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Predicting future climate hinges on our understanding of and ability to quantify air‐sea gas transfer. The latter relies on parameterizations of the gas transfer velocity k, which represents physical mass transfer mechanisms and is usually parameterized as a nonlinear function of wind forcing. In an attempt to reduce uncertainties in k, this study explores empirical parameterizations that incorporate both wind speed and sea state dependence via wave‐wind and breaking Reynolds numbers, RH and RB. Analysis of concurrent eddy covariance gas transfer and measured wavefield statistics supplemented by wave model hindcasts shows for the first time that wave‐related Reynolds numbers collapse four open ocean data sets that have a wind speed dependence of CO₂ transfer velocity ranging from lower than quadratic to cubic. Wave‐related Reynolds number and wind speed show comparable performance for parametrizing dimethyl sulfide (DMS) which, because of its higher solubility, is less affected by bubble‐mediated exchange associated with wave breaking.

Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2 > 0.95, 10 s averages) over a wide range of sampling conditions.

A variety of physical mechanisms are jointly responsible for facilitating air-sea gas transfer through turbulent processes at the atmosphere-ocean interface. The nature and relative importance of these mechanisms evolves with increasing wind speed. Theoretical and modeling approaches are advancing, but the limited quantity of observational data at high wind speeds hinders the assessment of these efforts. The HiWinGS project successfully measured gas transfer coefficients (k660) with coincident wave statistics under conditions with hourly mean wind speeds up to 24 m s−1 and significant wave heights to 8 m. Measurements of k660 for carbon dioxide (CO2) and dimethylsulfide (DMS) show an increasing trend with respect to 10-meter neutral wind speed (U10N), following a power-law relationship of the form: math formula and math formula. Among seven high wind speed events, CO2 transfer responded to the intensity of wave breaking, which depended on both wind speed and sea state in a complex manner, with k660 co2 increasing as the wind sea approaches full development. A similar response is not observed for DMS. These results confirm the importance of breaking waves and bubble injection mechanisms in facilitating CO2 transfer. A modified version of the Coupled Ocean-Atmosphere Response Experiment Gas transfer algorithm (COAREG ver. 3.5), incorporating a sea state-dependent calculation of bubble-mediated transfer, successfully reproduces the mean trend in observed k660 with wind speed for both gases. Significant suppression of gas transfer by large waves was not observed during HiWinGS, in contrast to results from two prior field programs.

We report simultaneous, underway eddy covariance measurements of the vertical flux of isoprene, total monoterpenes, and dimethyl sulfide (DMS) over the Northern Atlantic Ocean during fall. Mean isoprene and monoterpene sea-to-air vertical fluxes were significantly lower than mean DMS fluxes. While rare, intense monoterpene sea-to-air fluxes were observed, coincident with elevated monoterpene mixing ratios. A statistically significant correlation between isoprene vertical flux and short wave radiation was not observed, suggesting that photochemical processes in the surface microlayer did not enhance isoprene emissions in this study region. Calculations of secondary organic aerosol production rates (P_(SOA)) for mean isoprene and monoterpene emission rates sampled here indicate that P_(SOA) is on average

During the Pacific Atmospheric Sulfur Experiment (PASE), dimethyl sulfide (DMS) was not the principal source of non–sea salt sulfate (NSS) mass in the remote marine boundary layer (MBL), according to an Eulerian sulfur budget based on observations of chemical concentrations from the NCAR C-130 in relatively dry, subsiding regions of the tropical Pacific. Our three (DMS, SO2, and NSS) monthly-average budgets are mutually consistent. The PASE-average DMS emission was 3.0 ± 0.5μmol m−2 d−1 (our budget “units”). SO2 sources include DMS + OH (1.4 ± 0.4 units, assuming 75% of reacted DMS forms SO2) and entrainment from the free troposphere (FT) (0.8 ± 0.2 units). Clouds were the most important chemical reactors for SO2 (−1.0 ± 0.5 units). SO2 loss terms also include divergence (−0.9 ± 0.3 units), dry deposition (−0.5 ± 0.2 units), and OH + SO2 (−0.22 ± 0.05 units). The total SO2 loss balanced the SO2 source. We assume that no SO2 was lost to ozone oxidation on sea salt particles; we found negligible NSS on particles from 2.6 μm (the sea salt mass peak) to 10 μm diameter. Fine-particle NSS sources include in-cloud oxidation of SO2 by H2O2 (1.0 ± 0.5 units), OH + SO2 (0.19 ± 0.05 units), and entrainment (1.1 ± 0.3 units in clean conditions; twice that when continental pollution is present). NSS sources balance NSS loss to divergence. Only about one fourth of emitted DMS becomes NSS. FT entrainment supplied two thirds and DMS oxidation produced one third of MBL NSS, rather similar source terms.

Aerosol variations and trends over different land and ocean regions from 1980 to 2009 are analyzed with the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model and observations from multiple satellite sensors and available ground-based networks. Excluding time periods with large volcanic influence, aerosol optical depth (AOD) and surface concentration over polluted land regions generally vary with anthropogenic emissions, but the magnitude of this association can be dampened by the presence of natural aerosols, especially dust. Over the 30-year period in this study, the largest reduction in aerosol levels occurs over Europe, where AOD has decreased by 40–60% on average and surface sulfate concentrations have declined by a factor of up to 3–4. In contrast, East Asia and South Asia show AOD increases, but the relatively high level of dust aerosols in Asia reduces the correlation between AOD and pollutant emission trends. Over major dust source regions, model analysis indicates that the change of dust emissions over the Sahara and Sahel has been predominantly driven by the change of near-surface wind speed, but over Central Asia it has been largely influenced by the change of the surface wetness. The decreasing dust trend in the North African dust outflow region of the tropical North Atlantic and the receptor sites of Barbados and Miami is closely associated with an increase of the sea surface temperature in the North Atlantic. This temperature increase may drive the decrease of the wind velocity over North Africa, which reduces the dust emission, and the increase of precipitation over the tropical North Atlantic, which enhances dust removal during transport. Despite significant trends over some major continental source regions, the model-calculated global annual average AOD shows little change over land and ocean in the past three decades, because opposite trends in different land regions cancel each other out in the global average, and changes over large open oceans are negligible. This highlights the necessity for regional-scale assessment of aerosols and their climate impacts, as global-scale average values can obscure important regional changes.

