Robert W. Talbot

Relationships among aerosol constituents from Asia and the North Pacific during PEM‐West A

Aerosol particle samples collected from Asia and the North Pacific were analyzed to investigate the relationships among atmospheric sea salt, mineral aerosol, biogenic emissions (methanesulfonate (MSA)), and several anthropogenic substances (sulfate, nitrate, and various trace elements). These studies specifically focused on the sources for aerosol SO4= and on the long-range transport of continental materials to the North Pacific. Ground-based aerosol sampling was conducted at four coastal-continental sites: Hong Kong, Taiwan, Okinawa, and Cheju; and at three remote Pacific islands, Shemya, Midway, and Oahu. Non-sea-salt (nss) SO4= and MSA were uncorrelated at the East Asian sites presumably because pollution sources overwhelm the biogenic emissions of nss SO4=. At the coastal-continental sites, marine biogenic emissions accounted for only 10 to <5% of the total nss SO4=. In contrast, over the ocean the concentrations of nss SO4= and MSA were correlated (Midway r = 0.70; Oahu r = 0.59), and higher percentages of biogenic nss SO4= occurred, 55 and 70% at Oahu and Midway, respectively. The concentrations of nss SO4= and NO3− were correlated at Cheju, Hong Kong, Taiwan, Okinawa, Midway, and Oahu, indicating some similarities in their sources and the processes governing their transport; however, differences in the nss SO4=/NO3− ratios among sites suggest regional differences in the pollution component of the aerosol. At Shemya the concentrations of MSA during the summer (100 ng m−3 or more) are about 2 orders of magnitude higher than those in winter. The dimethylsulfide-derived fraction of the nss SO4= is highest in the summer when the monthly median nss SO4=/MSA ratios range from 2.7 to 4.5, i.e., comparable to the ratios observed over Antarctica and other high-latitude locations. However, the monthly median nss SO4=/MSA ratios increase, reaching 50 to 200 in the winter as productivity nearly ceases, and the biogenic fraction of nss SO4= at Shemya decreases dramatically; this suggests a strong seasonal pollution component to the sulfate aerosol. The meteorological conditions favoring the long-range transport of Asian dust to the North Pacific also lead to transport of anthropogenic materials. At Oahu the correlation between NO3− and Al (dust) was highly significant (r = 0.75; p < 0.001), while the correlations between nitrate and Al at the continental sites were low. These differences indicate that the composition of the air sampled at the coastal-continental stations may be quite different from the air transported to the remote ocean. This phenomenon also appeared to affect the relationship between nss SO4= and antimony. The correlations between nss SO4= and Sb were weak at the Asian sites but strong at the open ocean sites where the nss SO4=/Sb ratios were higher than those over the continent.

Origin of ozone and NOx in the tropical troposphere: A photochemical analysis of aircraft observations over the South Atlantic basin

The photochemistry of the troposphere over the South Atlantic basin is examined by modeling of aircraft observations up to 12-km altitude taken during the TRACE A expedition in September–October 1992. A close balance is found in the 0 to 12-km column between photochemical production and loss of O3, with net production at high altitudes compensating for weak net loss at low altitudes. This balance implies that O3 concentrations in the 0–12 km column can be explained solely by in situ photochemistry; influx from the stratosphere is negligible. Simulation of H2O2, CH3OOH, and CH2O concentrations measured aboard the aircraft lends confidence in the computations of O3 production and loss rates, although there appears to be a major gap in current understanding of CH2O chemistry in the marine boundary layer. The primary sources of NOx over the South Atlantic Basin appear to be continental (biomass burning, lightning, soils). There is evidence that NOx throughout the 0 to 12-km column is recycled from its oxidation products rather than directly transported from its primary sources. There is also evidence for rapid conversion of HNO3 to NOx in the upper troposphere by a mechanism not included in current models. A general representation of the O3 budget in the tropical troposphere is proposed that couples the large-scale Walker circulation and in situ photochemistry. Deep convection in the rising branches of the Walker circulation injects NOx from combustion, soils, and lightning to the upper troposphere, leading to O3 production; eventually, the air subsides and net O3 loss takes place in the lower troposphere, closing the O3 cycle. This scheme implies a great sensitivity of the oxidizing power of the atmosphere to NOx emissions in the tropics.

