Air-Sea Exchange in the Global Mercury Cycle

We present results from a new global atmospheric mercury model coupled with a mixed layer slab ocean. The ocean model describes the interactions of the mixed layer with the atmosphere and deep ocean, as well as conversion between elemental, divalent, and nonreactive mercury species. Our global mean aqueous concentrations of 0.07 pM elemental, 0.80 pM reactive, and 1.51 pM total mercury agree with observations. The ocean provides a 14.1 Mmol yr−1 source of mercury to the atmosphere, at the upper end of previous estimates. Re-emission of previously deposited mercury constitutes 89% of this flux. Ocean emissions are largest in the tropics and downwind of industrial regions. Midlatitude ocean emissions display a large seasonal cycle induced by biological productivity. Oceans contribute 54% (36%) of surface atmospheric mercury in the Southern (Northern) Hemisphere. We find a large net loss of mercury to the deep ocean (8.7 Mmol yr−1), implying a ∼0.7%/year increase in deep ocean concentrations.Earth and Planetary SciencesEngineering and Applied Science

El Niño-Southern Oscillation influence on tropospheric mercury concentrations

The El Nino-Southern Oscillation (ENSO) affects the tropospheric concentrations of many trace gases. Here we investigate the ENSO influence on mercury concentrations measured in the upper troposphere during Civil Aircraft for the Regular Investigation of the atmosphere Based on an instrumented Container flights and at ground at Cape Point, South Africa, and Mace Head, Ireland. Mercury concentrations cross-correlate with Southern Oscillation Index (SOI) with a lag of 8 +/- 2 months. Highest mercury concentrations are always found at the most negative SOI values, i.e., 8 months after El Nino, and the amplitude of the interannual variations fluctuates between similar to 5 and 18%. The time lag is similar to that of CO whose interannual variations are driven largely by emissions from biomass burning (BB). The amplitude of the interannual variability of tropospheric mercury concentrations is consistent with the estimated variations in mercury emissions from BB. We thus conclude that BB is a major factor driving the interannual variation of tropospheric mercury concentrations

Mercury plumes in the global upper troposphere observed during flights with the CARIBIC observatory from May 2005 until June 2013

Tropospheric sections of flights with the CARIBIC (Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrumented Container) observatory from May 2005 until June 2013, are investigated for the occurrence of plumes with elevated Hg concentrations. Additional information on CO, CO, CH, NO, O, hydrocarbons, halocarbons, acetone and acetonitrile enable us to attribute the plumes to biomass burning, urban/industrial sources or a mixture of both. Altogether, 98 pollution plumes with elevated Hg concentrations and CO mixing ratios were encountered, and the Hg/CO emission ratios for 49 of them could be calculated. Most of the plumes were found overEast Asia, in the African equatorial region, over South America and over Pakistan and India. The plumes encountered over equatorial Africa and over South America originate predominantly from biomass burning, as evidenced by the low Hg/CO emission ratios andelevated mixing ratios of acetonitrile, CHCl and particle concentrations. The backward trajectories point to the regions around the Rift Valley and the Amazon Basin, with its outskirts, as the source areas. The plumes encountered over East Asia and over Pakistan and India are predominantly of urban/industrial origin, sometimes mixed with products of biomass/biofuel burning. Backward trajectories point mostly to source areas in China andnorthern India. The Hg/CO and Hg/CH emission ratios for several plumes are also presented and discussed

A new mechanism for atmospheric mercury redox chemistry:implications for the global mercury budget