Popular summary: Atmospheric aerosols play an important role in the Earth's climate system, and can also have adverse effects on air quality and human health. The environmental impacts of aerosols, on the other hand, are highly regional, since their temporal/spatial distribution is inhomogeneous and highly depends on the regional emission sources. To better understand the effects of aerosols, intensive field experiments are necessary to characterize the chemical and physical properties on a region-by-region basis. From late February to early May in 2006, NASA/GSFC's SMARTLabs facility was deployed at a rural site in central Thailand, Southeast Asia, to conduct a field experiment dubbed BASE-ASIA (Biomass-burning Aerosols in South East-Asia: Smoke Impact Assessment). The group was joined by scientists from the University of Hawaii and other regional institutes. Comprehensive measurements were made during the experiment, including aerosol chemical composition, optical and microphysical properties, as well as surface energetics and local . meteorology. This study analyzes part of the data from the BASE-ASIA experiment. It was found that, even for the relatively remote rural site, the aerosol loading was still substantial. Besides agricultural burning in the area, industrial pollution near the Bangkok metropolitan area, about 200 km southeast of the site, and even long-range transport from China, also contribute to the area's aerosol loading. The results indicate that aerosol pollution has developed into a regional problem for northern Indochina, and may become more severe as the region's population and economy continue to grow. Abstract: Comprehensive measurements of atmospheric aerosols were made in Phimai, central Thailand (15.l83 N, 102.565 E, elevation: 206 m) during the BASE-ASIA field experiment from late February to early May in 2006. The observed aerosol loading was sizable for this rural site (mean aerosol scattering: 108 +/- 64 Mm(exp -1); absorption: 15 +/- 8 Mm(exp -1); PM(sub 10) concentration: 33 +/- 17 miro-g/ cubic m and dominated by submicron particles. Major aerosol compounds included carbonaceous (OC: 9.5 +/- 3.6miro-g/ cubic m; EC: 2.0 2.3 miro-g/ cubic m and secondary species (SO4(2-): 6.4 +/- 3.7 miro-g/ cubic m, NH4(+): 2.2 +/- 1.3 miro-g/ cubic m). While the site was seldom under the direct influence of large forest fires to its north, agricultural fires were ubiquitous during the experiment, as suggested by the substantial concentration of K+ (0.56 +/- 0.33 micro-g/ cubic m). Besides biomass burning, aerosols in Phimai during the experiment were also strongly influenced by industrial and vehicular emissions from the Bangkok metropolitan region and long-range transport from southern China. High humidity played an important role in determining the aerosol composition and properties in the region. Sulfate was primarily formed via aqueous phase reactions, and hygroscopic growth could enhance the aerosol light scattering by up to 60%, at the typical morning RH level of 85%. The aerosol single scattering albedo demonstrated distinct diurnal variation, ranging from 0.86 +/- 0.04 in the evening to 0.92 +/- 0.02 in the morning. This experiment marks the first time such comprehensive characterization of aerosols was made for rural central Thailand. Our results indicate that aerosol pollution has developed into a regional problem for northern Indochina, and may become more severe as the region's population and economy continue to grow.

In this paper, we present recent field studies conducted by NASA's SMART-COMMIT (and ACHIEVE, to be operated in 2013) mobile laboratories, jointly with distributed ground-based networks (e.g., AERONET, http://aeronet.gsfc.nasa.gov/ and MPLNET, http://mplnet.gsfc.nasa.gov/) and other contributing instruments over northern Southeast Asia. These three mobile laboratories, collectively called SMARTLabs (cf. http://smartlabs.gsfc.nasa.gov/, Surface-based Mobile Atmospheric Research & Testbed Laboratories) comprise a suite of surface remote sensing and in-situ instruments that are pivotal in providing high spectral and temporal measurements, complementing the collocated spatial observations from various Earth Observing System (EOS) satellites. A satellite-surface perspective and scientific findings, drawn from the BASE-ASIA (2006) field deployment as well as a series of ongoing 7-SEAS (2010-13) field activities over northern Southeast Asia are summarized, concerning (i) regional properties of aerosols from satellite and in situ measurements, (ii) cloud properties from remote sensing and surface observations, (iii) vertical distribution of aerosols and clouds, and (iv) regional aerosol radiative effects and impact assessment. The aerosol burden over Southeast Asia in boreal spring, attributed to biomass burning, exhibits highly consistent spatial and temporal distribution patterns, with major variability arising from changes in the magnitude of the aerosol loading mediated by processes ranging from large-scale climate factors to diurnal meteorological events. Downwind from the source regions, the tightly coupled-aerosolecloud system provides a unique, natural laboratory for further exploring the micro- and macro-scale relationships of the complex interactions. The climatic significance is presented through large-scale anti-correlations between aerosol and precipitation anomalies, showing spatial and seasonal variability, but their precise cause-and-effect relationships remain an open-ended question. To facilitate an improved understanding of the regional aerosol radiative effects, which continue to be one of the largest uncertainties in climate forcing, a joint international effort is required and anticipated to commence in springtime 2013 in northern Southeast Asia.

This report presents results from a field trial of ship-based air–sea flux measurements of carbon monoxide (CO) by direct eddy correlation with an infrared-laser trace gas analyzer. The analyzer utilizes Off-Axis Integrated-Cavity-Output Spectroscopy (OA-ICOS) to achieve high selectivity for CO, rapid response (~2 Hz) and low noise. Over a two-day sea trial, peak daytime seawater CO concentrations were ~1.5 nM and wind speeds were consistently 10–12 m s−1. A clear diel cycle in CO flux with an early afternoon maximum was observed. An analysis of flux error suggests the effects of non-stationarity are important, and air–sea CO flux measurements are best performed in regions remote from continental pollution sources.

The Pacific Atmospheric Sulfur Experiment (PASE) was a comprehensive airborne study of the chemistry and dynamics of the tropical trade wind regime (TWR) east of the island of Kiritibati (Christmas Island, 157o, 20′ W, 2o 52′ N). Christmas Island is located due south of Hawaii. Geographically it is in the northern hemisphere yet it is 6–12o south of the intertropical convergence zone (ITCZ) which places it in the southern hemisphere meteorologically. Christmas Island trade winds in August and September are from east south east at 3–15 ms−1. Clouds, if present, are fair weather cumulus located in the middle layer of the TWR which is frequently labeled the buffer layer (BuL). PASE provided clear support for the idea that small particles (80 nm) were subsiding into the tropical trade wind regime (TWR) where sulfur chemistry transformed them to larger particles. Sulfur chemistry promoted the growth of some of these particles until they were large enough to activate to cloud drops. This process, promoted by sulfur chemistry, can produce a cooling effect due to the increase in cloud droplet density and changes in cloud droplet size. These increases in particle size observed in PASE promote additional cooling due to direct scattering from the aerosol. These potential impacts on the radiation balance in the TWR are enhanced by the high solar irradiance and ocean albedo of the TWR. Finally because of the large area involved there is a large factional impact on earth’s radiation budget. The TWR region near Christmas Island appears to be similar to the TWR that persists in August and September, from southwest of the Galapagos to at least Christmas Island. Transport in the TWR between the Galapagos and Christmas involves very little precipitation which could have removed the aerosol thus explaining at least in part the high concentrations of CCN (≈300 at 0.5% supersaturation) observed in PASE. As expected the chemistry of sulfur in the trade winds was found to be initiated by the emission of DMS into the convective boundary layer (BL, the lowest of three layers). However, the efficiency with which this DMS is converted to SO2 has been brought into further question by this study. This unusual result has come about as result of our using two totally different approaches for addressing this long standing question. In the first approach, based on accepted kinetic rate constants and detailed steps for the oxidation of DMS reflecting detailed laboratory studies, a DMS to SO2 conversion efficiency of 60–73% was determined. This range of values lies well within the uncertainties of previous studies. However, using a completely different approach, involving a budget analysis, a conversion value of 100% was estimated. The latter value, to be consistent with all other sulfur studies, requires the existence of a completely independent sulfur source which would emit into the atmosphere at a source strength approximately half that measured for DMS under tropical Pacific conditions. At this time, however, there is no credible scientific observation that identifies what this source might be. Thus, the current study has opened for future scientific investigation the major question: is there yet another major tropical marine source of sulfur? Of equal importance, then, is the related question, is our global sulfur budget significantly in error due to the existence of an unknown marine source of sulfur? Pivotal to both questions may be gaining greater insight about the intermediate DMS oxidation species, DMSO, for which rather unusual measurements have been reported in previous marine sulfur studies. The 3 pptv bromine deficit observed in PASE must be lost over the lifetime of the aerosol which is a few days. This observation suggests that the primary BrO production rate is very small. However, considering the uncertainties in these observations and the possible importance of secondary production of bromine radicals through aerosol surface reactions, to completely rule out the importance of bromine chemistry under tropical conditions at this time cannot be justified. This point has been brought into focus from prior work that even at levels of 1 pptv, the effect of BrO oxidation on DMS can still be quite significant. Thus, as in the case of DMS conversion to SO2, future studies will be needed. In the latter case there will need to be a specific focus on halogen chemistry. Such studies clearly must involve specific measurements of radical species such as BrO.

