T. S. Bates

Sulfur emissions to the atmosphere from natural sourees

Emissions of sulfur gases from both natural and anthropogenic sources strongly influence the chemistry of the atmosphere. To assess the relative importance of these sources we have combined the measurements of sulfur gases and fluxes during the past decade to create a global emission inventory. The inventory, which is divided into 12 latitude belts, takes into account the seasonal dependence of sulfur emissions from biogenic sources. The total emissions of sulfur gases from natural sources are approximately 0.79 Tmol S/a. These emissions are 16% of the total sulfur emissions in the Northern Hemisphere and 58% in the Southern Hemisphere. The inventory clearly shows the impact of anthropogenic sulfur emissions in the region between 35° and 50°N.

A global database of sea surface dimethylsulfide (DMS) measurements and a procedure to predict sea surface DMS as a function of latitude, longitude, and month

A database of 15,617 point measurements of dimethylsulfide (DMS) in surface waters along with lesser amounts of data for aqueous and particulate dimethylsulfoniopropionate concentration, chlorophyll concentration, sea surface salinity and temperature, and wind speed has been assembled. The database was processed to create a series of climatological annual and monthly 1°×1° latitude-longitude squares of data. The results were compared to published fields of geophysical and biological parameters. No significant correlation was found between DMS and these parameters, and no simple algorithm could be found to create monthly fields of sea surface DMS concentration based on these parameters. Instead, an annual map of sea surface DMS was produced using an algorithm similar to that employed by Conkright et al. [1994]. In this approach, a first-guess field of DMS sea surface concentration measurements is created and then a correction to this field is generated based on actual measurements. Monthly sea surface grids of DMS were obtained using a similar scheme, but the sparsity of DMS measurements made the method difficult to implement. A scheme was used which projected actual data into months of the year where no data were otherwise present.

International Global Atmospheric Chemistry (IGAC) Project's First Aerosol Characterization Experiment (ACE 1): Overview

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.

Radiative absorption enhancements due to the mixing state of atmospheric black carbon

Dark Forcing Soot, or black carbon, is a ubiquitous atmospheric pollutant whose warming effect might be second only to carbon dioxide. When black carbon is emitted, it combines with other aerosols to form heterogeneous mixtures. Models have predicted that internal mixing of black carbon with other materials can double the amount of radiation absorbed. Cappa et al. (p. 1078) report that in situ measurements of the enhancement of radiation absorption by these mixed black carbon–containing particles in the atmosphere show a much smaller effect. Thus, many climate models may be overestimating the amount of warming caused by black carbon emissions. Direct measurements show that ambient atmospheric particulate black carbon absorbs less solar radiation than theory suggested. Atmospheric black carbon (BC) warms Earth’s climate, and its reduction has been targeted for near-term climate change mitigation. Models that include forcing by BC assume internal mixing with non-BC aerosol components that enhance BC absorption, often by a factor of ~2; such model estimates have yet to be clearly validated through atmospheric observations. Here, direct in situ measurements of BC absorption enhancements (Eabs) and mixing state are reported for two California regions. The observed Eabs is small—6% on average at 532 nm—and increases weakly with photochemical aging. The Eabs is less than predicted from observationally constrained theoretical calculations, suggesting that many climate models may overestimate warming by BC. These ambient observations stand in contrast to laboratory measurements that show substantial Eabs for BC are possible.

The case against climate regulation via oceanic phytoplankton sulphur emissions

More than twenty years ago, a biological regulation of climate was proposed whereby emissions of dimethyl sulphide from oceanic phytoplankton resulted in the formation of aerosol particles that acted as cloud condensation nuclei in the marine boundary layer. In this hypothesis—referred to as CLAW—the increase in cloud condensation nuclei led to an increase in cloud albedo with the resulting changes in temperature and radiation initiating a climate feedback altering dimethyl sulphide emissions from phytoplankton. Over the past two decades, observations in the marine boundary layer, laboratory studies and modelling efforts have been conducted seeking evidence for the CLAW hypothesis. The results indicate that a dimethyl sulphide biological control over cloud condensation nuclei probably does not exist and that sources of these nuclei to the marine boundary layer and the response of clouds to changes in aerosol are much more complex than was recognized twenty years ago. These results indicate that it is time to retire the CLAW hypothesis.