Distribution and fate of selected oxygenated organic species in the troposphere and lower stratosphere over the Atlantic

A large number of oxygenated organic chemicals (peroxyacyl nitrates, alkyl nitrates, acetone, formaldehyde, methanol, methylhydroperoxide, acetic acid and formic acid) were measured during the 1997 Subsonic Assessment (SASS) Ozone and Nitrogen Oxide Experiment (SONEX) airborne field campaign over the Atlantic. In this paper, we present a first picture of the distribution of these oxygenated organic chemicals (Ox-organic) in the troposphere and the lower stratosphere, and assess their source and sink relationships. In both the troposphere and the lower stratosphere, the total atmospheric abundance of these oxygenated species (ΣOx-organic) nearly equals that of total nonmethane hydrocarbons (ΣNMHC), which have been traditionally measured. A sizable fraction of the reactive nitrogen (10–30%) is present in its oxygenated organic form. The organic reactive nitrogen fraction is dominated by peroxyacetyl nitrate (PAN), with alkyl nitrates and peroxypropionyl nitrate (PPN) accounting for <5% of total NOy. Comparison of observations with the predictions of the Harvard three-dimensional global model suggests that in many key areas (e.g., formaldehyde and peroxides) substantial differences between measurements and theory are present and must be resolved. In the case of CH3OH, there appears to be a large mismatch between atmospheric concentrations and estimated sources, indicating the presence of major unknown removal processes. Instrument intercomparisons as well as disagreements between observations and model predictions are used to identify needed improvements in key areas. The atmospheric chemistry and sources of this group of chemicals is poorly understood even though their fate is intricately linked with upper tropospheric NOx and HOx cycles.

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.

The long-range transport of southern African aerosols to the tropical South Atlantic

Two episodes of long-range aerosol transport (4000 km) from southern Africa into the central tropical South Atlantic are documented. Stable nitrogen isotope analysis, multielemental analysis, and meteorological observations on local and regional scales are used to describe the observed surface aerosol chemistry during these transport episodes. The chemical, kinematic, and thermodynamic analyses suggest that for the central tropical South Atlantic, west Africa between 0° and 10°S is the primary air mass source region (over 50%) during austral spring. Over 70% of all air arriving in the lower and middle troposphere in the central tropical South Atlantic comes from a broad latitudinal band extending from 20°S to 10°N. Air coming from the east subsides and is trapped below the midlevel and trade wind inversion layers. Air from the west originates at higher levels (500 hPa) and contributes less than 30% of the air masses arriving in the central tropical South Atlantic. The source types of aerosols and precursor trace gases extend over a broad range of biomes from desert and savanna to the rain forest. During austral spring, over this broad region, processes include production from vegetation, soils, and biomass burning. The aerosol composition of air masses over and the atmospheric chemistry of the central South Atlantic is a function of the supply of biogenic, biomass burning, and aeolian emissions from tropical Africa. Rainfall is a common controlling factor for all three sources. Rain, in turn, is governed by the large-scale circulations which show pronounced interannual variability. The field measurements were taken in an extremely dry year and reflect the circulation and transport fields typical of these conditions.

Assessment of ozone photochemistry in the western North Pacific as inferred from PEM-West A observations during the fall 1991

This study examines the influence of photochemical processes on ozone distributions in the western North Pacific. The analysis is based on data generated during NASAs western Pacific Exploratory Mission (PEM-West A) during the fall of 1991. Ozone trends were best described in terms of two geographical domains: the western North Pacific rim (WNPR) and the western tropical North Pacific (WTNP). For both geographical regions, ozone photochemical destruction, D(O3), decreased more rapidly with altitude than did photochemical formation, F(O3). Thus the ozone tendency, P(O3), was typically found to be negative for z 6–8 km. For nearly all altitudes and latitudes, observed nonmethane hydrocarbon (NMHC) levels were shown to be of minor importance as ozone precursor species. Air parcel types producing the largest positive values of P(O3) included fresh continental boundary layer (BL) air and high-altitude (z > 7 km) parcels influenced by deep convection/lightning. Significant negative P(O3) values were found when encountering clean marine BL air or relatively clean lower free-tropospheric air. Photochemical destruction and formation fluxes for the Pacific rim region were found to exceed average values cited for marine dry deposition and stratospheric injection in the northern hemisphere by nearly a factor of 6. This region was also found to be in near balance with respect to column-integrated O3 photochemical production and destruction. By contrast, for the tropical regime column-integrated O3 showed photochemical destruction exceeding production by nearly 80%. Both transport of O3 rich midlatitude air into the tropics as well as very high-altitude (10–17 km) photochemical O3 production were proposed as possible additional sources that might explain this estimated deficit. Results from this study further suggest that during the fall time period, deep convection over Asia and Malaysia/Indonesia provided a significant source of high-altitude NOx to the western Pacific. Given that the high-altitude NOx lifetime is estimated at between 3 and 9 days, one would predict that this source added significantly to high altitude photochemical O3 formation over large areas of the western Pacific. When viewed in terms of strong seasonal westerly flow, its influence would potentially span a large part of the Pacific.

