Peter S. Liss

The atmospheric input of trace species to the world ocean

Over the past decade it has become apparent that the atmosphere is a significant pathway for the transport of many natural and pollutant materials from the continents to the ocean. The atmospheric input of many of these species can have an impact (either positive or negative) on biological processes in the sea and on marine chemical cycling. For example, there is now evidence that the atmosphere may be an important transport path for such essential nutrients as iron and nitrogen in some regions. In this report we assess current data in this area, develop global scale estimates of the atmospheric fluxes of trace elements, mineral aerosol, nitrogen species, and synthetic organic compounds to the ocean; and compare the atmospheric input rates of these substances to their input via rivers. Trace elements considered were Pb, Cd, Zn, Cu, Ni, As, Hg, Sn, Al, Fe, Si, and P. Oxidized and reduced forms of nitrogen were considered, including nitrate and ammonium ions and the gaseous species NO, NO2, HNO3, and NH3. Synthetic organic compounds considered included polychlorinated biphenyls (PCBs), hexachlorocyclohexanes (HCHs), DDTs, chlordane, dieldrin, and hexachlorobenzenes (HCBs). Making this assessment was difficult because there are very few actual measurements of deposition rates of these substances to the ocean. However, there are considerably more data on the atmospheric concentrations of these species in aerosol and gaseous form. Mean concentration data for 10° × 10° ocean areas were determined from the available concentration data or from extrapolation of these data into other regions. These concentration distributions were then combined with appropriate exchange coefficients and precipitation fields to obtain the global wet and dry deposition fluxes. Careful consideration was given to atmospheric transport processes as well as to removal mechanisms and the physical and physicochemical properties of aerosols and gases. Only annual values were calculated. On a global scale atmospheric inputs are generally equal to or greater than riverine inputs, and for most species atmospheric input to the ocean is significantly greater in the northern hemisphere than in the southern hemisphere. For dissolved trace metals in seawater, global atmospheric input dominates riverine input for Pb, Cd, and Zn, and the two transport paths are roughly equal for Cu, Ni, As, and Fe. Fluxes and basin-wide deposition of trace metals are generally a factor of 5-10 higher in the North Atlantic and North Pacific regions than in the South Atlantic and South Pacific. Global input of oxidized and reduced nitrogen species are roughly equal to each other, although the major fraction of oxidized nitrogen enters the ocean in the northern hemisphere, primarily as a result of pollution sources. Reduced nitrogen species are much more uniformly distributed, suggesting that the ocean itself may be a significant source. The global atmospheric input of such synthetic organic species as HCH,PCBs, DDT, and HCB completely dominates their input via rivers.

Air-Sea Gas Exchange Rates: Introduction and Synthesis

In this chapter we attempt to present a brief introduction to the subject of air-sea gas exchange. First the basic equations governing such exchange are given, then a review of some models proposed to describe the gas transfer process. Following this, experimental approaches through both laboratory (principally using wind/water tunnels) and field measurements are summarised. Finally, we present what seems to us to be the best current synthesis of the wind tunnel and field results for the prediction of gas exchange rates across the sea surface.

In situ evaluation of air-sea gas exchange parameterizations using novel conservative and volatile tracers

Measurements of air-sea gas exchange rates are reported from two deliberate tracer experiments in the southern North Sea during February 1992 and 1993. A conservative tracer, spores of the bacterium Bacillus globigii var. Niger, was used for the first time in an in situ air-sea gas exchange experiment. This nonvolatile tracer is used to correct for dispersive dilution of the volatile tracers and allows three estimations of the transfer velocity for the same time period. The first estimation of the power dependence of gas transfer on molecular diffusivity in the marine environment is reported. This allows the impact of bubbles on estimates of the transfer velocity derived from changes in the helium/sulphur hexafluoride ratio to be assessed. Data from earlier dual tracer experiments are reinterpreted, and findings suggest that results from all dual tracer experiments are mutually consistent. The complete data set is used to test published parameterizations of gas transfer with wind speed. A gas ex- change relationship that shows a dependence on wind speed intermediate between those ofLiss and Merlivat [1986] and Wanninkhof [1992] is found to be optimal. The dual tracer data are shown to be reasonably consistent with global estimates of gas exchange based on the uptake of natural and bomb-derived radiocarbon. The degree of scatter in the data when plotted against wind speed suggests that parameters not scaling with wind speed are also influencing gas exchange rates.

