G. P. Ayers

Airborne measurements of dimethylsulfide, sulfur dioxide, and aerosol ions over the southern Ocean South of Australia

Vertical distributions of dimethylsulfide (DMS), sulfur dioxide (SO2), aerosol methane-sulfonate (MSA), non-sea-salt sulfate (nss-SO42-), and other aerosol ions were measured in maritime air west of Tasmania (Australia) during December 1986. A few cloudwater and rainwater samples were also collected and analyzed for major anions and cations. DMS concentrations in the mixed layer (ML) were typically between 15–60 ppt (parts per trillion, 10−12; 24 ppt=1 nmol m−3 (20°C, 1013 hPa)) and decreased in the free troposphere (FT) to about <1–2.4 ppt at 3 km. One profile study showed elevated DMS concentrations at cloud level consistent with turbulent transport (‘cloud pumping’) of air below convective cloud cells. In another case, a diel variation of DMS was observed in the ML. Our data suggest that meteorological rather than photochemical processes were responsible for this behavior. Based on model calculations we estimate a DMS lifetime in the ML of 0.9 days and a DMS sea-to-air flux of 2–3 μmol m−2 d−1. These estimates pertain to early austral summer conditions and southern mid-ocean latitudes. Typical MSA concentrations were 11 ppt in the ML and 4.7–6.8 ppt in the FT. Sulfur-dioxide values were almost constant in the ML and the lower FT within a range of 4–22 ppt between individual flight days. A strong increase of the SO2 concentration in the middle FT (5.3 km) was observed. We estimate the residence time of SO2 in the ML to be about 1 day. Aqueous-phase oxidation in clouds is probably the major removal process for SO2. The corresponding removal rate is estimated to be a factor of 3 larger than the rate of homogeneous oxidation of SO2 by OH. Model calculations suggest that roughly two-thirds of DMS in the ML are converted to SO2 and one-third to MSA. On the other hand, MSA/nss-SO42- mole ratios were significantly higher compared to values previously reported for other ocean areas suggesting a relatively higher production of MSA from DMS oxidation over the Southern Ocean. Nss-SO42- profiles were mostly parallel to those of MSA, except when air was advected partially from continental areas (Africa, Australia). In contrast to SO2, nss-SO42- values decreased significantly in the middle FT. NH4+/nss-SO42- mole ratios indicate that most non-sea-salt sulfate particles in the ML were neutralized by ammonium.

Sulfate and methanesulfonate in the maritime aerosol at Cape Grim, Tasmania

High-volume aerosol filters, exposed in maritime air masses at Cape Grim since late 1976, were analysed for excess sulfate (not of seasalt origin) and methanesulfonate. The mean concentrations (standard errors) of 2.80(0.59) and 0.176(0.027) nmole/m3 respectively are about half those reported in a recent study of aerosol samples from various locations in the Atlantic and Pacific oceans.Methanesulfonate concentration varied seasonally by at least an order of magnitude with a summer maximum and winter minimum. No comparable cycle was found for excess sulfate.

Chloride and Bromide Loss from Sea-Salt Particles in Southern Ocean Air

Datasets on aerosol composition in Southern Ocean air at Cape Grim and Macquarie Island, and rainwater composition at Cape Grim, have been analysed for sea-salt components in order to test the validity of the multiphase autocatalytic halogen activation process proposed initially by Sander and Crutzen (1996) and developed fully for clean marine air by Vogt et al. (1996). Four distinct datasets from the two locations were analysed. All four datasets provided consistent evidence in support of three predictions of the autocatalytic model: (1) overall Cl- deficits in sea-salt aerosol were small, difficult to quantify against analytical uncertainty and at most a few percent; (2) Br- deficits were large, averaging −30% to −50% on an annual basis, with strong seasonality ranging from about −10% in some winter samples to −80% or more in some summer samples; and (3) the Br- and Cl- deficits were clearly linked to the availability of strong, S-acidity in the aerosol, confirming the importance of acid catalysis to the dehalogenation process.

The Annual Cycle of Peroxides and Ozone in Marine Air at Cape Grim, Tasmania

The concentration of gas-phase peroxides has been measured almost continuously at the Cape Grim baseline station (41° S) over a period of 393 days (7702 h of on-line measurements) between February 1991 and March 1992. In unpolluted marine air a distinct seasonal cycle in concentration was evident, from a monthly mean value of>1.4 ppbv in summer (December) to <0.2 ppbv in winter (July). In the summer months a distinct diurnal cycle in peroxides was also observed in clean marine air, with a daytime build-up in concentration and decay overnight. Both the seasonal and diurnal cycles of peroxides concentration were anticorrelated with ozone concentration, and were largely explicable using a simple photochemical box model of the marine boundary layer in which the central processes were daytime photolytic destruction of ozone, transfer of reactive oxygen into the peroxides under the low-NOx ambient conditions that favour self-reaction between peroxy radicals, and continuous heterogeneous removal of peroxides at the ocean surface. Additional factors affecting peroxides concentrations at intermediate timescales (days to a week) were a dependence on air mass origin, with air masses arriving at Cape Grim from higher latitudes having lower peroxides concentrations, a dependence on local wind speed, with higher peroxides concentrations at lower wind speeds, and a systematic decrease in peroxides concentration during periods of rainfall. Possible physical mechanisms for these synoptic scale dependencies are discussed.

