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Chloromethane (CH3Cl) is an important source of chlorine in the stratosphere, but detailed knowledge of the magnitude of its sources and sinks is missing. Here, we measured the stable chlorine isot...

Chloromethane (CH3Cl) is the most important natural input of reactive chlorine to the stratosphere, contributing about 16 % to stratospheric ozone depletion. Due to the phase-out of anthropogenic emissions of chlorofluorocarbons, CH3Cl will largely control future levels of stratospheric chlorine. The tropical rainforest is commonly assumed to be the strongest single CH3Cl source, contributing over half of the global annual emissions of about 4000 to 5000 Gg (1 Gg = 109 g). This source shows a characteristic carbon isotope fingerprint, making isotopic investigations a promising tool for improving its atmospheric budget. Applying carbon isotopes to better constrain the atmospheric budget of CH3Cl requires sound information on the kinetic isotope effects for the main sink processes: the reaction with OH and Cl in the troposphere. We conducted photochemical CH3Cl degradation experiments in a 3500 dm3 smog chamber to determine the carbon isotope effect (ε=k13C/k12C-1) for the reaction of CH3Cl with OH and Cl. For the reaction of CH3Cl with OH, we determined an ε value of (-11.2±0.8) ‰ (n=3) and for the reaction with Cl we found an ε value of (-10.2±0.5) ‰ (n=1), which is 5 to 6 times smaller than previously reported. Our smaller isotope effects are strongly supported by the lack of any significant seasonal covariation in previously reported tropospheric δ13C(CH3Cl) values with the OH-driven seasonal cycle in tropospheric mixing ratios. Applying these new values for the carbon isotope effect to the global CH3Cl budget using a simple two hemispheric box model, we derive a tropical rainforest CH3Cl source of (670±200) Gg a−1, which is considerably smaller than previous estimates. A revision of previous bottom-up estimates, using above-ground biomass instead of rainforest area, strongly supports this lower estimate. Finally, our results suggest a large unknown CH3Cl source of (1530±200) Gg a−1.

Bacteriohopanepolyols (BHPs) are lipid constituents of many bacterial groups. Geohopanoids, the diagenetic products, are therefore ubiquitous in organic matter of the geosphere. To examine the potential of BHPs as environmental markers in marine sediments, we investigated a Holocene sediment core from the Black Sea. The concentrations of BHPs mirror the environmental shift from a well-mixed lake to a stratified marine environment by a strong and gradual increase from low values (∼30 μg g−1 TOC) in the oldest sediments to ∼170 μg g−1 TOC in sediments representing the onset of a permanently anoxic water body at about 7500 years before present (BP). This increase in BHP concentrations was most likely caused by a strong increase in bacterioplanktonic paleoproductivity brought about by several ingressions of Mediterranean Sea waters at the end of the lacustrine stage (∼9500 years BP). δ15N values coevally decreasing with increasing BHP concentrations may indicate a shift from a phosphorus- to a nitrogen-limited setting supporting growth of N2-fixing, BHP-producing bacteria. In sediments of the last ∼3000 years BHP concentrations have remained relatively stable at about 50 μg g−1 TOC. The distributions of major BHPs did not change significantly during the shift from lacustrine (or oligohaline) to marine conditions. Tetrafunctionalized BHPs prevailed throughout the entire sediment core, with the common bacteriohopanetetrol and 35-aminobacteriohopanetriol and the rare 35-aminobacteriohopenetriol, so far only known from a purple non-sulfur α-proteobacterium, being the main components. Other BHPs specific to cyanobacteria and pelagic methanotrophic bacteria were also found but only in much smaller amounts. Our results demonstrate that BHPs from microorganisms living in deeper biogeochemical zones of marine water columns are underrepresented or even absent in the sediment compared to the BHPs of bacteria present in the euphotic zone. Obviously, the assemblage of molecular fossils in the sediments does not represent an integrated image of the entire community living in the water column. Remnants of organisms living in zones where effective transport mechanisms – such as the fecal pellet express – exist are accumulated while those of others are underrepresented. Our work shows a high stability of BHPs over geological time scales. Largely uniform distributions and only minor changes in structures like an increasing prevalence of saturated over unsaturated BHPs with time were observed. Consequently, sedimentary BHP distributions are less suitable as markers for in situ living bacteria but are useful for paleoreconstructions of bacterioplanktonic communities and productivity changes.

International audience; An international campaign involving six teams was organized in Ny-Ålesund, Svalbard, in order to understand better the origin of atmospheric mercury depletion events (AMDEs). Special emphasis was given to determining the source region of the observed events and the physical and chemical processes leading to AMDEs. Five AMDEs were recorded during a one-month field experiment (10 April-10 May, 2003). The different events presented various characteristics, especially in terms of mercury species formation, atmospheric particle variations and meteorological conditions. After careful examination of each event, we postulate that two were probably due to advection of already depleted air masses and three were a product of local or regional chemistry. The roles of different surfaces (frost flowers, snow, ice aerosol in clouds) involved in heterogeneous reactions leading to AMDEs are also discussed. We speculate that ice clouds may explain the particle variations observed during the three more local events.