Impacts of Atmospheric Anthropogenic Nitrogen on the Open Ocean

Increasing quantities of atmospheric anthropogenic fixed nitrogen entering the open ocean could account for up to about a third of the oceans external (nonrecycled) nitrogen supply and up to ∼3% of the annual new marine biological production, ∼0.3 petagram of carbon per year. This input could account for the production of up to ∼1.6 teragrams of nitrous oxide (N2O) per year. Although ∼10% of the oceans drawdown of atmospheric anthropogenic carbon dioxide may result from this atmospheric nitrogen fertilization, leading to a decrease in radiative forcing, up to about two-thirds of this amount may be offset by the increase in N2O emissions. The effects of increasing atmospheric nitrogen deposition are expected to continue to grow in the future.

Short‐lived alkyl iodides and bromides at Mace Head, Ireland: Links to biogenic sources and halogen oxide production

Automated in situ gas chromatograph/mass spectrometer (GC/MS) measurements of a range of predominantly biogenic alkyl halides in air, including CHBr3, CHBr2Cl, CH3Br, C2H5Br, CH3I, C2H5I, CH2ICl, CH2I2, and the hitherto unreported CH2IBr were made at Mace Head during a 3-week period in May 1997. C3H7I and CH3CHICH3 were monitored but not detected. Positive correlations were observed between the polyhalomethane pairs CHBr3/CHBr2Cl and CHBr3/CH2IBr and between the monohalomethane pair CH3I/C2H5I, which are interpreted in terms of common or linked marine sources. During periods when air masses were affected by emissions from local seaweed beds, the concentrations of CHBr3, CH2ICl, and CH2IBr not only showed remarkable correlation but also maximized at low water. These are the first field observations to provide evidence for a link between the tidal cycle, polyhalomethanes in air, and potential marine production. The calculated total flux of iodine atoms into the boundary layer at Mace Head from organic gaseous precursors was dominated by photolytic destruction of CH2I2. Photolysis of CH3I contributed less than 3%. The calculated peak flux of iodine atoms during the campaign coincided with the highest measured levels of iodine oxide radicals, as determined using Differential Optical Absorption Spectrometry (DOAS).

The sea surface and global change

Preface List of contributors 1. Report group 1: Physical processes in the microlayer and the air-sea exchange of trace gases P. S. Liss, A. J. Watson, E. J. Bock, B. Jaehne, W. E. Asher, N. M. Frew, L. Hasse, G. M. Korenowski, L. Merlivat, L. F. Phillips, P. Schluessel, D. K. Woolf 2. Report group 2: Biological effects of chemical and radiative change in the sea surface J. T. Hardy, K. A. Hunter, D. Calmet, J. J. Cleary, R. A. Duce, T. L. Forbes, M. L. Gladyshev, G. Harding, J. M. Shenker, P. Tratynek, Y. Zaitsev 3. Report group 3: Photochemistry in the sea-surface microlayer J. M. C. Plane, N. V. Blough, M. G. Ehrhardt, K. Waters, R. G. Zepp, R. G. Zika 4. Transport processes in the sea-surface microlayer L. Hasse 5. The role of organic films in air-sea gas exchange N. M. Frew 6. Bubbles and their role in gas exchange D. K. Woolf 7. The physical chemistry of air-sea gas exchange L. F. Phillips 8. The sea-surface microlayer and its effect on global air-water gas transfer W. Asher 9. Chemistry of the sea-surface microlayer K. A. Hunter 10. Biophysics of the surface film of aquatic ecosystems M. L. Gladyshev 11. Biological effects of chemicals in the sea-surface microlayer J. T. Hardy 12. Neuston of seas and oceans Y. Zaitsev 13. Photochemistry in the sea-surface microlayer N. V. Blough 14. Hydrocarbon breakdown in the sea-surface microlayer M. G. Ehrhardt 15. Applications of laser technology and laser spectroscopy in studies of the ocean microlayer G. M. Korenowski 16. Remote sensing of the sea-surface microlayer I. Robinson Index.

An updated climatology of surface dimethlysulfide concentrations and emission fluxes in the global ocean