Mass spectrometric measurement of DMS by atmospheric pressure ionization with an isotopically labeled standard (APIMS-ILS) is a sensitive method with sufficient bandpass for direct flux measurements by eddy correlation. Use of an isotopically labeled internal standard greatly reduces instrumental drift, improving accuracy and precision. APIMS-ILS has been used in several recent campaigns to study ocean-atmosphere gas transfer and the chemical budget of DMS in the marine boundary layer. This paper provides a comprehensive description of the method and errors associated with DMS flux measurement from ship platforms. The APIMS-ILS instrument used by most groups today has a sensitivity of 100–200 counts s−1 pptv−1, which is shown to be more than sufficient for flux measurement by eddy covariance. Mass spectral backgrounds (blanks) are determined by stripping DMS from ambient air with gold. The instrument is found to exhibit some high frequency signal loss, with a half-power frequency of ≈1 Hz, but a correction based on an empirically determined instrument response function is presented. Standard micrometeorological assumptions of steady state and horizontal uniformity are found to be appropriate for DMS flux measurement, but rapid changes in mean DMS mixing ratio may serve as a warning that measured flux does not represent the true surface flux. In addition, bias in surface flux estimates arising from the flux divergence is not generally significant in the surface layer, but under conditions of lowered inversion and high flux may become so. The effects of error in motion corrections and of vertical motion within the surface layer concentration gradient are discussed and the estimated maximum error from these effects is ≤18%.

The hydroxyl radical (OH) is an important oxidant in the troposphere due to its high reactivity and relative abundance. Measuring the concentration of OH in situ, however, is technically challenging. Here we present a simple method of estimating an OH-equivalent oxidant concentration ("effective OH") in the marine boundary layer (MBL) from the mass balance of dimethylsulfide (DMS). We use shipboard eddy covariance measurements of the sea-to-air DMS flux from the Vamos Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) in October and November of 2008. The persistent stratocumulus cloud-cover off the west coast of South America and the associated strong inversion between MBL and the free troposphere (FT) greatly simplify the dynamics in this region and make our budget estimate possible. From the observed diurnal cycle in DMS concentration, the nighttime entrainment velocity at the inversion is estimated to be 4 mm s−1. We calculate 1.4(±0.2)×106 OH molecules cm−3 from the DMS budget, which represents a monthly effective concentration and is well within the range of previous estimates. Furthermore, when linearly proportioned according to the intensity of solar flux, the resultant diel OH profile, together with DMS surface and entrainment fluxes, enables us to accurately replicate the observed diurnal cycle in DMS (correlation coefficient over 0.9). The nitrate radical (NO3) is found to have little contribution to DMS oxidation during VOCALS-REx. An upper limit estimate of 1 pptv of bromine oxide radical (BrO) would account for 30% of DMS oxidation and lower the OH concentration to 1.0)×106 OH molecules cm−3. Our effective OH estimate includes the oxidation of DMS by such radicals.

This document is a supplement to “Physical Exchanges at the Air–Sea Interface: UK–SOLAS Field Measurements,” by Ian M. Brooks, Margaret J. Yelland, Robert C. Upstill-Goddard, Philip D. Nightingale, Steve Archer, Eric d’Asaro, Rachael Beale, Cory Beatty, Byron Blomquist, A. Anthony Bloom, Barbara J. Brooks, John Cluderay, David Coles, John Dacey, Michael DeGrandpre, Jo Dixon, William M. Drennan, Joseph Gabriele, Laura Goldson, Nick Hardman-Mountford, Martin K. Hill, Matt Horn, Ping-Chang Hsueh, Barry Huebert, Gerrit de Leeuw, Timothy G. Leighton, Malcolm Liddicoat, Justin J. N. Lingard, Craig McNeil, James B. McQuaid, Ben I. Moat, Gerald Moore, Craig Neill, Sarah J. Norris, Simon O’Doherty, Robin W. Pascal, John Prytherch, Mike Rebozo, Erik Sahlee, Matt Salter, Ute Schuster, Ingunn Skjelvan, Hans Slagter, Michael H. Smith, Paul D. Smith, Meric Srokosz, John A. Stephens, Peter K. Taylor, Maciej Telszewski, Roisin Walsh, Brian Ward, David K. Woolf, Dickon Young, and Henk Zemmelink (Bull. Amer. Meteor. Soc., 90, 629–644) • ©2009 American Meteorological Society • Corresponding author: Ian M. Brooks, Institute for Climate and Atmospheric Science, School of Earth and Environment, University of Leeds, Leeds LS2 9JT, United Kingdom • E-mail: i.brooks@see.leeds.ac.uk • DOI:10.1175/2008BAMS2578.2

Black carbon, brown carbon, and mineral dust are three of the most important light absorbing aerosols. Their optical properties differ greatly and are distinctive functions of the wavelength of light. Most optical instruments that quantify light absorption, however, are unable to distinguish one type of absorbing aerosol from another. It is thus instructive to separate total absorption from these different light absorbers to gain a better understanding of the optical characteristics of each aerosol type. During the EAST-AIRE (East Asian Study of Tropospheric Aerosols: an International Regional Experiment) campaign near Beijing, we measured light scattering using a nephelometer, and light absorption using an aethalometer and a particulate soot absorption photometer. We also measured the total mass concentrations of carbonaceous (elemental and organic carbon) and inorganic particulates, as well as aerosol number and mass distributions. We were able to identify periods during the campaign that were dominated by dust, biomass burning, fresh (industrial) chimney plumes, other coal burning pollution, and relatively clean (background) air for Northern China. Each of these air masses possessed distinct intensive optical properties, including the single scatter albedo and Ångstrom exponents. Based on the wavelength-dependence and particle size distribution, we apportioned total light absorption to black carbon, brown carbon, and dust; their mass absorption efficiencies at 550 nm were estimated to be 9.5, 0.5 (a lower limit value), and 0.03 m2/g, respectively. While agreeing with the common consensus that black carbon is the most important light absorber in the mid-visible, we demonstrated that brown carbon and dust could also cause significant absorption, especially at shorter wavelengths.

Lagrangian time series of dimethylsulfide (DMS) concentrations from a cyclonic and an anticyclonic eddy in the Sargasso Sea were used in conjunction with measured DMS loss rates and a model of vertical mixing to estimate gross DMS production in the upper 60 m during summer 2004. Loss terms included biological consumption, photolysis, and ventilation to the atmosphere. The time- and depth (0–60 m)-averaged gross DMS production was estimated to be 0.73±0.09 nM d −1 in the cyclonic eddy and 0.90±0.15 nM d −1 in the anticyclonic eddy, with respective DMS replacement times of 5±1 and 6±1 d. The higher estimated rate of gross production and lower measured loss rate constants in the anticyclonic eddy were equally responsible for this eddy's 50% higher DMS inventory (0–60 m). When normalized to chlorophyll and total dimethylsulfoniopropionate (DMSP), estimated gross production in the anticyclonic eddy was about twice that in the cyclonic eddy, consistent with the greater fraction of phytoplankton that were DMSP producers in the anticyclonic eddy. Higher rates of gross production were estimated below the mixed layer, contributing to the subsurface DMS maximum found in both eddies. In both eddies, gas exchange, microbial consumption, and photolysis were roughly equal DMS loss terms in the surface mixed layer (0.2–0.4 nM d −1 ). Vertical mixing was a substantial source of DMS to the surface mixed layer in both eddies (0.2–0.3 nM d −1 ) owing to the relatively high DMS concentrations below the mixed layer. Estimated net biological DMS production rates (gross production minus microbial consumption) in the mixed layer were substantially lower (by almost a factor of 3) than those estimated in a previous study of the Sargasso Sea, which may explain the relatively low mixed-layer DMS concentrations found here during July 2004 (∼3 nM) compared to previous summers (∼4–6 nM).

