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Transparent exopolymer particles (TEP) exhibit the properties of gels and are ubiquitously found in the world oceans. Possibly, TEP may enter the atmosphere as part of sea spray aerosol. Here, we report number concentrations of TEP (diameter > 4.5 µm) in ambient aerosol and cloud water samples from the tropical Atlantic Ocean as well as in generated aerosol particles using a plunging waterfall tank that was filled with the ambient sea water. The ambient TEP concentrations ranged between 7 × 102 and 3 × 104 #TEP m−3 in supermicron aerosol particles and correlations to sodium (Na+) and calcium (Ca2+) (R2 = 0.5) suggested some contribution via bubble bursting. Cloud water TEP concentrations were between 4 × 106 and 9 × 106 #TEP L−1 corresponding to equivalent air concentrations of 2–4 × 103 #TEP m−3. The TEP concentrations in the tank-generated aerosol particles, produced from the same waters and sampled with an equivalent system, were significantly lower (4 × 102–2 × 103 #TEP m−3) compared to the ambient concentrations. Based on Na+ concentrations in seawater and in the atmosphere, the enrichment factor for TEP in the atmosphere was calculated. The tank-generated TEP were enriched by a factor of 50 compared to sea water and, therefore, in-line with published enrichment factors for supermicron organic matter in general and TEP specifically. TEP enrichment in the ambient atmosphere was on average 1 × 103 in cloud water and 9 × 103 in ambient aerosol particles and therefore about two orders of magnitude higher than the corresponding enrichment from the tank study. Such high enrichment of supermicron particulate organic constituents in the atmosphere is uncommon and we propose that atmospheric TEP concentrations resulted from a combination of enrichment during bubble bursting transfer from the ocean and TEP in-situ formation in atmospheric phases. Abiotic in-situ formation might have occurred from aqueous reactions of dissolved organic precursors that were present in particle and cloud water samples, while biotic formation involves bacteria, which were abundant in the cloud water samples. The ambient TEP number concentrations were two orders of magnitude higher than recently reported ice nucleating particle (INP) concentrations measured at the same location. As TEP likely possess good properties to act as INP, in future experiments it is worth studying if a certain part of TEP contributes a fraction of the biogenic INP population.

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...

Knowledge related to sulfur isotope ratios of carbonyl sulfide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. An earlier method developed for sulfur isotopic analysis for OCS using S + fragmentation by an isotope ratio mass spectrometer is inapplicable for ambient air samples because of the large samples required (approx. 500 L of 500 pmol mol −1 OCS). To overcome this difficulty, herein we present a new sampling system for collecting approximately 10 nmol of OCS from ambient air coupled with a purification system. Salient system features are (i) accommodation of samples up to 500 L (approx. 10 nmol) of air at 5 L min −1 ; (ii) portability of adsorption tubes ( 1∕4 in. (0.64 cm) outer diameter, 17.5 cm length, approximately 1.4 cm 3 volume) for preserving the OCS amount and δ34 S(OCS) values at − 80 ∘ C for up to 90 days and 14 days; and (iii) purification OCS from other compounds such as CO2 . We tested the OCS collection efficiency of the systems and sulfur isotopic fractionation during sampling. Results show precision (1 σ ) of δ34 S(OCS) values as 0.4 ‰ for overall procedures during measurements for atmospheric samples. Additionally, this report presents diurnal variation of δ34 S(OCS) values collected from ambient air at the Suzukakedai campus of the Tokyo Institute of Technology located in Yokohama, Japan. The observed OCS concentrations and δ34 S(OCS) values were, respectively, 447–520 pmol mol −1 and from 10.4 ‰ to 10.7 ‰ with a lack of diurnal variation. The observed δ34 S(OCS) values in ambient air differed greatly from previously reported values of δ34 S(OCS) = ( 4.9±0.3 ) ‰ for compressed air collected at Kawasaki, Japan, presumably because of degradation of OCS in cylinders and collection processes for that sample. The difference of atmospheric δ34 S(OCS) values between 10.5 ‰ in Japan (this study) and ∼13 ‰ recently reported in Israel or the Canary Islands indicates that spatial and temporal variation of δ34 S(OCS) values is expected due to a link between anthropogenic activities and OCS cycles. The system presented herein is useful for application of δ34 S(OCS) for investigation of OCS sources and sinks in the troposphere to elucidate its cycle.

