chemistry alone. Based on the minimum ethane depletion that can be detected by our measurements, a daytime upper limit of roughly 3 × 104 atom Cl cm-3 is indirectly estimated for heterogeneous chlorine activation by cirrus clouds in the UT in tropical- and mid-latitudes during spring. © 2003 by the American Geophysical Union.

Airborne measurements of formaldehyde (CH2O) were acquired employing tunable diode laser absorption spectroscopy (TDLAS) during the 2000 Tropospheric Ozone Production About the Spring Equinox (TOPSE) study. This study consisted of seven deployments spanning the time period from 4 February to 23 May 2000 and covered a wide latitudinal band from 40°N to 85°N. The median measured CH2O concentrations, with a few exceptions, did not show any clear temporal trends from February to May in each of five altitude and three latitude bins examined. Detailed measurement-model comparisons were carried out using a variety of approaches employing two different steady state models. Because recent emissions of CH2O and/or its precursors often result in model underpredictions, background conditions were identified using a number of chemical tracers. For background conditions at temperatures warmer than -45°C, the measurement-model agreement on average ranged between -13% and +5% (measurement- model/measurement), which corresponded to mean and median (measurement- model) differences of 3 ± 69 and -6 parts per trillion by volume (pptv), respectively. At very low temperatures starting at around -45°C, significant and persistent (measurement-model) differences were observed from February to early April from southern Canada to the Arctic Ocean in the 6-8 km altitude range. In such cases, measured CH2O was as much as 392 pptv higher than modeled, and the median difference was 132 pptv (83%). Low light conditions as well as cold temperatures may be important in this effect. A number of possible mechanisms involving the reaction of CH3O2 with HO2 to produce CH2O directly were investigated, but in each case the discrepancy was only minimally reduced. Other possibilities were also considered but in each case there was no compelling evidence to support any of the hypotheses. Whatever the cause, the elevated CH2O concentrations significantly impact upper tropospheric HOx levels at high latitudes (>57°N ) in the February-April time frame.

Canister sampling for the determination of atmospheric mixing ratios of nonmethane hydrocarbons (NMHCs), selected halocarbons, and methyl nitrate was conducted aboard the National Center for Atmospheric Research (NCAR) C-130 aircraft over the Pacific and Southern Oceans as part of the First Aerosol Characterization Experiment (ACE 1) during November and December 1995. A latitudinal profile, flown from 76°N to 60°S, revealed latitudinal gradients for most trace gases. NMHC and halocarbon gases with predominantly anthropogenic sources, including ethane, ethyne, and tetrachloroethene, exhibited significantly higher mixing ratios in the northern hemisphere at all altitudes. Methyl chloride exhibited its lowest mixing ratios at the highest northern hemisphere latitudes, and the distributions of methyl nitrate and methyl iodide were consistent with tropical and subtropical oceanic sources. Layers containing continental air characteristic of aged biomass burning emissions were observed above about 3 km over the remote southern Pacific and near New Zealand between approximately 19°S and 43°S. These plumes originated from the west, possibly from fires in southern Africa. The month-long intensive investigation of the clean marine southern midlatitude troposphere south of Australia revealed decreases in the mixing ratios of ethane, ethyne, propane, and tetrachloroethene, consistent with their seasonal mixing ratio cycle. By contrast, increases in the average marine boundary layer concentrations of methyl iodide, methyl nitrate, and dimethyl sulfide (DMS) were observed as the season progressed to summer conditions. These increases were most appreciable in the region south of 44°S over Southern Ocean waters characterized as subantarctic and polar, indicating a seasonal increase in oceanic productivity for these gases. Copyright 1999 by the American Geophysical Union.