ACE-Asia was a multi-national collaboration organized to investigate and understand the chemistry, radiative properties, and climatic effects of mineral dust and other aerosol particles in the East Asia/Northwest Pacific region. Studies conducted at the Gosan and Zhenbeitai surface supersites show striking variations in aerosol concentrations and properties that were affected by the occurrence and origins of the Asian dust storms, air mass pathways, and mixing during the transport. Investigations conducted on the R/V Ronald H. Brown (RHB) showed that dust had a pervasive influence on the chemical composition, size distribution, and optical properties of the aerosol. Analyses using an aerosol time-of-flight mass spectrometer on the RHB showed that most of the coarse-particle nitrate and sulfate in post-frontal air was associated with dust, and more remarkably, that competitive or exclusionary processes evidently are involved in the uptake or production of these substances. Studies conducted onboard the NCAR C-130 aircraft showed that coarse-mode dust was less absorbing and less hygroscopic than pollution aerosol and that there was little correlation in light scattering and absorption by the sub- vs. super-micrometer aerosol. Below ∼2 km, dust was commonly mixed with pollutants, and this had a stronger influence on the optical properties of the submicrometer particles than the coarse-mode dust; at higher altitudes, the dust was less affected by pollution. Single particle analyses of C-130 samples showed that the mixing of black carbon (BC) with dust was common, but only certain types of BC particles were aggregated. Models were used in the planning, execution and interpretative phases of ACE-Asia; and summaries of modeling results are presented to illustrate the progress being made in identifying new dust sources; in depicting the time-varying, three-dimensional structure of dust plumes; and in quantifying the production, transport, and deposition of Asian dust.

A low-turbulence, aerosol sampling inlet (LTI) has been developed for use on aircraft. The inlet makes use of boundary layer suction in a porous diffuser to slow the sample flow from aircraft air speeds near 150 m/s to velocities near 5 m/s without generating turbulence. The reduction of turbulence reduces losses of supermicron particles by turbulent deposition and permits the use of laminar flow calculations and well-understood drag formulations to accurately predict particle motion. Large particles are enhanced in the sample flow due to inertia. These enhancements are predicted with numerical analysis of fluid flow and integration of the equations of motion for the particles. The diffuser discussed in this article has been used in a number of field experiments, and the enhancement factors have been provided to the experimenters measuring aerosol downstream of the inlet. Some particles are doubtless lost in transport from the LTI to the aircraft fuselage. Estimates of those losses have also been made and...

In an effort to improve the accuracy of airborne aerosol studies, we compared a new porous-diffuser low-turbulence inlet (LTI) with three other inlets on the NSF/NCAR C-130, using both dust and sea salt as test aerosols. Analysis of bulk filters behind the LTI and an external reference total aerosol sampler (TAS) found no significant differences, while both the NASA shrouded solid diffuser inlet (SD) and NCAR community aerosol inlet (CAI) passed smaller amounts. However, scanning electron microscopic analyses of particles behind the LTI and TAS confirmed the model prediction that the LTI porous diffuser (PD) enhanced 7 μm particle concentrations by about 60%. Aerodynamic particle size distributions behind the other inlets began to diverge from enhancement-corrected LTI values above 2 μm, with mass concentrations of larger particles lower by as much as a factor of ten behind the CAI and a factor of 2 behind the SD. We conclude that the corrected LTI distributions were closer to ambient values than those fr...

The cycling of inorganic bromine in the marine boundary layer (mbl) has received increased attention in recent years. Bromide, a constituent of sea water, is injected into the atmosphere in association with sea-salt aerosol by breaking waves on the ocean surface. Measurements reveal that supermicrometer sea-salt aerosol is substantially depleted in bromine (often exceeding 50%) relative to conservative tracers, whereas marine submicrometer aerosol is often enriched in bromine. Model calculations, laboratory studies, and field observations strongly suggest that the supermicrometer depletions reflect the chemical transformation of particulate bromide to reactive inorganic gases that influence the processing of ozone and other important constituents of marine air. Mechanisms for the submicrometer enrichments are not well understood. Currently available techniques cannot reliably quantify many Br containing compounds at ambient concentrations and, consequently, our understanding of inorganic Br cycling over the oceans and its global significance are uncertain. To provide a more coherent framework for future research, we have reviewed measurements in marine aerosol, the gas phase, and in rain. We also summarize sources and sinks, as well as model and laboratory studies of chemical transformations. The focus is on inorganic bromine over the open oceans outside the polar regions. The generation of sea-salt aerosol at the ocean surface is the major tropospheric source producing about 6.2 Tg/a of bromide. The transport of Br from continents (as mineral aerosol, and as products from biomass-burning and fossil-fuel combustion) can be of local importance. Transport of degradation products of long-lived Br containing compounds from the stratosphere and other sources contribute lesser amounts. Available evidence suggests that, following aerosol acidification, sea-salt bromide reacts to form Br2 and BrCl that volatilize to the gas phase and photolyze in daylight to produce atomic Br and Cl. Subsequent transformations can destroy tropospheric ozone, oxidize dimethylsulfide (DMS) and hydrocarbons in the gas phase and S(IV) in aerosol solutions, and thereby potentially influence climate. The diurnal cycle of gas-phase Br and the corresponding particulate Br deficits are correlated. Higher values of Br in the gas phase during daytime are consistent with expectations based on photochemistry. We expect that the importance of inorganic Br cycling will vary in the future as a function of both increasing acidification of the atmosphere (through anthropogenic emissions) and climate changes. The latter affects bromine cycling via meteorological factors including global wind fields (and the associated production of sea-salt aerosol), temperature, and relative humidity.

The semi-volatile nature of carbonaceous aerosols complicates their collection, and for this reason special air sampling configurations must be utilized. ACE-Asia provided a unique opportunity to compare different sampling techniques for collecting carbonaceous aerosols. In this paper detailed comparisons between filter-based carbonaceous aerosol sampling methods are made. The majority of organic carbon (OC) present on a backup quartz fiber filter (QFF) in an undenuded-filter sampler resulted from the adsorption of native gaseous OC rather than OC evaporated from collected particles. The level of OC on a backup QFF placed behind a QFF was lower than the level present on a backup QFF placed behind a Teflon membrane filter (TMF) indicating that gas/filter equilibrium may not be achieved in some QFF front and backup filter pairs. Gas adsorption artifacts can result in a 20–100% overestimation of the ambient particle-phase OC concentration. The gas collection efficiency of XAD-coated and carbon-impregnated filter-lined denuders were not always 100%, but, nonetheless, such denuders minimize gas adsorption artifacts. The median fraction of particle-phase OC that is estimated to evaporate from particles collected by denuder-filter samplers ranged from 0 to 0.2; this value depends on the sampler configuration, chemical composition of the OC, and sampling conditions. After properly correcting for sampling artifacts, the measured OC concentration may differ by 10% between undenuded- and denuder-filter samplers. Uncorrected, such differences can be as large as a factor two, illustrating the importance of sampling configurations in which gas adsorption or evaporation artifacts are reduced or can be corrected.

Fog or cloud water (CW) deposition plays an important role in particle scavenging and the delivery of trace constituents to the Earth's surface. In this study, CW concentrations of total dissolvable iron (Fe) and aluminum (Al) were measured in 60 samples spanning 26 individual CW events throughout 1999 in Hawaii Volcanoes National Park on the island of Hawaii. Al concentrations ranged from 8 to 10,489 nM, with a median of 344 nM while Fe concentrations ranged from < 1 to 6419 nM with a median of 32 nM. CW deposition fluxes for Fe and Al ranged from 0.15-0.52 mmol Fe m(-2) yr(-1) and 0.62-1.35 mmol Al m(-2) yr(-1), depending on the estimation method used. The large range in concentrations is higher than expected for a relatively pristine ecosystem. It appears that this inconsistency is due to emissions from the currently active nearby volcano, Kilauea. Categorizing CW events into volcanically versus less or non-volcanically impacted events suggests that although volcanically impacted events only accounted for 12% of fog water deposition, Kilauea Volcano was responsible at least 42% of the measured CW Al deposition and 61% of the CW Fe deposition measured for 1999. (C) 2002 Elsevier Science Ltd. All rights reserved.