International audience; Six groups participated in an international study of springtime atmospheric mercury depletion events (AMDEs) at Ny-Ålesund in the Norwegian Arctic during April and May 2003 with the aim to compare analytical methods for measurements of atmospheric mercury species and study the physical and chemical processes leading to AMDEs. Five groups participated in the method comparison that was conducted at three different locations within Ny-Ålesund. Various automated and manual instrumentation were used to sample, measure and compare gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated with particles (Hg-P). The concentration of GEM was reproducible during background conditions. For the first time using ambient air, the statistics associated with round robin test procedures were applied. This was found to be an appropriate tool to investigate the reproducibility of GEM measurements in ambient air. The precision for each group measuring GEM concentrations was found to be consistently good (within 5%). Five AMDEs were recorded during the study. Using four different methods, including single and replicate samples, all groups recorded higher values of RGM and Hg-P during AMDEs. The results show that measuring comparable atmospheric mercury species at both the same and different locations (within the Ny-Ålesund area) is difficult. Not only do site location and site characteristics create challenges when trying to intercompare results but there are difficulties, as well, in obtaining comparable results with similar sampling and analysis methods. Nevertheless, with our current procedures for atmospheric mercury identification we can differentiate with certainty between “high” and “low” concentration values of RGM and Hg-P.

In this study we report fluxes of chloromethane (CH3Cl), bromomethane (CH3Br), iodomethane (CH3I), and bromoform (CHBr3) from two sampling campaigns (summer and spring) in the seagrass dominated subtropical lagoon Ria Formosa, Portugal. Dynamic flux chamber measurements were performed when seagrass patches were either air-exposed or submerged. Overall, we observed highly variable fluxes from the seagrass meadows and attributed them to diurnal cycles, tidal effects, and the variety of possible sources and sinks in the seagrass meadows. The highest emissions with up to 130 nmol m−2 h−1 for CH3Br were observed during tidal changes, from air exposure to submergence and conversely. Furthermore, during the spring campaign, the emissions of halocarbons were significantly elevated during tidal inundation as compared to air exposure. Accompanying water sampling performed during both campaigns revealed elevated concentrations of CH3Cl and CH3Br, indicating productive sources within the lagoon. Stable carbon isotopes of halocarbons from the air and water phase along with source signatures were used to allocate the distinctive sources and sinks in the lagoon. Results suggest that CH3Cl was rather originating from seagrass meadows and water column than from salt marshes. Aqueous and atmospheric CH3Br was substantially enriched in 13C in comparison to source signatures for seagrass meadows and salt marshes. This suggests a significant contribution from the water phase on the atmospheric CH3Br in the lagoon. A rough global upscaling yields annual productions from seagrass meadows of 2.3–4.5 Gg yr−1, 0.5–1.0 Gg yr−1, 0.6–1.2 Gg yr−1, and 1.9–3.7 Gg yr−1 for CH3Cl, CH3Br, CH3I, and CHBr3 respectively. This suggests a minor contribution from seagrass meadows to the global production of CH3Cl and CH3Br with about 0.1 and 0.7%, respectively. In comparison to the known marine sources for CH3I and CHBr3, seagrass meadows are rather small sources.

Coastal zones are important source regions for a variety of trace gases including halocarbons and sulphur-bearing species. While salt-marshes, macroalgae and phytoplankton communities have been intensively studied, little is known about trace gas fluxes in seagrass meadows. Here we report results of a newly developed dynamic flux chamber system that can be deployed in intertidal areas over full tidal cycles allowing for high time resolved measurements. The trace gases measured in this study included carbon dioxide (CO2), methane (CH4) and a variety of hydrocarbons, halocarbons and sulphur-bearing compounds. The high time resolved CO2 and CH4 flux measurements revealed a complex dynamic mediated by tide and light. In contrast to most previous studies our data indicate significantly enhanced fluxes during tidal immersion relative to periods of air exposure. Short emission peaks occured with onset of the feeder current at the sampling site. We suggest an overall strong effect of advective transport processes to explain the elevated fluxes during tidal immersion. Many emission estimates from tidally influenced coastal areas still rely on measurements carried out during low tide only. Hence, our results may have significant implications for budgeting trace gases in coastal areas. This dynamic flux chamber system provides intensive time series data of community respiration (at night) and net community production (during the day) of shallow coastal systems.

