Eric S. Saltzman

Processes controlling the distribution of aerosol particles in the lower marine boundary layer during the First Aerosol Characterization Experiment (ACE 1)

The goals of the International Global Atmospheric Chemistry (IGAC) Programs First Aerosol Characterization Experiment (ACE 1) are to determine and understand the properties and controlling factors of the aerosol in the remote marine atmosphere that are relevant to radiative forcing and climate. A key question in terms of this goal and the overall biogeochemical sulfur cycle is what factors control the formation, growth, and evolution of particles in the marine boundary layer (MBL). To address this question, simultaneous measurements of dimethylsulfide (DMS), sulfur dioxide (SO2), the aerosol chemical mass size distribution, and the aerosol number size distribution from 5 to 10,000 nm diameter were made on the National Oceanic and Atmospheric Administration (NOAA) ship Discoverer. From these data we conclude that the background MBL aerosol during ACE 1 often was composed of four distinct modes: an ultrafine (UF) mode (Dp = 5–20 nm), an Aitken mode (Dp = 20–80 nm), an accumulation mode (Dp = 80–300 nm), and a coarse mode (Dp > 300 nm). The presence of UF mode particles in the MBL could be explained by convective mixing between the free troposphere (FT) and the MBL associated with cloud pumping and subsidence following cold frontal passages. There was no evidence of major new particle production in the MBL. Oceanic emissions of DMS appeared to contribute to the growth of Aitken and accumulation mode particles. Coarse mode particles were comprised primarily of sea salt. Although these particles result from turbulence at the air-sea interface, the instantaneous wind speed accounted for only one third of the variance in the coarse mode number concentration in this region.

Methanesulfonic acid and non-sea-salt sulfate in pacific air: Regional and seasonal variations

Concentrations of aerosol methanesulfonic acid (MSA) and non-sea-salt (nss) sulfate were measured at six island stations in the Pacific Ocean to investigate regional and seasonal patterns of organosulfur emissions and the origin of nss sulfate over the Pacific. The mean MSA concentrations, in μg/m3, at the stations were: Shemya, 0.097±0.098; Midway, 0.029±0.021; Fanning, 0.044±0.012; American Samoa, 0.026±0.012; New Caledonia, 0.021±0.009; Norfolk, 0.024±0.019. The extremely high MSA levels found at Shemya indicate a major source of organosulfur emissions in the western North Pacific. Significant seasonal trends in MSA were observed, with higher MSA occurring during warm months. The amplitude of the seasonal variation was greatest at higher latitude stations. At Fanning and American Samoa, which have minimal input of continental material, there is a significant positive correlation between MSA and nss sulfate. MSA/nss sulfate ratios at other Pacific stations exhibit greater variability, which may be related to variations in: the input of continentally derived sulfate, the composition of oceanic organosulfur emissions, and atmospheric reaction pathways.

Spatial and temporal variations of hydrogen peroxide in Gulf of Mexico waters

Abstract Hydrogen peroxide concentrations in the Gulf of Mexico were measured on two cruises in May and August, 1982, in a variety of locations ranging from oligotrophic oceanic stations to highly productive coastal sites. Measurements were made using a fluorescence decay technique. Depth profiles of H 2 O 2 exhibit surface maxima of 1−2 × 10 −7 mol L −1 and decreasing concentrations with depth. Peroxide concentrations decreased only slightly or were invariant with depth in the mixed layer but decreased sharply to below the limit of detection (5 × 10 −9 mol L −1 ) in the region of the pycnocline at the base of the mixed layer. Surface concentrations were generally highest in coastal regions but did not vary by more than a factor of three among all stations studied. There was a marked diel variation in peroxide profiles, with the highest values occurring during the late afternoon, and the lowest values occurring at dawn. Diel variations were more pronounced in coastal surface waters than in oligotrophic waters. The observations are consistent with photochemical formation of H 2 O 2 by photooxidation of dissolved organic matter. However, other formation pathways, such as biological formation or atmospheric deposition, cannot be ruled out at this point.