The mass concentrations of TSP, PM-10, several secondary aerosol species, and up to 20 elements were determined for bulk aerosol samples collected from four ground-based monitoring sites in XiAn, China. The samples were collected during four seasons from September 1996 to August 1997; and in July 1998. Daily concentrations of TSP, SO2 and NOx from 1995 to 1997 were also obtained from the same sampling sites. Representative concentrations (annual averages) of TSP, SO2 and NOx were 410, 39, 43 μg m−3, respectively. PM-10 accounted for about 60–70% of TSP in summer 1998. The most abundant elements in the samples were Si, Ca, Al, Fe, Cl, P, K and S. A fraction of the Ca, which in typically associated with dust, was from non-crustal sources, especially in coarse particles. In winter, the element with the highest concentration was S, and it was primarily in the form of sulfate. The seasonal mean sulfate concentrations, averaged over all sites, were 100, 340, 59 and 27 μg SO2−4 m−3 for autumn, winter, spring and summer, respectively. The corresponding loadings of ammonium ion were 49, 140, 40 and 17 μg NH4+ m−3 for the same seasons and those for nitrate were 22, 65, 33, 16 μg NO3− m−3. Dispersed sources of coal-combustion (most likely residential heating), as opposed to stationary point sources, evidently play an important role in the large increases in TSP and three-fold increases in sulfate, nitrate and ammonium loading during XiAn's space-heating season.

Based on both in-flight measurements and a fluid dynamics model, airflow in the National Center for Atmospheric Research (NCAR) Community Aerosol Inlet (CAI) is similar to fully developed pipe flow. Distortions of the velocity field were pronounced when suction to inlet tubes was shut off, but conditions were otherwise insensitive to all flight parameters but airspeed. The principal value of the multiuser CAI system for NCAR's C-130 is that it decelerates air with no curves until the velocity has been reduced to 10 m s−1. It then supplies uniformly modified air (after turbulent losses) to all users, enabling valid closure experiments. Chemical data from both the First Aerosol Characterization Experiment (ACE-1) and the Second Community Aerosol Inlet Evaluation Program (CAINE-II) clearly indicate that while passing efficiency for submicron aerosol is acceptable, very little of the sea salt mode mass is transmitted by the CAI to instruments inside the aircraft. Comparisons between chemical samples ...

Water-soluble organic nitrogen (ON) is an important component of fixed nitrogen in clean marine aerosol and rainwater collected at a site on the windward coast of Oahu, Hawaii. Aerosol material associated with the predominant trade winds carries 3.3 ± 2.0 nmol ON m-3, which makes up roughly one third of the total nitrogen in aerosol (11 ± 4 nmol N m-3). The inorganic nitrogen (65% as nitrate) is predominantly found in coarse-mode aerosol, consistent with displacement reactions of sea-salt chloride. In contrast, most of the ON is found in fine particle (submicrometer) aerosol, and may be associated with gas-to-particle conversions and with long-range transport in the atmosphere. At times, aerosol ON also appears to have a local, anthropogenic source, and when meteorological conditions are favorable, large pulses of ON from these local sources can dominate the total fixed nitrogen in the sampled aerosol (30-50 nmol ON m-3, contributing about 80% of the total aerosol nitrogen). About one fifth of rainwater dissolved nitrogen at this site is organic nitrogen. The average rainwater concentration of dissolved ON was 2.8 µmol N L-1, and of inorganic nitrogen (nitrate plus ammonium) was 15 µmol N L-1. In both rainwater and aerosol, urea was a major component of the ON, contributing about half of the ON and about 15% of total nitrogen. This quantitative importance of urea as a component of ON has not previously been seen in continental locations.

Organic aerosols are gaining increasing attention because of their importance in studies ofradiative forcing of climate. However, there is a potential for large and unquantified biases inmost of the published data, which has been derived using variations on the evolved gas analysismethod (EGA).We argue that the magnitude of these putative uncertainties makes it impossibleboth to test hypotheses concerning the variation of organic carbon (OC) with altitude and todevelop realistic models of radiative climate forcing.DOI: 10.1034/j.1600-0889.2000.01146.x

We present a detailed evaluation of the atmospheric sulfur cycle simulated in the Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model. The model simulations of SO2, sulfate, dimethylsulfide (DMS), and methanesulfonic acid (MSA) are compared with observations from different regions on various timescales. The model agrees within 30% with the regionally averaged sulfate concentrations measured over North America and Europe but overestimates the SO2 concentrations by more than a factor of 2 there. This suggests that either the emission rates are too high, or an additional loss of SO2 which does not lead to a significant sulfate production is needed. The average wintertime sulfate concentrations over Europe in the model are nearly a factor of 2 lower than measured values, a discrepancy which may be attributed largely to the sea-salt sulfate collected in the data. The model reproduces the sulfur distributions observed over the oceans in both long-term surface measurements and short-term aircraft campaigns. Regional budget analyses show that sulfate production from SO2 oxidation is 2 to 3 times more efficient and the lifetimes of SO2 and sulfate are nearly a factor of 2 longer over the ocean than over the land. This is due to a larger free tropospheric fraction of SO2 column over the ocean than over the land, hence less loss to the surface. The North Atlantic and northwestern Pacific regions are heavily influenced by anthropogenic activities, with more than 60% of the total SO2 originating from anthropogenic sources. The average production efficiency of SO2 from DMS oxidation is estimated at 0.87 to 0.91 in most oceanic regions.

This study reports comparisonsbetween model simulations, based on current sulfurmechanisms, with the DMS, SO2 and DMSOobservational data reported by Bandy et al.(1996) in their 1994 Christmas Island field study. For both DMS and SO2, the model results werefound to be in excellent agreement with theobservations when the observations were filtered so asto establish a common meteorological environment. Thisfiltered DMS and SO2 data encompassedapproximately half of the total sampled days. Basedon these composite profiles, it was shown thatoxidation of DMS via OH was the dominant pathway withno more than 5 to 15% proceeding through Cl atoms andless than 3% through NO3. This analysis wasbased on an estimated DMS sea-to-air flux of 3.4 ×109 molecs cm-2 s-1. The dominant sourceof BL SO2 was oxidation of DMS, the overallconversion efficiency being evaluated at 0.65 ± 0.15. The major loss of SO2 was deposition to theocean's surface and scavenging by aerosol. Theresulting combined first order k value was estimated at 1.6 × 10-5 s-1. In contrast to the DMSand SO2 simulations, the model under-predictedthe observed DMSO levels by nearly a factor of 50. Although DMSO instrument measurement problems can notbe totally ruled out, the possibility of DMSO sourcesother than gas phase oxidation of DMS must beseriously considered and should be explored in futurestudies.