Reactive nitrogen and ozone over the western Pacific: Distribution, partitioning, and sources

Measurements of important reactive nitrogen species (NO, NO2, HNO3, PAN, PPN, NO3−, NOy), C1 to C6 hydrocarbons, O3, chemical tracers (C2Cl4, CO), and meteorological parameters were made in the troposphere (0 to 12 km) over the western Pacific (0°–50°N) during the Pacific Exploratory Mission-West A campaign (September–October 1991). Under clean conditions, mixing ratios of NO, NO2, NOy, and O3 increased with altitude and showed a distinct latitudinal gradient. PAN showed a midtropospheric maximum, while nitric acid mixing ratios were generally highest near the surface. Measured NOy concentrations were significantly greater than the sum of individually measured nitrogen species (mainly NOx, PAN, and HNO3), suggesting that a large fraction of reactive nitrogen present in the atmosphere is made up of hitherto unknown species. This shortfall was larger in the tropics (≈65%) compared to midlatitudes (≈40%) and was minimal in air masses with high HNO3 mixing ratios (>100 ppt). A global three-dimensional photochemical model has been used to compare observations with predictions and to assess the significance of major sources. It is possible that the tropical lightning source is much greater than commonly assumed, and both lightning source and its distribution remain a major area of uncertainty in the budgets of NOy and NOx. A large disagreement between measurement and theory exists in the atmospheric distribution of HNO3. It appears that surface-based anthropogenic emissions provide nearly 65% of the global atmospheric NOy reservoir. Relatively constant NOx/NOy ratios imply that NOy and NOx are in chemical equilibrium and the NOy reservoir may be an important in situ source of atmospheric NOx. Data are interpreted to suggest that only about 20% of the upper tropospheric (7–12 km) NOx is directly attributable to its surface NOx source, and free tropospheric sources are dominant. In situ release of NOx from the NOy reservoir, lightning, direct transport of surface NOx, aircraft emissions, and small stratospheric input collectively maintain the NOx balance in the atmosphere. It is shown that atmospheric ratios of reactive nitrogen and sulfur species, along with trajectory analysis, can be used to pinpoint the source of Asian continental outflow. Compared to rural atmospheres over North America, air masses over the Pacific are highly efficient in net O3 production. Sources of tropospheric NOx cannot yet be accurately defined due to shortcomings in measurements and theory.

Ozone and aerosol distributions and air mass characteristics over the South Pacific during the burning season

In situ and laser remote measurements of gases and aerosols were made with airborne instrumentation to establish a baseline chemical signature of the atmosphere above the South Pacific Ocean during the NASA Global Tropospheric Experiment (GTE)/Pacific Exploratory Mission-Tropics A (PEM-Tropics A) conducted in August-October 1996. This paper discusses general characteristics of the air masses encountered during this experiment using an airborne lidar system for measurements of the large-scale variations in ozone (O3) and aerosol distributions across the troposphere, calculated potential vorticity (PV) from the European Centre for Medium-Range Weather Forecasting (ECMWF), and in situ measurements for comprehensive air mass composition. Between 8°S and 52°S, biomass burning plumes containing elevated levels of O3, over 100 ppbv, were frequently encountered by the aircraft at altitudes ranging from 2 to 9 km. Air with elevated O3 was also observed remotely up to the tropopause, and these air masses were observed to have no enhanced aerosol loading. Frequently, these air masses had some enhanced PV associated with them, but not enough to explain the observed O3 levels. A relationship between PV and O3 was developed from cases of clearly defined O3 from stratospheric origin, and this relationship was used to estimate the stratospheric contribution to the air masses containing elevated O3 in the troposphere. The frequency of observation of the different air mass types and their average chemical composition is discussed in this paper.