Ozone observations and a model of marine boundary layer photochemistry during SAGA 3

A major purpose of the third joint Soviet-American Gases and Aerosols (SAGA 3) oceanographic cruise was to examine remote tropical marine O3 and photochemical cycles in detail. On leg 1, which took place between Hilo, Hawaii, and Pago-Pago, American Samoa, in February and March 1990, shipboard measurements were made of O3, CO, CH4, nonmethane hydrocarbons (NMHC), NO, dimethyl sulfide (DMS), H2S, H2O2, organic peroxides, and total column O3. Postcruise analysis was performed for alkyl nitrates and a second set of nonmethane hydrocarbons. A latitudinal gradient in O3 was observed on SAGA 3, with O3 north of the intertropical convergence zone (ITCZ) at 15–20 parts per billion by volume (ppbv) and less than 12 ppbv south of the ITCZ but never ≤3 ppbv as observed on some previous equatorial Pacific cruises (Piotrowicz et al., 1986; Johnson et al., 1990). Total column O3 (230–250 Dobson units (DU)) measured from the Akademik Korolev was within 8% of the corresponding total ozone mapping spectrometer (TOMS) satellite observations and confirmed the equatorial Pacific as a low O3 region. In terms of number of constituents measured, SAGA 3 may be the most photochemically complete at-sea experiment to date. A one-dimensional photochemical model gives a self-consistent picture of O3-NO-CO-hydrocarbon interactions taking place during SAGA 3. At typical equatorial conditions, mean O3 is 10 ppbv with a 10–15% diurnal variation and maximum near sunrise. Measurements of O3, CO, CH4, NMHC, and H2O constrain model-calculated OH to 9 × 105 cm−3 for 10 ppbv O3 at the equator. For DMS (300–400 parts per trillion by volume (pptv)) this OH abundance requires a sea-to-air flux of 6–8 × 109 cm−2 s−1, which is within the uncertainty range of the flux deduced from SAGA 3 measurements of DMS in seawater (Bates et al., this issue). The concentrations of alkyl nitrates on SAGA 3 (5–15 pptv total alkyl nitrates) were up to 6 times higher than expected from currently accepted kinetics, suggesting a largely continental source for these species. However, maxima in isopropyl nitrate and bromoform near the equator (Atlas et al., this issue) as well as for nitric oxide (Torres and Thompson, this issue) may signify photochemical and biological sources of these species.

Photoreduction of iron(III) in marine mineral aerosol solutions

Although there have been a number of studies of the solubility of Fe in marine mineral aerosols, there have been few studies of the oxidation states of the soluble iron fraction and of the factors that affect the solubility of iron in aerosol solutions. In this paper we present measurements of the concentrations of total Fe (including particulate), total soluble Fe and total soluble Fe(II) in marine aerosol particles. Only 1% of the total Fe and 7.5% of the soluble Fe was in the Fe(II) form. Photolysis experiments were performed with solutions extracted from aerosol filter samples and with solutions of Fe(III) in acidic sodium chloride. In both systems, Fe(II) concentrations increased rapidly when the solutions were exposed to sunlight and they attained steady state within an hour. However, in all cases Fe(II) is only a minor component even when conditions are favorable for photolysis. Fe(II) formation is hindered at the low pH that is believed to be characteristic of marine aerosol solutions. Solutions with added oxalate yielded greatly increased concentrations of Fe(II); this is probably related to the fact that Fe(III) oxalate complexes have strong ligand to metal charge transfer bands in the tropospheric solar UV-visible region. However, the presence of oxalate also leads to the formation of H2O2; when the radiation level decreased, the Fe(II) was partially or totally oxidized back to Fe(III) due to reactions with H2O2. The photoreduction of Fe(III) to Fe(II) did not appear to significantly increase the dissolution of Fe(III) from the dust mineral matrix.

Climate Change During the Last Deglaciation in Antarctica

Greenland ice core records provide clear evidence of rapid changes in climate in a variety of climate indicators. In this work, rapid climate change events in the Northern and Southern hemispheres are compared on the basis of an examination of changes in atmospheric circulation developed from two ice cores. High-resolution glaciochemical series, covering the period 10,000 to 16,000 years ago, from a central Greenland ice core and a new site in east Antarctica display similar variability. These findings suggest that rapid climate change events occur more frequently in Antarctica than previously demonstrated.

Shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide in the Caribbean and Gulf of Mexico

Simultaneous shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide were made on three cruises in the Gulf of Mexico and the Caribbean. The cruise tracks include both oligotrophic and coastal waters and the air masses sampled include both remote marine air and air masses heavily influenced by terrestrial or coastal inputs. Using samples from two north-south Caribbean transects which are thought to represent remote subtropical Atlantic air, mean concentrations of DMS and H2S were found to be 57 pptv (74 ng S m-3, σ=29 pptv, n=48) and 8.5 pptv (11 ng S m-3, σ=5.3 pptv, n=36), respectively. The ranges of measured concentrations for all samples were 0–800 pptv DMS and 0–260 pptv H2S. Elevated concentrations were found in coastal regions and over some shallow waters. Statistical analysis reveals slight nighttime maxima in the concentrations of both DMS and H2S in the remote marine atmosphere. The diurnal nature of the H2S data is only apparent after correcting the measurements for interference due to carbonyl sulfide. Calculations using the measured ratio of H2S to DMS in remote marine air suggest that the oxidation of H2S contributes only about 11% to the excess (non-seasalt) sulfate in the marine boundary layer.

Hydrogen peroxide concentrations in the Peru upwelling area

Zika, R.G., Saltzman, E.S. and Cooper, W.J., 1985. Hydrogen peroxide concentrations in the Peru upwelling area. Mar. Chem., 17: 265--275. The concentration of hydrogen peroxide was measured in waters off the coast of Peru during June and July 1983. The study period coincided with the end of the 1982/83 E1 Ni/~o and the onset of coastal upwelling. Depth profiles of hydrogen peroxide concentration exhibit surface maxima and decrease with depth to the base of the mixed layer. Surface peroxide concentrations ranged from 0.8 to 5 x 10 -8 M. Below the mixed layer hydrogen peroxide was below the detection limit (5 x 10 -9 M). Diel variations were observed, with surface peroxide levels increasing during the day and decreasing at night. The nearshore station exhibited lower hydrogen peroxide concentrations than offshore stations, a reversal of the trend found in other coastal regions. This is attributed to the lack of coastal vegetation and runoff, and to active coastal upwelling of deeper water with low hydrogen peroxide concentrations.

Spatial and temporal variations of methanesulfonic acid and non sea salt sulfate in Antarctic ice

A simultaneous glaciochemical study of methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO4-) has been conducted on the Antarctic plateau (South Pole, Vostok) and in more coastal regions. The objective was to investigate marine sulfur emissions in very remote areas. Firstly, our data suggest that MSA and nss-SO4 present in antarctic ice are mainly marine in origin and that DMS emissions have been significantly modulated by short term (eg. El Nino Southern Oscillation events) as well as long term climatic changes in the past. Secondly, our study of spatial variations of these two sulfur species seems to indicate that the atmosphere of coastal antarctic regions are mainly supplied by local DMS emissions whereas the atmosphere of the high plateau is also influenced by DMS emissions from more temperate marine latitudes. Thirdly, our study of the partitioning between MSA and nss-SO4 suggest that the temperature could have been an important parameter controlling the final composition of the high southern latitude atmosphere over the last climatic cycle; colder temperature favoring the formation of MSA. However, our data also support a possible role played by changes in the transport pattern of marine air to the high antarctic plateau.

Removal of methyl bromide in coastal seawater: Chemical and biological rates

A stable isotope tracer technique was used to investigate the loss rate of methyl bromide in surface ocean waters. Unfiltered and 0.2 μm-filtered or autoclaved aliquants of Biscayne Bay seawater samples were spiked with 13CH3Br at roughly 10–100 times ambient concentrations (50–800 pM) and incubated for 10–30 hours. The concentration of 13CH3Br was monitored using gas chromatography with isotope dilution mass spectrometry, with CD3Br as the isotope spike. Removal rates in unfiltered aliquants were significantly faster than in the 0.2 μm-filtered or autoclaved aliquants, indicating that some of the loss of methyl bromide was associated with particulate matter. Filtration experiments indicate that the particulate material responsible for methyl bromide loss is between 0.2 and 1.2 μm in diameter, suggesting that bacteria are likely to be responsible. The particulate-related removal of methyl bromide was inhibited by autoclaving, supporting a biological mechanism.