A one-dimensional Lagrangian model is used to simulate vertical profiles and temporal evolution of dimethylsulfide (DMS), sulfur dioxide (SO2), aerosol methane sulfonate, and non-sea-salt sulfate (nss sulfate) that were measured during the three flights of the second First Aerosol Characterization Experiment (ACE 1) Lagrangian (Lagrangian B) experiment. Entrainment rate, mixing heights, and cloud occurrence are calculated prognostically in this type of model. The model is forced by geostrophic winds and large scale subsidence from European Centre for Medium-Range Weather Forecasts (ECMWF) analysis and sea surface temperature measured on board Research Vessel Discoverer. Gas phase oxidation and heterogeneous oxidation of SO2 to nss sulfate in clouds and sea-salt particles are considered. The evolution of dynamical variables in the column is found to be well reproduced by the model. The model captures 82% of the variance of observed DMS assuming OH is the only oxidant and a DMS flux term calculated from Liss and Merlivat [1986] parameterization and seawater DMS concentrations measured aboard R/V Discoverer. However, uncertainties in DMS oxidation rates and regional seawater concentrations are too great to identify a best fit wind speed-transfer velocity relationship. SO2 mixing ratios are correctly represented in the model (least squares correlation coefficient r2 = 75%) using a DMS to SO2 conversion efficiency of about 70%. Oxidation of SO2 in sea-salt particle appears to be a dominant process and controls SO2 lifetime during the Lagrangian B at least in the well mixed lower layer. Removing heterogeneous loss of SO2 in sea salt significantly deteriorates the simulation (r2 = 50%). Under cloudy conditions, heterogeneous loss in cloud droplets and in sea-salt particles are competitive (relative rates are 35% and 41%, respectively, during flight 26). Model-generated aerosol methane sulfonate mixing ratios agree with the observations (r2 = 62.5%) when high branching ratio for an addition oxidation pathway is used. The model estimates nss sulfate mixing ratios with little bias (median simulated-to-observed concentration ratio 1.03 and slope of the regression line 0.7) but captures only one third of the observed variance of nss sulfate. Part of the discrepancy could be due to the assumption of a decrease of nss sulfate mixing ratios with altitude in the model, whereas observations revealed high concentrations at 4500 m during the last two flights suggesting that horizontal transport could be more important than vertical mixing in this region. Nss sulfate is found to be produced photochemically under non cloudy, low wind speed conditions encountered during the first flight. During the last two flights, nss sulfate is produced mainly by oxidation in cloud droplets (48% during flight 25 and 69% during flight 26) and sea-salt particles (50% during flight 25 and 22% during flight 26).

Results are presented of measurements of the concentration of gas phase H2SO4 and methane sulfonic acid (MSA) performed aboard the NASA P3-b aircraft during the Pacific Exploratory Mission (PEM) Tropics study using the selected ion chemical ionization mass spectrometry (SICIMS) technique. During a nighttime portion of one flight the [H2SO4] was found to increase with decreasing relative humidity (RH). When compared to laboratory measurements of H2SO4 vapor pressure as a function of RH and particle neutralization (NH4+ and SO42− ionic composition) and model predictions using a liquid drop hydrate model, these measurements indicate that the particles from which the H2SO4 is evaporating are relatively unneutralized, a result which is in good agreement with filter measurements. Overall, the same increase in the gas phase [MSA] with decreasing RH or decreasing [NH4+] (obtained from filter measurements) was also observed, indicating a high volatility of MSA at low RH values or particle neutralization. When gas phase MSA values are compared to methane sulfonate (MS) values obtained from filter measurements, it was found that MSA was totally volatilized at low RH values, while MSA resides mainly in the particulate form at high RH values. Combining the gas phase and filter measurements, the boundary layer MS/(MS + SO42−) ratio showed a distinct increase with decreasing temperature and suggests that little or no MS or MSA is produced in the boundary layer at temperatures above 300 K.

As soils develop in humid environments, rock-derived elements are gradually lost, and under constant conditions it seems that ecosystems should reach a state of profound and irreversible nutrient depletion. We show here that inputs of elements from the atmosphere can sustain the productivity of Hawaiian rainforests on highly weathered soils. Cations are supplied in marine aerosols and phosphorus is deposited in dust from central Asia, which is over 6,000 km away.

Precipitation, dry deposition, and cloud water deposition of fixed nitrogen (nitrate and ammonium ions) were measured on the Island of Hawaii. The first two were small N inputs, averaging 0.6±0.2 and 0.15±0.08 kg N ha−1 yr−1 respectively. We estimate cloud water deposition to be 8–22 kg inorganic N ha−1 yr−1. If an estimate of organic N is included, it may be as high as 50 kg N ha−1 yr−1. Additionally, cloud water deposition is of hydrological significance as it comprised 37% of the total water input. Cloud water interception was certainly lower in the past, as the developing ecosystem would have had less collection surface area.

Hawaiian montane ecosystems developing on recent tephra deposits contain more fixed nitrogen than conventional sources can explain. Heath and Huebert (1999) demonstrated that cloud water interception is the mechanism by which this extra nitrogen is deposited, but could not identify its source. We show here that atmospheric dinitrogen is fixed at the surface of active lava flows, producing concentrations of NO which are higher than those found in most urban rush hour air pollution. Over a period of hours this NO is blown away from the island and oxidized to nitrate. Interruptions in the trade wind flow can return this nitrate to the island to be deposited in cloud water. Thus, fixation on active lava flows is able to provide nitrogen to developing ecosystems on flows emplaced earlier.

The southern hemisphere marine Aerosol Characterization Experiment (ACE 1) was the first of a series of experiments that will quantify the chemical and physical processes controlling the evolution and properties of the atmospheric aerosol relevant to radiative forcing and climate. The goals of this series of process studies are to reduce the overall uncertainty in the calculation of climate forcing by aerosols and to understand the multiphase atmospheric chemical system sufficiently to be able to provide a prognostic analysis of future radiative forcing and climate response. ACE 1, which was conducted from November 15 to December 14, 1995, over the southwest Pacific Ocean, south of Australia, quantified the chemical, physical, radiative, and cloud nucleating properties and furthered our understanding of the processes controlling the aerosol properties in this minimally polluted marine atmosphere. The experiment involved the efforts of scientists from 45 research institutes in 11 countries.

During Lagrangian experiment B (LB in the following) of the First Aerosol Characterization Experiment (ACE 1), a clean maritime air mass was followed over a period of 28 hours. During that time span, the vertical distribution of aerosols and their gas phase precursors were characterized by a total of nine aircraft soundings which were performed during three research flights that followed the trajectory of a set of marked tetroons. The objective of this paper is to study the time evolution of gas phase photochemistry in this Lagrangian framework. A box model approach to the wind shear driven and vertically stratified boundary layer is questionable, since its basic assumption of instantaneous turbulent mixing of the entire air column is not satisfied here. To overcome this obstacle, a one-dimensional Lagrangian boundary layer meteorological model with coupled gas phase photochemistry is used. To our knowledge, this is the first time that such a model is applied to a Lagrangian experiment and that enough measurements are available to fully constrain the simulations. A major part of this paper is devoted to the question of to what degree our model is able to reproduce the time evolution and the vertical distribution of the observed species. Comparison with observations of O3, OH, H2O2, CH3OOH, DMS, and CH3I, made on the nine Lagrangian aircraft soundings shows that this is in general the case, although the dynamical simulation started to deviate from the observations on the last Lagrangian flight. In agreement with experimental findings reported by Q. Wang et al. (unpublished manuscript, 1998b), generation of turbulence in the model appears to be most sensitive to the imposed sea surface temperature. Concerning the different modeled and observed chemical species, a number of conclusions are drawn: (1) Ozone, having a relatively long photochemical lifetime in the clean marine boundary layer, is found to be controlled by vertical transport processes, in particular synoptic-scale subsidence or ascent. (2) Starting with initally constant vertical profiles, the model is able to “create” qualitatively the vertical structure of the observed peroxides. (3) OH concentrations are in agreement with observations, both on cloudy and noncloudy days. On the first flight, a layer of dry ozone rich air topped the boundary layer. The model predicts a minimum in OH and peroxides at that altitude consistent with observations. (4) Atmospheric DMS concentrations are modeled correctly only when using the Liss and Merlivat [1986] flux parameterization, the Wanninkhof [1992] flux parameterization giving values twice those observed. To arrive at this conclusion, OH is assumed to be the major DMS oxidant, but no assumptions about mixing heights or entrainment rates are necessary in this type of model. DMS seawater concentrations are constrained by observations.