Chemical characteristics of continental outflow from Asia to the troposphere over the western Pacific Ocean during February-March 1994: Results from PEM-West B

We present here the chemical composition of outflow from the Asian continent to the atmosphere over the western Pacific basin during the Pacific Exploratory Mission-West (PEM-West B) in February–March 1994. Comprehensive measurements of important tropospheric trace gases and aerosol particulate matter were performed from the NASA DC-8 airborne laboratory. Backward 5 day isentropic trajectories were used to partition the outflow from two major source regions: continental north (>20°N) and continental south (<20°N). Air parcels that had not passed over continental areas for the previous 5 days were classified as originating from an aged marine source. The trajectories and the chemistry together indicated that there was extensive rapid outflow of air parcels at altitudes below 5 km, while aged marine air was rarely encountered and only at <20°N latitude. The outflow at low altitudes had enhancements in common industrial solvent vapors such as C2Cl4, CH3CCl3, and C6H6, intermixed with the combustion emission products C2H2, C2H6, CO, and NO. The mixing ratios of all species were up to tenfold greater in outflow from the continental north compared to the continental south source region, with 210Pb concentrations reaching 38 fCi (10−15 curies) per standard cubic meter. In the upper troposphere we again observed significant enhancements in combustion-derived species in the 8–10 km altitude range, but water-soluble trace gases and aerosol species were depleted. These observations suggest that ground level emissions were lofted to the upper troposphere by wet convective systems which stripped water-soluble components from these air parcels. There were good correlations between C2H2 and CO and C2H6 (r2=0.70–0.97) in these air parcels and much weaker ones between C2H2 and H2O2 or CH3OOH (r2 ≈0.50). These correlations were the strongest in the continental north outflow where combustion inputs appeared to be recent (1–2 days old). Ozone and PAN showed general correlation in these same air parcels but not with the combustion products. It thus appears that several source inputs were intermixed in these upper tropospheric air masses, with possible contributions from European or Middle Eastern source regions. In aged marine air mixing ratios of O3 (≈20 parts per billion by volume) and PAN (≤10 parts per trillion by volume) were nearly identical at <2 km and 10–12 km altitudes due to extensive convective uplifting of marine boundary layer air over the equatorial Pacific even in wintertime. Comparison of the Pacific Exploratory Mission-West A and PEM-West B data sets shows significantly larger mixing ratios of SO2 and H2O2 during PEM-West A. Emissions from eruption of Mount Pinatubo are a likely cause for the former, while suppressed photochemical activity in winter was probably responsible for the latter. This comparison also highlighted the twofold enhancement in C2H2, C2H6, and C3H8 in the continental north outflow during PEM-West B. Although this could be due to reduced OH oxidation rates of these species in wintertime, we argue that increased source emissions are primarily responsible.

Summertime photochemistry of the troposphere at high northern latitudes

The budgets of O3, NOx (NO+NO2), reactive nitrogen (NOy), and acetic acid in the 0–6 km column over western Alaska in summer are examined by photochemical modeling of aircraft and ground-based measurements from the Arctic Boundary Layer Expedition (ABLE 3A). It is found that concentrations of O3 in the region are regulated mainly by input from the stratosphere, and losses of comparable magnitude from photochemistry and deposition. The concentrations of NOx (10–50 ppt) are sufficiently high to slow down O3 photochemical loss appreciably relative to a NOx-free atmosphere; if no NOx were present, the lifetime of O3 in the 0–6 km column would decrease from 46 to 26 days because of faster photochemical loss. The small amounts of NOx present in the Arctic troposphere have thus a major impact on the regional O3 budget. Decomposition of peroxyacetyl nitrate (PAN) can account for most of the NOx below 4-km altitude, but for only 20% at 6-km altitude. Decomposition of other organic nitrates might supply the missing source of NOx. The lifetime of NOy, in the ABLE 3A flight region is estimated at 29 days, implying that organic nitrate precursors of NOx could be supplied from distant sources including fossil fuel combustion at northern mid-latitudes. Biomass fire plumes sampled during ABLE 3A were only marginally enriched in O3; this observation is attributed in part to low NOx emissions in the fires, and in part to rapid conversion of NOx to PAN promoted by low atmospheric temperatures. It appears that fires make little contribution to the regional O3 budget. Only 30% of the acetic acid concentrations measured during ABLE 3A can be accounted for by reactions of CH3CO3 with HO2 and CH3O2. There remains a major unidentified source of acetic acid in the atmosphere.