Dimethylsulfide in marine air at Cape Grim, 41°S

Atmospheric dimethylsulfide measurements made in marine air at Cape Grim, Tasmania, have been combined with a simple photochemical box model to provide estimates of monthly mean flux of dimethylsulfide from the Southern Ocean upwind of Cape Grim. The flux estimates for midsummer agree remarkably well with the independent estimates made for the latitude of Cape Grim based on oceanic surface water data and simple sea-air transport models. However, for midwinter the flux estimates made here, based on atmospheric dimethlysidfide data, are as much as an order of magnitude lower than those made elsewhere based on oceanic surface water data.

Ozone in the Marine Boundary Layer at Cape Grim: Model Simulation

A photochemical box model has been used to simulate the mixing ratio ofozone under conditions reflecting those encountered in the marine boundarylayer at Cape Grim, Tasmania, where a decade-long record of ozone mixingratio is available. The model is based on the proposition that ozone loss byphotolysis, atmospheric reaction with hydroperoxy and hydroxyl radicals, andsurface deposition is balanced by ozone gain via entrainment from the lowerfree troposphere with a small additional source in summer from photolysis ofnitrogen dioxide. This model simulates very well the observed ozone records,reproducing both the small diurnal cycle in ozone mixing ratio observedduring the summer months, and the factor of two seasonal ozone cycle showinga distinct winter maximum and summer minimum. The model result confirms thatunder the low-NOx conditions of the clean marine boundarylayer net photochemical loss of ozone occurs at all times of year.

Numerical study of droplet size dependent chemistry in oceanic, wintertime stratus cloud at southern mid-latitudes

Cloud droplet chemistry is modelled for the first 150 m of rise in a wintertime, mid-latitude, marine stratus cloud using observations made at and near the Cape Grim Baseline Station as a source of input parameters. The emphasis in this work was to study the variation in droplet chemistry as a function of both droplet size and nucleus composition, with a particular focus on the way in which oxidation of dissolved sulfur dioxide varied.At 150 m above the condensation level, solute concentration as a function of droplet size was found to increase by as much as 2 to 3 orders of magnitude for only a factor of 2 increase in droplet radius, primarily as a consequence of the 1/r dependence in the droplet growth equation. This type of size dependence exists at all levels in the model cloud, and has a significant influence on oxidation rate of sulfur dioxide in droplets growing on ‘sulfate’ nuclei, oxidation by ozone being favoured in the smallest droplets, but oxidation by hydrogen peroxide being favoured in the larger droplets. Oxidation by ozone is favoured at all sizes in droplets formed on sea-salt nuclei as a result of the initially high alkalinity of these droplets, and in the cloud overall is calculated to be the more important oxidation pathway. Although based on a simplified chemical scheme, these results suggest that both size-dependent and nucleus-dependent chemistry of cloud droplets may need to be considered explicitly in cloud modelling work.Volume-weighted mean pH values in the range 5 to 6 were predicted from sensitivity studies in which input variables were varied over reasonable ranges, in agreement with two sets of bulk cloud-water pH data obtained by aircraft near Cape Grim.

Dimethylsulfide oxidation and the ratio of methanesulfonate to non sea-salt sulfate in the marine aerosol

A box model of DMS oxidation in the clean, low-NOx marine atmospheric boundary layer has been used to predict the latitude dependence of the aerosol methanesulfonate to non sea-salt sulfate ratio. The observed latitude dependence of this ratio in the Southern Hemisphere can be reproduced reasonably well if the full suite of reactions proposed by Yin et al. (1990a) is employed, and a strong temperature dependence is specified in the rates of decomposition of CH3SO2 and CH3SO3 radicals.

Isoprene emissions from vegetation and hydrocarbon emissions from bushfires in tropical Australia

Information from a variety of sources, including an airborne field expedition in November 1985, is used to produce estimates of the annual emissions of some hydrocarbons from bushfires, and isoprene from trees, in tropical Australia. For the continent north of 23° S the annual bushfires (biomass burning) input was estimated, in units of Tg carbon, to be 2 TgC (uncertainty range 0.8–5 TgC), emitted predominantly during the May to October dryseason. Isoprene emissions during this period were estimated also to be 2 TgC (uncertainty range 0.5–8 TgC), but were estimated to be an order of magnitude higher during the November to April wet season, at a level of 23 TgC (uncertainty range 6–100 TgC).The large annual emission of isoprene over the tropical part of the Australian continent yields ppbv levels of isoprene measured at the surface in summertime. Isoprene reactivity with hydroxyl radical is such that at these concentrations isoprene must be a dominant factor in controlling the concentration of OH radical in the convective boundary layer. Simple arguments based on the convective velocity scale suggest that the shape of the isoprene vertical profile in November 1985 would be consistent with available data on the OH-isoprene reaction rate if OH concentration in the boundary layer averaged about 2.5×106 cm-3 over the middle part of the day.

Thymol as a Biocide in Japanese Rainwater

Rainwater samples (wet-only; event samples) collected in Niigata in late autumn 1996 and springtime 1997 were used to assess the effectiveness of thymol as a biocide in Japanese rainwater. Upon collection each rainwater sample was divided into sub-samples, with thymol added to one sub-sample. Sub-samples with and without thymol were shipped to CSIRO, Australia, for chemical analysis. Comparison of analytical results for each pair of sub-samples proved the effectiveness of thymol in preventing biological action in this region where effects of rainwater microflaura and fauna on rainwater composition have not before been studied. Sub-samples without thymol exhibited lowered electrical conductivity, loss of the cations H+ and NH4-, and loss of the anions HCOO-, CH3COO-, C2O42-, CH3SO3- and PO43-. Nitrate showed no change in all but one of the samples, indicating that ammonia was the preferred source of nitrogen for the biological processes that consumed the rainwater organic acids and phosphate. These results suggest that thymol is a suitable rainwater biocide for use under Japanese conditions.