During the First Aerosol Characterization Experiment (ACE 1) field campaign, 1419 whole air samples were collected over the Southern Ocean, of which approximately 700 samples were collected in the marine boundary layer (MBL), 300 samples were taken in the free troposphere (FT), and the remainder were collected in the buffer layer (BuL), the layer between the MBL and FT. Concentrations of tetrachloroethene, ethane, ethyne, and propane decayed over the 24 day duration of the intensive portion of the field campaign, which began November 18, 1995. This decline was consistent with what is known about seasonal increase of HO and the seasonal decrease in biomass burning. Using a simple empirical model, the best fit to the observations was obtained when the average [HO] was 6.1 ± 0.3 × 105 HO cm-3, and an average [Cl] of 720 ± 100 Cl cm-3. The corresponding exchange times were 14 ± 2 days between the MBL and FT, and 49 +40/-13 days between the MBL in the intensive campaign region and the MBL region to the north (nMBL). Copyright 1999 by the American Geophysical Union.

Aircraft measurements of nonmethane hydrocarbons (NMHCs) and halocarbons were made over the remote South Pacific Ocean during late August-early October 1996 for NASA's Global Tropospheric Experiment (GTE) Pacific Exploratory Mission-Tropics A (PEM-Tropics A). This paper discusses the large-scale spatial distributions of selected trace gases encountered during PEM-Tropics A. The PEM-Tropics A observations are compared to measurements made over the southwestern pacific in early November 1995 as part of Aerosol Characterization Experiment (ACE 1). Continental pollution in the form of layers containing elevated levels of O3 was observed during a majority of PEM-Tropics flights, as well as during several ACE 1 flights. The chemical composition of these air masses indicates that they were not fresh and were derived from nonurban combustion sources. The substantial impact of biomass burning on the vertical structure of the South Pacific troposphere is discussed. Copyright 1999 by the American Geophysical Union.

Although removal of tropospheric methyl bromide (CH3Br) is dominated by the reaction with the seasonally varying hydroxyl (HO) radical concentration, the anticipated corresponding seasonal dependence of CH3Br, as found for other gases with major HO sinks, has been sought previously without success [WMO, 1995]. Our observations of northern hemispheric boundary layer CH3Br concentrations do reveal substantial seasonal changes. The high latitude CH3Br North/South interhemispheric concentration ratio (IHR) varies from a maximum of 1.35±0.04 (1σ) in March-April to 1.10±0.04 in September, with an equal area and seasonally (EAS) weighted average IHR of 1.21±0.03. These observations suggest northern hemispheric emissions are about 15 kilotons/year less than when an IHR of 1.3 is considered [WMO, 1995]. The observed seasonality also partially explains the differences in the IHR reported by several research groups [WMO, 1995] and places needed constraints on the magnitude and seasonality of sources and sinks of CH3Br.

Aircraft measurements of selected nonmethane hydrocarbon and halocarbon species were made in the lower troposphere of the NE Atlantic near the Azores, Portugal, during June 1992 as part of the Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange. In this paper, the impact of continental outflow from both Europe and North America on the study region were assessed. Four main air mass types were characterized from trajectories and trace gas concentrations: clean marine from the Atlantic, and continental air from the Iberian Peninsula, the British Isles and Northern Europe, and North America. Each classification exhibited trace gas concentrations that had been modified en route by photochemical processes and mixing. Comparison with the clean marine boundary layer (MBL) shows that the boundary layer of the predominantly continental air masses were enhanced in hydrocarbons and halocarbons by factors of approximately 2 for ethane, 5 for propane, 2-6 for ethyne and benzene, and 2-3 for C2Cl4. The same air masses also exhibited large ozone enhancements, with 2 to 3 times higher mixing ratios in the continental boundary layer air compared to the clean MBL. This indicates a primarily anthropogenic photochemical source for a significant fraction of the lower tropospheric ozone in this region. Methyl bromide exhibited on average 10-20% higher concentrations in the boundary layer affected by continental outflow than in the clean MBL, and was seen to be enhanced in individual plumes of air of continental origin. This is consistent with significant anthropogenic sources for methyl bromide. In addition, median MBL concentrations of ethene and methyl iodide showed enhancements of approximately a factor of 2 above free tropospheric values, suggesting primarily coastal/oceanic sources for these species. Copyright 1996 by the American Geophysical Union.

