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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.

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.

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.

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.

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.

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−.