Abstract. Global models of atmospheric mercury generally assume that gas-phase OH and ozone are the main oxidants converting Hg 0 to Hg II and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br) as an alternative Hg 0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming gas-phase Br to be the sole Hg 0 oxidant (Hg + Br model) and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O 3 model). We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O 3 models, we add an aqueous photochemical reduction of Hg II in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM) concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O 3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of Hg II deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to aCorrespondence to: C. D. Holmes (cdholmes@post.harvard.edu) net deposition flux to the Arctic of 60 Mg a −1 . Summertime events of depleted Hg 0 at Antarctic sites due to subsidence are much better simulated by the Hg + Br model. Model comparisons to observed wet deposition fluxes of mercury in the US and Europe show general consistency. However the Hg + Br model does not capture the summer maximum over the southeast US because of low subtropical Br concentrations while the Hg + OH/O 3 model does. Vertical profiles measured from aircraft show a decline of Hg 0 above the tropopause that can be captured by both the Hg + Br and Hg + OH/O 3 models, except in Arctic spring where the observed decline is much steeper than simulated by either model; we speculate that oxidation by Cl species might be responsible. The Hg + Br and Hg + OH/O 3 models yield similar global budgets for the cycling of mercury between the atmosphere and surface reservoirs, but the Hg + Br model results in a much larger fraction of mercury deposited to the Southern Hemisphere oceans.

[1] The sea breeze system (SBS) occurs at coastal locations throughout the world and consists of many spatially and temporally nested phenomena. Cool marine air propagates inland when a cross-shore mesoscale (2-2000 km) pressure gradient is created by daytime differential heating. The circulation is also characterized by rising currents at the sea breeze front and diffuse sinking currents well out to sea and is usually closed by seaward flow aloft. Coastal impacts include relief from oppressive hot weather, development of thunderstorms, and changes in air quality. This paper provides a review of SBS research extending back 2500 years but focuses primarily on recent discoveries. We address SBS forcing mechanisms, structure and related phenomena, life cycle, forecasting, and impacts on air quality.

Abstract. Atmospheric deposition of Hg(II) represents a major input of mercury to surface environments. The phase of Hg(II) (gas or particle) has important implications for deposition. We use long-term observations of reactive gaseous mercury (RGM, the gaseous component of Hg(II)), particle-bound mercury (PBM, the particulate component of Hg(II)), fine particulate matter (PM 2.5 ), and temperature (T ) at five sites in North America to derive an empirical gas-particle partitioning relationship log 10 (K −1 ) = (10±1)-(2500±300)/T where K = (PBM/PM 2.5 )/RGM with PBM and RGM in common mixing ratio units, PM 2.5 in µg m −3 , and T in K. This relationship is within the range of previous work but is based on far more extensive data from multiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition Hg(II) between the gas and particle phases. The resulting gas-phase fraction of Hg(II) ranges from over 90 % in warm air with little aerosol to less than 10 % in cold air with high aerosol. Hg deposition to high latitudes increases because of more efficient scavenging of particulate Hg(II) by precipitating snow. Model comparison to Hg observations at the North American surface sites suggests that subsidence from the free troposphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associated with high aerosol loads. Simulation of RGM and PBM at these sites is improved by including fast in-plume reduction of Hg(II) emitted from coal combustion and by assuming that anthropogenic particulate Hg(p) behaves as semivolatile Hg(II) rather than as a refractory particulate component. We improve the simulation of Hg wet deposition fluxes in the US relative to a previous version of GEOS-Chem; this largely reflects independent improvement of the washout algorithm. The observed wintertime minimum in wet deposition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II).

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[1] Airborne measurements of a large number of oxygenated volatile organic chemicals (OVOC) were carried out in the Pacific troposphere (0.1-12 km) in winter/spring of 2001 (24 February to 10 April). Specifically, these measurements included acetone (CH 3 COCH 3 ), methylethyl ketone (CH 3 COC 2 H 5 , MEK), methanol (CH 3 OH), ethanol (C 2 H 5 OH), acetaldehyde (CH 3 CHO), propionaldehyde (C 2 H 5 CHO), peroxyacylnitrates (PANs) (C n H 2n+1 COO 2 NO 2 ), and organic nitrates (C n H 2n+1 ONO 2 ). Complementary measurements of formaldehyde (HCHO), methyl hydroperoxide (CH 3 OOH), and selected tracers were also available. OVOC were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Background mixing ratios were typically highest in the lower troposphere and declined toward the upper troposphere and the lowermost stratosphere. Their total abundance (SOVOC) was nearly twice that of nonmethane hydrocarbons (SC 2 -C 8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NMHC. A comparison of these data with western Pacific observations collected some 7 years earlier (February-March 1994) did not reveal significant differences. Mixing ratios of OVOC were strongly correlated with each other as well as with tracers of fossil and biomass/biofuel combustion. Analysis of the relative enhancement of selected OVOC with respect to CH 3 Cl and CO in 12 plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. A three-dimensional global model that uses state of the art chemistry and source information is used to compare measured and simulated mixing ratios of selected OVOC. While there is reasonable agreement in many cases, measured aldehyde concentrations are significantly larger than predicted. At their observed levels, acetaldehyde mixing ratios are shown to be an important source of HCHO (and HO x ) and PAN in the troposphere. On the basis of presently known chemistry, measured mixing ratios of aldehydes and PANs are mutually incompatible. We provide rough estimates of the global sources of several OVOC and conclude that collectively these are extremely large (150-500 Tg C yr À1 ) but remain poorly quantified.

Abstract. 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 (ZOx-organic) nearly equals that of total nonmethane hydrocarbons (ZNMHC), which have been traditionally measured.

Abstract. Peroxyacetyl nitrate (PAN) formed in the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) is the principal tropospheric reservoir for nitrogen oxide radicals (NOx = NO + NO2). PAN enables the transport and release of NOx to the remote troposphere with major implications for the global distributions of ozone and OH, the main tropospheric oxidants. Simulation of PAN is a challenge for global models because of the dependence of PAN on vertical transport as well as complex and uncertain NMVOC sources and chemistry. Here we use an improved representation of NMVOCs in a global 3-D chemical transport model (GEOS-Chem) and show that it can simulate PAN observations from aircraft campaigns worldwide. The immediate carbonyl precursors for PAN formation include acetaldehyde (44% of the global source), methylglyoxal (30%), acetone (7%), and a suite of other isoprene and terpene oxidation products (19%). A diversity of NMVOC emissions is responsible for PAN formation globally including isoprene (37%) and alkanes (14%). Anthropogenic sources are dominant in the extratropical Northern Hemisphere outside the growing season. Open fires appear to play little role except at high northern latitudes in spring, although results are very sensitive to plume chemistry and plume rise. Lightning NOx is the dominant contributor to the observed PAN maximum in the free troposphere over the South Atlantic.

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.