The project MarParCloud (marine biological production, organic aerosol particles and marine clouds: a process chain) aims at achieving a better understanding of the biological production of organic matter (OM)in the oceans, its export into marine aerosol particles and finally its ability to act as ice and cloud condensation nuclei (INP and CCN). The core of MarParCloud comprised a field campaign at the Cape Verde Atmosphere Observatory (CVAO) in autumn 2017, where a variety of chemical, physical, biological and meteorological approaches were applied. The investigations included concerted measurements of the bulk water, the Sea Surface Microlayer (SML), ambient aerosol particles on the ground (30 m a.s.l.) and in mountain heights (744 m) as well as cloud water. Important aspects of the ocean atmosphere Interactions focusing on marine OM have been addressed through detailed observation and modeling approaches.Key variables comprised the chemical characterization of the atmospherically relevant OM components (e.g. lipids, proteins, sugars) in the ocean and the atmosphere as well as measurements of INP and CCN. Moreover, bacterial cell counts, mercury species and trace gases were analysed. To interpret the results, the measurements were accompanied by various auxiliary parameters such as air mass back trajectory analysis, vertical atmospheric profile analysis, cloud observations and pigment measurements in seawater. Additional modelling studies supported the experimental analysis.Here we show the proof of concept of the connection between organic matter emission from the ocean to the atmosphere and up to the cloud level. A link between the ocean and the atmosphere was clearly observed as (i) the particles measured at the surface are well mixed within the marine boundary layer up to cloud level and (ii) ocean-derived compounds can be found in the aerosol particles at mountain height and in the cloud water. The organic measurements will be implemented in a new source function for the oceanic emission of OM. However, from a perspective of particle number concentrations, the marine contributions to both CCN and INP are rather limited.

Knowledge related to sulfur isotopic composition of carbonyl sulphide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. Earlier method developed for sulfur isotopic analysis for OCS using S + fragmentation is inapplicable for ambient air samples because of the large samples required (approx. 500 L of 500 pmol mol −1 OCS). To overcome this difficulty, herein we present a new sampling system for collecting approx. 10 nmol of OCS from ambient air coupled with a purification system. Salient system features are (i) accommodation of samples up to 500 L (= approx. 10 nmol) of air at 5 L min −1 , (ii) portability of 7 inch tubes (approx. 1 cm 3 ) for preserving samples, and (iii) purification OCS from other compounds such as CO 2 . We tested the OCS collection efficiency of the systems and sulfur isotopic fractionation during sampling. Results show precision (1σ) of δ 33 S(OCS), δ 34 S(OCS), and Δ 33 S(OCS) values, respectively, as 0.4 ‰, 0.2 ‰, and 0.4 ‰. Additionally, this report presents diurnal variation of δ 34 S(OCS) values collected from ambient air at Suzukakedai campus of Tokyo Institute of Technology located in Yokohama, Japan. The observed OCS concentrations and δ 34 S(OCS) values were, respectively, 447–520 pmol mol −1 and from 10.4 ‰ to 10.7 ‰. No significant difference was found between values obtained during the day and night. The observed δ 34 S(OCS) values in ambient air differed greatly from previously reported values ((4.9 ± 0.3) ‰) for compressed air collected at Kawasaki, Japan, presumably because of sampling conditions and collection processes for that sample. Consequently, previous values of δ 34 S(OCS) = (4.9 ± 0.3) ‰ were not representative samples for a global signal. When considering (10.5 ± 0.4) ‰ is postulated as the global signal of δ 34 S(OCS), this revised δ 34 S(OCS) value is consistent with previous estimation based on terrestrial and oceanic sulfur sources. The δ 34 S(OCS) value explains the reported δ 34 S(OCS) values for background stratospheric sulfate. The system presented herein is useful for application of δ 34 S(OCS) for investigation of OCS sources and sinks in the troposphere to elucidate its cycle and its contribution to background stratospheric sulfate.

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.

Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but yet lacks detailed knowledge of its budget. Stable isotope analysis is potentially a powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog-chamber at 293 ± 1 K. We measured the increasing stable hydrogen isotope values of the unreacted CH3Cl using compound specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −242 ± 7 mUr (or ‰) and −280 ± 11 mUr, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of −205 ± 6 mUr which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

Halocarbons are important vectors of reactive halogens to the atmosphere, where the latter participate in several chemical key processes. Many efforts have been made to quantify their sources and sinks. However, those are still designated to large uncertainties. In contrast to other coastal habitats such as salt marshes and kelp communities, seagrass meadows have so far not been investigated with regard to trace gases. In order to study seagrass meadows as a potential source for halocarbons to the atmosphere, we conducted dynamic flux chamber measurements at a coastal site in List/Sylt, Northern Germany. Emissions of halocarbons from seagrass meadows into the atmosphere were found for chloromethane (CH 3 Cl), bromomethane (CH 3 Br), iodomethane (CH 3 I), and bromoform (CHBr 3 ) being the main compounds, while the sediment seems to be a net sink for CH 3 Cl and CH 3 Br. Stable carbon isotopes of halocarbons were determined using a newly developed comprehensive coupled isotope and mass balance for dynamic flux chambers. Mean stable carbon isotope compositions of the emitted halocarbons were −50‰ (CH 3 Cl), −52‰ (CH 3 Br), −63‰ (CH 3 I) and −14‰ (CHBr 3 ).