The isotopic composition of volatile organic compounds (VOCs) can provide valuable information on their sources and fate not deducible from mixing ratios alone. In particular the reported carbon stable isotope ratios of chloromethane and bromomethane from different sources cover a δ13C-range of almost 100‰ making isotope ratios a very promising tool for studying the biogeochemistry of these compounds. So far, the determination of the isotopic composition of C1 and C2 halocarbons others than chloromethane is hampered by their low mixing ratios. In order to determine the carbon isotopic composition of C1 and C2 halocarbons with mixing ratios as low as 1 pptv (i) a field suitable cryogenic high volume sampling system and (ii) a chromatographic set up for processing these samples have been developed and validated. The sampling system was tested at two different sampling sites, an urban and a coastal location in Northern Germany. The average δ13C-values for bromomethane at the urban site were −42.9 ± 1.1‰ and agreed well with previously published results. But at the coastal site bromomethane was substantially enriched in 13C by almost 10‰. Less pronounced differences were observed for chlorodifluoromethane, 1,1,1-trichloroethane and chloromethane. We suggest that these differences are related to the turnover of these compounds in ocean surface waters. Furthermore we report first carbon isotope ratios for iodomethane (−40.4‰ to −79.8‰), bromoform (−13.8‰ to 22.9‰), and other halocarbons.

International audience; In March 2005, an extensive mercury study was performed just before snowmelt at Col de Porte, an alpine site close to Grenoble, France. Total mercury concentration in the snowpack ranged from 80 ± 08 to 160 ± 15 ng l−1, while reactive mercury was below detection limit (0.2 ng l−1). We observed simultaneously a production of gaseous elemental mercury (GEM) in the top layer of the snowpack and an emission flux from the snow surface to the atmosphere. Both phenomena were well correlated with solar irradiation, indicating photo-induced reactions in the snow interstitial air (SIA). The mean daily flux of GEM from the snowpack was estimated at ∼9 ng m−2 d−1. No depletion of GEM concentrations was observed in the SIA, suggesting no occurrence of oxidation processes. The presence of liquid water in the snowpack clearly enhanced GEM production in the SIA. Laboratory flux chamber measurements enabled us to confirm that GEM production from this alpine snowpack was first driven by solar radiation (especially UVA and UVB radiation), and then by liquid water in the snowpack. Finally, a large GEM emission from the snow surface occurred during snowmelt, and we report total mercury concentrations in meltwater of about 72 ng l−1.

International audience; Snow surfaces play an important role in the biogeochemical cycle of mercury in high-latitude regions. Snowpacks act both as sources and sinks for gaseous compounds. Surprisingly, the roles of each environmental parameter that can govern the air–surface exchange over snow are not well understood owing to the lack of systematic studies. A laboratory system called the laboratory flux measurement system was used to study the emission of gaseous elemental mercury from a natural snowpack under controlled conditions. The first results from three snowpacks originating from alpine, urban and polar areas are presented. Consistent with observations in the field, we were able to reproduce gaseous mercury emissions and showed that they are mainly driven by solar radiation and especially UV-B radiation. From these laboratory experiments, we derived kinetic constants which show that divalent mercury can have a short natural lifetime of about 4–6 h in snow.

International audience; The study of mercury (Hg) cycle in Arctic regions is a major subject of concern due to the dramatic increases of Hg concentrations in ecosystem in the last few decades. The causes of such increases are still in debate, and an important way to improve our knowledge on the subject is to study the exchanges of Hg between atmosphere and snow during springtime. We organized an international study from 10 April to 10 May 2003 in Ny-Ålesund, Svalbard, in order to assess these fluxes through measurements and derived calculations. Snow-to-air emission fluxes of Hg were measured using the flux chamber technique between 0 and 50 ng m−2 h−1. A peak in Gaseous Elemental Mercury (GEM) emission flux from the snow to the atmosphere has been measured just few hours after an Atmospheric Mercury Depletion Event (AMDE) recorded on 22 April 2004. Surprisingly, this peak in GEM emitted after this AMDE did not correspond to any increase in Hg concentration in snow surface. A peak in GEM flux after an AMDE was observed only for this single event but not for the four other AMDEs recorded during this spring period. In the snow pack which is seasonal and about 40 cm depth above permafrost, Hg is involved in both production and incorporation processes. The incorporation was evaluated to 5-40 pg m2 h. Outside of AMDE periods, Hg flux from the snow surface to the atmosphere was the consequence of GEM production in the air of snow and was about 15-50 ng m−2 h−1, with a contribution of deeper snow layers evaluated to 0.3-6.5 ng m−2 h−1. The major part of GEM production is then mainly a surface phenomenon. The internal production of GEM was largely increasing when snow temperatures were close to melting, indicating a chemical process occurring in the quasi-liquid layer at the surface of snow grains.