Vertical distribution of dimethylsulfide, sulfur dioxide, aerosol ions, and radon over the Northeast Pacific Ocean

Dimethylsulfide (DMS), sulfur dioxide (SO2), methanesulfonate (MSA), nonsea-salt sulfate (nss-SO42−), sodium (Na+), ammonium (NH4+), and nitrate (NO3−) were determined in samples collected by aircraft over the open ocean in postfrontal maritime air masses off the northwest coast of the United States (3–12 May 1985). Measurements of radon daughter concentrations and isentropic trajectory calculations suggested that these air masses had been over the Pacific for 4–8 days since leaving the Asian continent. The DMS and MSA profiles showed very similar structures, with typical concentrations of 0.3–1.2 and 0.25–0.31 nmol m−3 (STP) respectively in the mixed layer, decreasing to 0.01–0.12 and 0.03–0.13 nmol m−3 (STP) at 3.6 km. These low atmospheric DMS concentrations are consistent with low levels of DMS measured in the surface waters of the northeastern Pacific during the study period.The atmospheric SO2 concentrations always increased with altitude from <0.16–0.25 to 0.44–1.31 nmol m−3 (STP). The nonsea-salt sulfate (ns-SO42−) concentrations decreased with altitude in the boundary layer and increased again in the free troposphere. These data suggest that, at least under the conditions prevailing during our flights, the production of SO2 and nss-SO42− from DMS oxidation was significant only within the boundary layer and that transport from Asia dominated the sulfur cycle in the free troposphere. The existence of a ‘sea-salt inversion layer’ was reflected in the profiles of those aerosol components, e.g., Na+ and NO3−, which were predominantly present as coarse particles. Our results show that long-range transport at mid-tropospheric levels plays an important role in determining the chemical composition of the atmosphere even in apparently ‘remote’ northern hemispheric regions.

ACE-ASIA Regional Climatic and Atmospheric Chemical Effects of Asian Dust and Pollution

Although continental-scale plumes of Asian dust and pollution reduce the amount of solar radiation reaching the earths surface and perturb the chemistry of the atmosphere, our ability to quantify these effects has been limited by a lack of critical observations, particularly of layers above the surface. Comprehensive surface, airborne, shipboard, and satellite measurements of Asian aerosol chemical composition, size, optical properties, and radiative impacts were performed during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) study. Measurements within a massive Chinese dust storm at numerous widely spaced sampling locations revealed the highly complex structure of the atmosphere, in which layers of dust, urban pollution, and biomass-burning smoke may be transported long distances as distinct entities or mixed together. The data allow a first-time assessment of the regional climatic and atmospheric chemical effects of a continental-scale mixture of dust and pollution. Our results show that radiative flux reductions during such episodes are sufficient to cause regional climate change.

The 2nd Aerosol Characterization Experiment (ACE-2): general overview and main results