Nonmethane hydrocarbons and halocarbons were measured during two Lagrangian experiments conducted in the lower troposphere of the North Atlantic as part of the June 1992, Atlantic Stratosphere Transition Experiment/Marine Aerosol and Gas Exchange (ASTEX/MAGE) expedition. The first experiment was performed in very clean marine air. Meteorological observations indicate that the height of the marine boundary layer rose rapidly, entraining free tropospheric air. However, the free tropospheric and marine boundary layer halocarbon concentrations were too similar to allow this entrainment to be quantified by these measurements. The second Lagrangian experiment took place along the concentration gradient of an aged continental air mass advecting from Europe. The trace gas measurements confirm that the National Center for Atmospheric Research (NCAR) Electra aircraft successfully intercepted the same air mass on consecutive days. Two layers, a surface layer and a mixed layer with chemically distinct compositions, were present within the marine boundary layer. The composition of the free troposphere was very different from that of the mixed layer, making entrainment from the free troposphere evident Concentrations of the nonmethane hydrocarbons in the Lagrangian surface layer were observed to become depleted relative to the longer-lived tetrachloroethene. A best fit to the observations was calculated using various combinations of the three parameters, loss by reaction with hydroxyl, loss by reaction with chlorine, and/or dilution from the mixed layer. These calculations provided estimated average concentrations in the surface layer for a 5-hour period from dawn to 11 UT of 0.3±0.5 ×106 molecules cm-3 for HO, and 3.3±;1.1 ×104 molecules cm-3 for Cl. Noontime concentration estimates were 2.6±0.7 ×106 molecules cm-3 for HO and 6.5±1.4 ×104 molecules cm-3 for Cl. Copyright 1996 by the American Geophysical Union.

A total of 1667 whole air samples were collected onboard the NASA DC-8 aircraft during the 6-week Pacific Exploratory Mission over the western Pacific (PEM-West A) in September and October 1991. The samples were assayed for 15 C2-C7 hydrocarbons and six halocarbons. Latitudinal (0.5°S to 59.5°N) and longitudinal (114°E to 122°W) profiles were obtained from samples collected between ground level and 12.7 km. Thirteen of the 18 missions exhibited at least one vertical profile where the hydrocarbon mixing ratios increased with altitude. Longitude-latitude color patch plots at three altitude levels and three-dimensional color latitudealtitude and longitude-altitude contour plots exhibit a significant number of middle-upper tropospheric pollution events. These and several lower tropospheric pollution plumes were characterized by comparison with urban data from Tokyo and Hong Kong, as well as with natural gas and the products from incomplete combustion. Elevated levels of nonmethane hydrocarbons (NMHC) and other trace gases in the upper-middle free troposphere were attributed to deep convection over the Asian continent and to typhoon-driven convection near the western Pacific coast of Asia. In addition, NMHCs and CH3CCI3 were found to be useful tracers with which to distinguish hydrocarbon and halocarbon augmented plumes emitted from coastal Asian cities into the northwestern Pacific.

An innovative cryogen-free concentrator system for measurement of atmospheric trace gases at the parts per trillion level has been developed with detection by routinely used gas chromatographic methods. The firstgeneration system was capable of reaching a trapping temperature of -186 [degrees]C, while the current version can reach -195 [degrees]C. A Kleemenko cooler is used to create liquid nitrogen equivalent trapping conditions and eliminate the use of solid absorbents, a potential source of artifacts. The method utilizes dual-stage trapping with individual cold regions. The two stages are cooled to -20 and -175 [degrees]C for water management and sample enrichment, respectively. Both stages house a Silonite-coated stainless steel sample loop; the second stage loop is filled with 1-mm-diameter glass beads, which provide an inert surface area for analyte concentration. In our application, the complete system employed four channels utilizing two flame ionization detectors, one electron capture detector, and a mass spectrometer. The system was automated for unattended operation and was deployed off the New England east coast on Appledore Island to measure a suite of ambient non-methane hydrocarbons, halocarbons, alkyl nitrates, and oxygenated volatile organic compounds during the International Consortium for Atmospheric Research on Transport and Transformation field campaign in summer 2004. This robust system quantified 98 ambient volatile organic compounds with precisions ranging from 0.3 to 15%.