Mercury (Hg) is emitted to the atmosphere mainly as volatile elemental Hg0. Oxidation to water-soluble HgII plays a major role in Hg deposition to ecosystems. Here, we implement a new mechanism for atmospheric Hg0 ∕ HgII redox chemistry in the GEOS-Chem global model and examine the implications for the global atmospheric Hg budget and deposition patterns. Our simulation includes a new coupling of GEOS-Chem to an ocean general circulation model (MITgcm), enabling a global 3-D representation of atmosphere–ocean Hg0 ∕ HgII cycling. We find that atomic bromine (Br) of marine organobromine origin is the main atmospheric Hg0 oxidant and that second-stage HgBr oxidation is mainly by the NO2 and HO2 radicals. The resulting chemical lifetime of tropospheric Hg0 against oxidation is 2.7 months, shorter than in previous models. Fast HgII atmospheric reduction must occur in order to match the  ∼  6-month lifetime of Hg against deposition implied by the observed atmospheric variability of total gaseous mercury (TGM  ≡  Hg0 + HgII(g)). We implement this reduction in GEOS-Chem as photolysis of aqueous-phase HgII–organic complexes in aerosols and clouds, resulting in a TGM lifetime of 5.2 months against deposition and matching both mean observed TGM and its variability. Model sensitivity analysis shows that the interhemispheric gradient of TGM, previously used to infer a longer Hg lifetime against deposition, is misleading because Southern Hemisphere Hg mainly originates from oceanic emissions rather than transport from the Northern Hemisphere. The model reproduces the observed seasonal TGM variation at northern midlatitudes (maximum in February, minimum in September) driven by chemistry and oceanic evasion, but it does not reproduce the lack of seasonality observed at southern hemispheric marine sites. Aircraft observations in the lowermost stratosphere show a strong TGM–ozone relationship indicative of fast Hg0 oxidation, but we show that this relationship provides only a weak test of Hg chemistry because it is also influenced by mixing. The model reproduces observed Hg wet deposition fluxes over North America, Europe, and China with little bias (0–30 %). It reproduces qualitatively the observed maximum in US deposition around the Gulf of Mexico, reflecting a combination of deep convection and availability of NO2 and HO2 radicals for second-stage HgBr oxidation. However, the magnitude of this maximum is underestimated. The relatively low observed Hg wet deposition over rural China is attributed to fast HgII reduction in the presence of high organic aerosol concentrations. We find that 80 % of HgII deposition is to the global oceans, reflecting the marine origin of Br and low concentrations of organic aerosols for HgII reduction. Most of that deposition takes place to the tropical oceans due to the availability of HO2 and NO2 for second-stage HgBr oxidation

Multi-model study of mercury dispersion in the atmosphere: vertical and interhemispheric distribution of mercury species

Atmospheric chemistry and transport of mercury play a key role in the global mercury cycle. However, there are still considerable knowledge gaps concerning the fate of mercury in the atmosphere. This is the second part of a model intercomparison study investigating the impact of atmospheric chemistry and emissions on mercury in the atmosphere. While the first study focused on ground-based observations of mercury concentration and deposition, here we investigate the vertical and interhemispheric distribution and speciation of mercury from the planetary boundary layer to the lower stratosphere. So far, there have been few model studies investigating the vertical distribution of mercury, mostly focusing on single aircraft campaigns. Here, we present a first comprehensive analysis based on various aircraft observations in Europe, North America, and on intercontinental flights. The investigated models proved to be able to reproduce the distribution of total and elemental mercury concentrations in the troposphere including interhemispheric trends. One key aspect of the study is the investigation of mercury oxidation in the troposphere. We found that different chemistry schemes were better at reproducing observed oxidized mercury patterns depending on altitude. High concentrations of oxidized mercury in the upper troposphere could be reproduced with oxidation by bromine while elevated concentrations in the lower troposphere were better reproduced by OH and ozone chemistry. However, the results were not always conclusive as the physical and chemical parameterizations in the chemistry transport models also proved to have a substantial impact on model results

Large scale distribution of nitrogen oxides in the UTLS - Results of NO and NOy measurements during CARIBIC

Measurements of nitrogen oxides performed in the upper troposphere and lower stratosphere are presented. NO and NOy measurements contribute to the identification of specific sources determining the trace gas budget around the tropopause. These observations were carried out within the CARIBIC project (Civil aircraft for the regular investigation on the atmosphere based on an instrument container). Since its first deployment in spring 2002 the NO and NOy instrument has been successfully operated during more than 70 flights with a Lufthansa Airbus. Most of the flights have been performed between Germany and South America (Sao Paulo and Santiago de Chile) and between Germany and the Far East (Guangzhou and Manila). During these long-haul flights NO and NOy concentrations in the upper troposphere and lowermost stratosphere have been determined along with species as CO, O3, particles, and others. These data were used to study the influence of long range transport, deep convection, lightning, and air traffic emissions on the nitrogen oxides budget in the UTLS region. Case studies and correlation analyses are presented. First attempts have also been made at assessing the seasonal variation of nitrogen oxides in the probed UTLS region. Average NO and NOy concentrations obtained during CARIBIC are compared to the results obtained during other aircraft measuring campaigns like NOXAR and SCOUT

In-Flight Measurement of Aircraft Non-Methane Hydrocarbon Emission Indices

Concentrations of non-methane hydrocarbons (NMHC) and CO were measured in exhaust plumes of the DLR experimental aircraft ATTAS equipped with Rolls Royce M 45H MK501 engines. The emission indices (EI) of individual light NMHC were determined from ratios of NMHC and CO concentration enhancements measured in grab samples and the concurrent in-flight measurements of EI of CO by FTIR emission spectroscopy. Alkenes and alkynes generated by cracking of larger NMHC molecules and aromatic compounds originating from unburnt fuel constituted a larger and a smaller fraction of the NMHC emissions, respectively