During the First Aerosol Characterization Experiment (ACE 1), we measured the concentrations of aerosol non-sea-salt sulfate (NSS), methane sulfonate (MS), ammonium, sodium, nitrate, and a variety of other anions and cations from the National Center for Atmospheric Research C-130Q aircraft and the Cape Grim Baseline Air Monitoring Station. We used the data to test a variety of hypotheses concerning the sources and properties of aerosol in remote environments. We noted a large gradient in free tropospheric (FT) MS, with much more in the spring (southern) hemisphere, but FT NSS showed no latitudinal gradient. Most species had strong vertical concentration gradients, generally with more material near the biogenic sources of the marine boundary layer (MBL) than in the FT. During the Lagrangian experiments and in time series measurements at Cape Grim, we saw daytime increases of photochemically derived MS, with more constant or decreasing concentrations at night. NSS also increased in the daytime during the Lagrangian experiments. At Cape Grim, we were unable to account for the gravimetric mass of particles on impactor substrates using the measured ions, which implies that a substantial fraction of the aerosol at that location must be either organic or mineral matter. Our FT ratios of MS/NSS exhibited a strong latitudinal gradient, with the southernmost values similar to those found in Antarctic plateau snowfall.

Cascade impactors separate aerosol particles inertially and collect them for later analysis. While laboratory calibrations typically indicate performance close to design specifications, during field operation impactors are subject to a number of sampling artifacts, including particle bounce, inlet and internal losses, and particle size changes as pressure drops within the impactor. To test the vulnerability of some commonly used impactors to these problems under Held conditions, we participated in a shipboard intercomparison off the coast of Washington state between a micro-orifice uniform deposit impactor (MOUDI), a Berner low-pressure impactor, and a Sierra high-volume slotted impactor. Since there were some inconsistencies in the results, a second intercomparison was performed at Bellows Beach, Hawaii, between two MOUDIs and the Berner impactor. Impactor samples were analyzed for soluble inorganic ions including Na+, K+, Cl−, and NO− 3, primarily from large (>1 μm) sea salt particles and NH+ 4...

Although the variation of aerosol optical properties with humidity depends critically on particle size and chemical composition, existing models usually employ empirical growth factors for water uptake. For some size ranges and many types of particles these empirical factors are not well known. We describe here a model that applies a thermodynamic analysis to arbitrary aerosol chemical size distributions to compute water uptake, refractive index, number distribution, and optical extinction. By starting with the fundamental chemistry of the aerosols the model is able to compute the derivative of extinction with sulfate, sulfate plus ammonium, and other scenarios that may be derived from global change and pollution control strategies. It can also supply information on the variation of aerosol size and extinction with humidity and with details of the aerosol size distribution. We demonstrate this model using five detailed chemical size distributions measured with a cascade impactor in the marine boundary layer. The results are in good agreement with published extinction coefficients and with nephelometer data collected in concert with one of our samples. Calculated non-sea-salt sulfate mass-scattering efficiencies of our samples ranged from 0.6 to 2.6 g m -2 for dry particles and 5.3 to 13 g m -2 at 80% relative humidity.

Aerosol variations and trends over different land and ocean regions during 1980–2009 are analyzed with the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model and observations from multiple satellite sensors and ground-based networks. Excluding time periods with large volcanic influences, the tendency of aerosol optical depth (AOD) and surface concentration over polluted land regions is consistent with the anthropogenic emission changes. The largest reduction occurs over Europe, and regions in North America and Russia also exhibit reductions. On the other hand, East Asia and South Asia show AOD increases, although relatively large amount of natural aerosols in Asia makes the total changes less directly connected to the pollutant emission trends. Over major dust source regions, model analysis indicates that the dust emissions over the Sahara and Sahel respond mainly to the near-surface wind speed, but over Central Asia they are largely influenced by ground wetness. The decreasing dust trend in the tropical North Atlantic is most closely associated with the decrease of Sahel dust emission and increase of precipitation over the tropical North Atlantic, likely driven by the sea surface temperature increase. Despite significant regional trends, the model-calculated global annual average AOD shows little changes over land and ocean in the past three decades, because opposite trends in different regions cancel each other in the global average. This highlights the need for regional-scale aerosol assessment, as the global average value conceals regional changes, and thus is not sufficient for assessing changes in aerosol loading.

We measured the concentrations of aerosol methanesulfonate (MSA) and non-sea salt sulfate (NSS) in the remote Pacific marine boundary layer (MBL) at Christmas Island (157°W, 2°N) in July and August of 1994. The project-average MSA displayed a distinct diurnal variation, decreasing to 8.6 ppt at sunrise and increasing to 12.1 ppt by sunset. The average NSS diurnal variation ranged from 196 ppt at sunrise to 235 ppt at sunset. Large-particle dry deposition may account for 10–20% of the observed nighttime decrease, with entrainment of cleaner free tropospheric air responsible for the rest. The entrainment velocity inferred from the nighttime decrease averaged 0.5±0.2 cm/s. A simple model suggests that NSS and MSA were produced at rates of about 74 and 6 ppt per day, respectively. Between 30 and 40% of the daily dimethylsulfide (DMS) flux forms NSS and 3% forms MSA.

As part of the Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange (ASTEX/MAGE), ship-based aerosol size distribution measurements have been carried out with a scanning electrical mobility spectrometer (SEMS) aboard the R/V Oceanus. The fast time resolution of these measurements illustrates some of the short-timescale variability of both the marine background aerosol and the anthropogenically influenced continental air masses. The resulting total number concentrations are largely in agreement with those from a collocated condensation nucleus counter (CNC). The aerosol size distributions provide characteristic signatures for different atmospheric conditions, showing low-concentration bimodal distributions in cleaner air masses and higher-concentration single-mode distributions in air masses with apparent recent continental influence.

The Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange (ASTEX/MAGE) was a multinational experiment designed to study the relationship between marine chemistry, aerosols, clouds, and air/sea exchange. Several aircraft, ships, and island sites supported measurements of marine boundary layer chemistry in both pristine and polluted North Atlantic air masses in the vicinity of the Azores in June of 1992. The International Global Atmospheric Chemistry (IGAC) Program's MAGE activity organized the chemical experiments in ASTEX because such experiments are beyond the capabilities of any one platform, discipline, or nation working alone. One highlight of ASTEX/MAGE was the development of a Lagrangian experimental strategy. It offered a unique way of constraining fluxes and reaction rates by observing the effect those processes have on a tagged parcel of air.

Measurements of vertical profiles and level averages of ozone over the north central Atlantic near the Azores are presented. Lagrangian experiments were carried out in clean air and polluted air, and differences between the cases are discussed. Significant vertical structure was found in the profiles from both cases. Trajectory analysis indicates that the source regions for ozone in the marine boundary layer and in the air above the inversion capping the boundary layer were different. No significant production or destruction of ozone in the boundary layer was observed in the clean case. No substantial differences in ozone concentration between cloudy and clear air were observed, although cloud processes in the polluted case may have been partially responsible for an observed overall reduction in boundary layer ozone concentration.