[1] The potentially significant role of the biogenic trace gas dimethylsulfide (DMS) in determining the Earth’s radiation budget makes it necessary to accurately reproduce seawater DMS distribution and quantify its global flux across the sea/air interface. Following a threefold increase of data (from 15,000 to over 47,000) in the global surface ocean DMS database over the last decade, new global monthly climatologies of surface ocean DMS concentration and sea‐to‐air emission flux are presented as updates of those constructed 10 years ago. Interpolation/extrapolation techniques were applied to project the discrete concentration data onto a first guess field based on Longhurst’s biogeographic provinces. Further objective analysis allowed us to obtain the final monthly maps. The new climatology projects DMS concentrations typically in the range of 1–7 nM, with higher levels occurring in the high latitudes, and with a general trend toward increasing concentration in summer. The increased size and distribution of the observations in the DMS database have produced in the new climatology substantially lower DMS concentrations in the polar latitudes and generally higher DMS concentrations in regions that were severely undersampled 10 years ago, such as the southern Indian Ocean. Using the new DMS concentration climatology in conjunction with state‐of‐the‐art parameterizations for the sea/air gas transfer velocity and climatological wind fields, we estimate that 28.1 (17.6–34.4) Tg of sulfur are transferred from the oceans into the atmosphere annually in the form of DMS. This represents a global emission increase of 17% with respect to the equivalent calculation using the previous climatology. This new DMS climatology represents a valuable tool for atmospheric chemistry, climate, and Earth System models.

Some aspects of the transfer of atmospheric trace constituents past the air-sea interface☆

Abstract This review addresses known and unknown aspects of wet and dry fluxes of atmospheric trace constituents past the air-sea interface. First, various methods for parameterizing these fluxes are developed from coupled continuity equations; also, the need for parameterizing various meteorological phenomena is illustrated. Next, different theoretical analyses of precipitation scavenging are outlined and data for collection efficiencies and washout ratios summarized. A resistance model for dry deposition illustrates that the rate-limiting stage of dry removal can occur in different layers depending on atmospheric and oceanic conditions and on properties of the pollutants; recent results for the dry fluxes of both particles and gases are summarized. After this review of known aspects of wet and dry removal processes, an interluding section uses the reviewed material to illustrate, with a number of worked examples, present capabilities to predict air pollution fluxes past the air-sea interface. Atmospheric residence times are also estimated. The second half of the paper emphasizes future research required to improve predictions of atmospheric removal processes and residence times.

Persistent sulfate formation from London Fog to Chinese haze

Significance Exceedingly high levels of fine particulate matter (PM) occur frequently in China, but the mechanism of severe haze formation remains unclear. From atmospheric measurements in two Chinese megacities and laboratory experiments, we show that the oxidation of SO2 by NO2 occurs efficiently in aqueous media under two polluted conditions: first, during the formation of the 1952 London Fog via in-cloud oxidation; and second, on fine PM with NH3 neutralization during severe haze in China. We suggest that effective haze mitigation is achievable by intervening in the sulfate formation process with NH3 and NO2 emission control measures. Hence, our results explain the outstanding sulfur problem during the historic London Fog formation and elucidate the chemical mechanism of severe haze in China. Sulfate aerosols exert profound impacts on human and ecosystem health, weather, and climate, but their formation mechanism remains uncertain. Atmospheric models consistently underpredict sulfate levels under diverse environmental conditions. From atmospheric measurements in two Chinese megacities and complementary laboratory experiments, we show that the aqueous oxidation of SO2 by NO2 is key to efficient sulfate formation but is only feasible under two atmospheric conditions: on fine aerosols with high relative humidity and NH3 neutralization or under cloud conditions. Under polluted environments, this SO2 oxidation process leads to large sulfate production rates and promotes formation of nitrate and organic matter on aqueous particles, exacerbating severe haze development. Effective haze mitigation is achievable by intervening in the sulfate formation process with enforced NH3 and NO2 control measures. In addition to explaining the polluted episodes currently occurring in China and during the 1952 London Fog, this sulfate production mechanism is widespread, and our results suggest a way to tackle this growing problem in China and much of the developing world.

On temperate sources of bromoform and other reactive organic bromine gases

Current estimates of annual bromoform production by temperate marine algae underestimate, by at least an order of magnitude, the flux required to sustain atmospheric concentrations. In the light of recent evidence of the potential of bromoform to deplete upper-tropospheric/lower-stratospheric ozone, such a substantial discrepancy in global emission rates is of considerable concern. Here we present new information on air and seawater CHBr3, CH2Br2, and CHBr2Cl concentrations in the coastal east Atlantic and review previous data from widespread locations which suggest that concentrations and ratios of reactive organobromines are consistent with marine macroalgal emissions. Detailed reviews of algal halocarbon emissions and biomass estimates imply that macroalgae produce around 70% of the worlds bromoform, rather than only ∼20% as previously thought, and that the underestimation was most likely caused by over conservative biomass estimates. Our total global source strength estimate of 2.2×1011 g CHBr3 yr−1 agrees well with recent calculations derived from atmospheric data. Given the dominant role of macroalgae in producing bromoform, the effect of changing climate and environment on seaweed populations and consequent effect on biogenic bromine emissions should be investigated.