Oceanic iron (Fe) fertilization experiments have advanced the understanding of how Fe regulates biological productivity and air-sea carbon dioxide (C[O.sub.2]) exchange. However, little is known about the production and consumption of halocarbons and other gases as a result of Fe addition. Besides metabolizing inorganic carbon, marine microorganisms produce and consume many other trace gases. Several of these gases, which individually impact global climate, stratospheric ozone concentration, or local photochemistry, have not been previously quantified during an Feenrichment experiment. We describe results for selected dissolved trace gases including methane (C[H.sub.4)], isoprene ([C.sub.5][H.sub.8]), methyl bromide (C[H.sub.3]Br), dimethyl sulfide, and oxygen ([O.sub.2]), which increased subsequent to Fe fertilization, and the associated decreases in concentrations of carbon monoxide (CO), methyl iodide (C[H.sub.3]l), and C[O.sub.2] observed during the Southern Ocean Iron Enrichment Experiments.

Oceanic iron (Fe) fertilization experiments have advanced the understanding of how Fe regulates biological productivity and air-sea carbon dioxide (CO2) exchange. However, little is known about the production and consumption of halocarbons and other gases as a result of Fe addition. Besides metabolizing inorganic carbon, marine microorganisms produce and consume many other trace gases. Several of these gases, which individually impact global climate, stratospheric ozone concentration, or local photochemistry, have not been previously quantified during an Fe-enrichment experiment. We describe results for selected dissolved trace gases including methane (CH4), isoprene (C5H8), methyl bromide (CH3Br), dimethyl sulfide, and oxygen (O2), which increased subsequent to Fe fertilization, and the associated decreases in concentrations of carbon monoxide (CO), methyl iodide (CH3I), and CO2 observed during the Southern Ocean Iron Enrichment Experiments. [ABSTRACT FROM AUTHOR]

Abstract: Hourly measurement of 56 ozone precursors was conducted by a monitoring station located in a metropolitan area in central Taiwan. After nearly a year of continuous operation at this urban site, both diurnal and seasonal cycles of nonmethane hydrocarbons (NMHCs) were clearly observed, which was caused by the interplay between source, chemical loss, and meteorology. Selected species representing three different types of major sources namely the household fuel leakage, vehicular exhaust and gasoline evaporation, as well as biogenic emissions exhibit dramatic diurnal or seasonal cycles with each displaying its own unique characteristics. Ethane and propane, largely originated from leakage of natural gas or liquefied petroleum gases (LPG), showed concentrations elevating throughout the night and early morning, but began to decrease towards noon as the nocturnal temperature inversion elevated. Because of the lower chemical reactivity and somewhat more constant emissions than other measured target compounds, their diurnal cycles were presumably the direct reflection of the mixing height over the metropolitan area. For compounds originating from vehicular plus evaporative emissions such as benzene, which accounts for most of the monitored compounds, their diurnal cycles were also largely controlled by the variation in the height of temperature inversion. Of all the 56 species monitored, isoprene, an abundant biogenic species largely released by plants, showed distinct diurnal and seasonal cycles different from the other measured NMHCs. Its concentration usually peaked at noon in summer and fall when temperature and solar radiation reached their maximum level, demonstrating the close relationship of isoprene with photosynthesis. Seasonal variation was also clearly observed for the other NMHCs quantified. With the exception of isoprene, most species show higher average concentration in winter and lower in summer with the fall values being the intermediate, which presumably is caused by both the seasonal variation in HO abundance and the height of the temperature inversion. [Copyright &y& Elsevier]