During the Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange (ASTEX/MAGE) program, we made repeated measurements of ammonium aerosol in a European air mass as it passed over the North Atlantic Ocean near the Azores. After tracking balloons had been launched from the R/V Oceanus, the National Center for Atmospheric Research (NCAR) Electra followed a tagged parcel of this air mass for about 42 hours in four successive flights. A different part of this air mass passed over Santa Maria Island, where we measured its aerosol size distribution with a micro-orifice uniform deposit impactor (MOUDI) impactor and used diffusion denuders to determine that virtually all available ammonia vapor had reacted with sulfuric acid to form ammonium aerosol. We have used a continuity equation to evaluate the budget of total ammonia in this air mass, and conclude that during this experiment the North Atlantic was emitting ammonia vapor. The aircraft observations show that ammonium concentrations stayed relatively constant, in spite of dilution by low-ammonia free tropospheric air. Balancing that budget requires a surface ammonia source of 26 ± 20 μmol m−2 d−1. By contrast, non-sea-salt sulfate (nss SO4=) concentrations decreased with time, causing the neutralization ratio (NH4+/nss SO4=) to increase from about 0.8 to 1.3. Ships at the beginning and end of the track recorded near-surface ratios of 0.73 and 1.65, respectively. This increasing ratio is further evidence of a substantial sea-to-air ammonia flux. Previous estimates of marine ammonia emissions have been in the range of 1.8 to 15 μmol m−2 d−1. Since our flux estimate was made at the end of the spring productivity cycle when the demand for fixed nitrogen may have been at a minimum, it may not be representative of global average ammonia fluxes. It does suggest, however, that the atmosphere may redistribute marine ammonia over hundreds or thousands of kilometers by vapor emission, conversion to aerosols, and deposition in rainfall.

We measured aerosol methanesulfonic acid (MSA), Cl−, NO3−, SO4=, Na+, and NH4+ concentrations and size distributions and gaseous ammonia and nitric acid concentrations from Santa Maria, Azores during the Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange (ASTEX/MAGE) experiment in June 1992. We also sampled some of these species in the free troposphere and marine boundary layer (MBL) from the National Center for Atmospheric Research's (NCAR's) Electra aircraft and at the surface from the R/V Oceanus. In relatively clean Atlantic marine air masses the mean (and standard error of the mean) observed MSA concentrations (27 ± 2 parts per trillion molar mixing ratio, ppt) were smaller than in continental polluted air masses (36 ± 6 ppt), reflecting either longer aerosol lifetimes in air with higher cloud condensation nuclei (CCN) concentrations or more active photochemical production in polluted air. Mean NH4+/non-sea-salt (nss) SO4= molar ratios in marine and continental air masses were 0.65 ± 0.05 and 1.3 ± 0.2, respectively, indicating that continental sulfate was neutralized by ammonia to a greater extent than marine sulfate was. Most of the NH4+ and nss SO4= was contained in submicrometer modes; Na+, Cl−, and NO3− were in supermicron modes; and MSA showed bimodal behavior, with major and minor peaks at 0.3–0.4 μm and 1.5 μm, respectively. The molar ratio NH4+/nss SO4= relative to size confirms that most ammonia vapor condensed on submicron nss SO4=. The average dry deposition fluxes for aerosol nss SO4=, MSA, NH4+ and NO3− during ASTEX/MAGE were 1.49, 0.09, 0.18, and 3.25 μmol m−2 d−1, respectively.

Daily total particulate matter observations of sulfate, sodium, and methanesulfonate were collected at Mauna Loa Observatory (19.54°N, 155.57°W, 3397m ASL) during 1995-2008. Observations were restricted to nighttime, downslope conditions and were thus representative of free tropospheric air masses. In this paper we focus analyses on 2008, when active volcanoes in Hawaii, Alaska, Indonesia, and elsewhere may have perturbed the northern hemisphere sulfur budget. The 2008 seasonal cycle of aerosol species was broadly consistent with the 1995-2008 mean, although the springtime peaks of anthropogenically-derived sulfate were larger than typical. Trajectories originated from East Asia less frequently and from North America more frequently in spring 2008 than in the long term data record, possibly linked to the strong La Nina conditions that year.

Aerosol particles can act as cloud condensation nuclei and thereby influence the number and size of droplets in clouds. Consequently, anthropogenic particles have the potential to influence global climate by increasing cloud albedo and decreasing precipitation efficiencies. Enhanced cloud reflectances associated with increases in panicle number have been observed, but our understanding of these interactions has been hindered by incomplete empirical studies and models of limited scope. In this study, aerosol and droplet size distributions were measured on 13 research flights in stratiform clouds within 300 km west of the northern California coast. The chemical composition of the droplet solute was also assessed. Microphysical and chemical properties indicated that most of the clouds were influenced by pollution from the North American continent, but pristine marine clouds were sampled on one flight during westerly flow conditions. Data from this flight and another, representing a pristine and poll...

[1] Updates for the Coupled Ocean-Atmosphere Response Experiment (COARE) physically based meteorological and gas transfer bulk flux algorithms are examined. The current versions are summarized and a generalization of the gas transfer codes to 79 gases is described. The current meteorological version COARE3.0 was compared with a collection of 26,700 covariance observations of drag and heat transfer coefficients (compiled from three independent research groups). The algorithm agreed on average to within 5% with observations for a wind speed range of 2 to 18 m s−1. Covariance observations of CO2 and dimethyl sulfide (DMS) gas transfer velocity k were normalized to Schmidt number 660 and compared to an ensemble of gas flux observations from six research groups and nine field programs. A reasonable fit of the mean k660 versus U10n values was obtained for both CO2 and DMS with a new version of the COARE gas transfer algorithm (designated COAREG3.1) using friction velocity associated with viscous (tangential) stress, u*ν, in the nonbubble term. In the wind speed range 5 to 16 m s−1, tracer-derived estimates of k660 are 10% to 20% lower than the CO2 covariance estimates presented here.

[1] In the Southern Ocean Gas Exchange Experiment (SO GasEx), we measured an atmospheric dimethylsulfide (DMS) concentration of 118 ± 54 pptv (1σ), a DMS sea-to-air flux of 2.9 ± 2.1 μmol m−2 d−1 by eddy covariance, and a seawater DMS concentration of 1.6 ± 0.7 nM. Dividing flux by the concurrent air-sea concentration difference yields the transfer velocity of DMS (kDMS). The kDMS in the Southern Ocean was significantly lower than previous measurements in the equatorial east Pacific, Sargasso Sea, northeast Atlantic, and southeast Pacific. Normalizing kDMS for the temperature dependence in waterside diffusivity and solubility results in better agreement among various field studies and suggests that the low kDMS in the Southern Ocean is primarily due to colder temperatures. The higher solubility of DMS at a lower temperature results in greater airside control and less transfer of the gas by bubbles formed from breaking waves. The final normalized DMS transfer velocity is similar to k of less soluble gases such as carbon dioxide in low-to-moderate winds; in high winds, DMS transfer velocity is significantly lower because of the reduced bubble-mediated transfer.

Dimethylsulfide (DMS) emitted from the ocean is a biogenic precursor gas for sulfur dioxide (SO2) and non-sea-salt sulfate aerosols (SO42−). During the VAMOS-Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) in 2008, multiple instrumented platforms were deployed in the Southeastern Pacific (SEP) off the coast of Chile and Peru to study the linkage between aerosols and stratocumulus clouds. We present here observations from the NOAA Ship Ronald H. Brown and the NSF/NCAR C-130 aircraft along ~20° S from the coast (70° W) to a remote marine atmosphere (85° W). While SO42− and SO2 concentrations were distinctly elevated above background levels in the coastal marine boundary layer (MBL) due to anthropogenic influence (~800 and 80 pptv, respectively), their concentrations rapidly decreased west of 78° W (~100 and 25 pptv). In the remote region, entrainment from the free troposphere (FT) increased MBL SO2 burden at a rate of 0.05 ± 0.02 μmoles m−2 day−1 and diluted MBL SO42 burden at a rate of 0.5 ± 0.3 μmoles m−2 day−1, while the sea-to-air DMS flux (3.8 ± 0.4 μmoles m−2 day−1) remained the predominant source of sulfur mass to the MBL. In-cloud oxidation was found to be the most important mechanism for SO2 removal and in situ SO42− production. Surface SO42− concentration in the remote MBL displayed pronounced diel variability, increasing rapidly in the first few hours after sunset and decaying for the rest of the day. We theorize that the increase in SO42− was due to nighttime recoupling of the MBL that mixed down cloud-processed air, while decoupling and sporadic precipitation scavenging were responsible for the daytime decline in SO42−.