This overview summarizes the objectives of the Aerosol Characterization Experiments (ACEs) of the International Global Atmospheric Chemistry (IGAC) project and the research strategy implemented in the second of this series of experiments (ACE-2). ACE-2 took place from 16 June to 24 July 1997, over the sub-tropical North-East Atlantic. It provided an opportunity to study the properties, processes and effects of contrasting aerosol types in this region, including background marine and anthropogenic pollution aerosol in the marine boundary layer (MBL), and background aerosol and mineral dust in the overlaying free troposphere (FT). The major achievements of ACE-2 include:(a) identification of entrainment, in-cloud scavenging and coagulation as the major processes transforming a pollution aerosol transported within the MBL; (b) the first documentation of the indirect radiative effect of aerosols at the scale of a cloud ensemble in continental pollution outflow; (c) observation of a wide range in the contribution of organic material to the sub-micron aerosol mass, with possibly the highest contribution in the free tropospheric; (d) improved understanding of the role of condensing HCl, HNO3 and NH3 as a growth mechanism of sub-micron aerosols in polluted air masses advecting over the ocean. A close connection was observed between meteorological factors (such as horizontal and vertical wind speed, boundary layer development, entrainment, humidity fields) and aerosol and cloud characteristics. In the ACE-2 region, these meteorological factors, rather than aerosol microphysics and chemistry, often dominated the shaping of the aerosol size distribution and/or their effect on radiation and clouds. The ACE-2 data presently analyzed provide a qualitative, and in many cases a quantitative understanding of the complex gas/aerosol/cloud system in the sub-tropical marine environment. This will guide future model development. Some major data sets are still to be analyzed.

International Consortium for Atmospheric Research on Transport and Transformation (ICARTT): North America to Europe—Overview of the 2004 summer field study

In the summer of 2004 several separate field programs intensively studied the photochemical, heterogeneous chemical and radiative environment of the troposphere over North America, the North Atlantic Ocean, and western Europe. Previous studies have indicated that the transport of continental emissions, particularly from North America, influences the concentrations of trace species in the troposphere over the North Atlantic and Europe. An international team of scientists, representing over 100 laboratories, collaborated under the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) umbrella to coordinate the separate field programs in order to maximize the resulting advances in our understanding of regional air quality, the transport, chemical transformation and removal of aerosols, ozone, and their precursors during intercontinental transport, and the radiation balance of the troposphere. Participants utilized nine aircraft, one research vessel, several ground-based sites in North America and the Azores, a network of aerosol-ozone lidars in Europe, satellites, balloon borne sondes, and routine commercial aircraft measurements. In this special section, the results from a major fraction of those platforms are presented. This overview is aimed at providing operational and logistical information for those platforms, summarizing the principal findings and conclusions that have been drawn from the results, and directing readers to specific papers for further details.

Impact of dimethylsulfide photochemistry on methyl sulfur cycling in the equatorial Pacific Ocean

Shipboard experiments were conducted in the equatorial Pacific Ocean to ascertain the relative importance of atmospheric ventilation, biological consumption, and photolysis in the removal of dimethylsulfide (DMS) from seawater. Comparisons were made at a series of sampling locations in a transect from 12°N 140°W to 12°S 135°W, as part of the International Global Atmospheric Chemistry projects Marine Aerosol and Gas Exchange cruise in February–March 1992. Turnover rate constants for DMS were used to compare the different removal pathways over three depth intervals (0–1 m, 0–20 m, and 0–60 m). In the surface mixed layer (0–60 m), the DMS turnover rate constants ranged from 0.02 to 0.19 day−1 for atmospheric ventilation, 0.04 to 0.66 day−1 for biological consumption, and 0.05 to 0.15 day−1 for photolysis. When all three processes are considered, the corresponding turnover time for DMS ranges from 1 to 4 days, with photolysis accounting for 7%–40% of the total turnover of DMS. Laboratory irradiations were conducted with stored seawater samples to study the kinetics and wavelength dependence of DMS photolysis. Salient results were (1) the photolysis of DMS followed pseudo first-order kinetics, (2) dimethylsulfoxide was a minor (14%) product of DMS photolysis, and (3) the photolysis of DMS in seawater under natural light conditions occurred primarily at wavelengths between 380 and 460 nm. On the basis of these results, we predict that the photolysis of DMS will occur at appreciable depths in the photic zone in oligotrophic marine environments (∼60 m). An important finding of this study is that atmospheric loss, biological consumption, and photolysis are all important removal pathways for DMS in the photic zone of the equatorial Pacific Ocean. The relative importance of each pathway is a function of the depth interval considered, sampling location, and meteorological conditions.