Sedimentary δ15N records are valuable archives of ocean history but they are often modified during early diagenesis. Here we quantify the effect of early diagenetic enrichment on sedimentary N-isotope composition in order to obtain the pristine signal of reactive N assimilated in the euphotic zone. This is possible by using paired data of δ15N and amino acid composition of sediment samples, which can be applied to estimate the degree of organic matter degradation. We determined δ15N and amino acid composition in coeval sediments from Ocean Drilling Program (ODP) Hole 772 B in the central Arabian Sea and from Hole 724 C situated on the Oman Margin in the western Arabian Sea coastal upwelling area. The records span the last 130 kyr and include two glacial–interglacial cycles. These new data are used in conjunction with data available for surface sediments that cover a wide range of organic matter degradation states, and with other cores from the northern and eastern Arabian Sea to explore spatial variations in the isotopic signal. In order to reconstruct pristine N values we apply the relationship between organic matter degradation and 15N enrichment in surface sediments to correct the core records for early diagenetic enrichment. Reconstructed δ15N values suggest a significant role of N2-fixation during glacial stages. An evaluation of two preservation indices based on amino acid composition (Reactivity Index, RI; Jennerjahn and Ittekkot, 1997; and the Degradation Index, DI; Dauwe et al., 1999) in both recent sediments and core samples suggests that the RI is more suitable than the DI in correcting Arabian Sea δ15N records for early diagenetic enrichment.

In the present study, we analyze the fate of airborne nitrogen in heathland ecosystems (NW Germany) by means of a 15N tracer experiment. Our objective was to quantify N sequestration and N allocation patterns in an ecosystem that is naturally limited by N, but that has been exposed to airborne N inputs exceeding critical loads for more than 3 decades. We hypothesized that the system has a tendency towards N saturation, which should be indicated by low N sequestration and high N leaching. We analyzed 15N partitioning (aboveground biomass and soil horizons) and investigated 15N leaching over 2 years following a 15N tracer pulse addition. 15N tracer recovery was 90% and 76% in the first and second year, respectively. Contrary to our expectations, more than 99% of the tracer recovered was sequestered in the biomass and soil, while leaching losses were

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.

Nitrogen isotopes of organic matter are increasingly studied in marine biogeochemistry and geology, plant and animal ecology, and paleoceanography. Here, we present results of an inter-laboratory test on determination of nitrogen isotope ratios in marine and lacustrine sediments. Six different samples covering a wide range of total nitrogen content and delta N-15 values were analyzed by eight different laboratories using their routine procedures. The laboratories were asked to measure three batches with three replicates for each sample to assess accuracy and variability within and among laboratories; this permits assessment of repeatability and reproducibility, which are essential in meta analysis of the increasing database on delta N-15 values in marine sediments. The grand average delta N-15 values for individual samples ranged from 1.65-10.90 parts per thousand One laboratory exhibited an average bias of -0.27 parts per thousand compared to the mean of all other laboratories. Apart from one sample, which showed an exceptionally high overall standard deviation (OSD) of 0.51 parts per thousand, the analytical precision (1 s) averaged 0.24 parts per thousand, ranging from 0.18-0.31 parts per thousand. for individual samples. Out of the eight participating laboratories, two showed a significantly elevated within-laboratory standard deviation (WLSD) of 0.41 parts per thousand and 0.32 parts per thousand compared to an average WLSD of 0.15 parts per thousand for the other laboratories. The WLSD was inversely correlated with the ratio of peak height to peak width, which was taken as a simple measure of peak shape. Moreover, our data also revealed an inverse correlation between total nitrogen content and measurement precision. These correlations may provide guidance for improving the measurement precision of individual laboratories. Based on the results of this round robin test, we have estimated the expanded measurement uncertainty on the 2 sigma level to 0.45 parts per thousand for sediment samples with a nitrogen content >0.07 wt%. Sediment samples with lower nitrogen contents cannot be measured with sufficient precision without additional precautions and care should be taken when interpreting delta N-15 signatures and records for sediments with nitrogen concentrations

To elucidate the fate of river-borne nitrate in the estuarine environment, we measured nitrate concentrations and d15N and d18O of nitrate along the salinity gradient in the estuary of the river Elbe, one of the largest German rivers discharging into the North Sea. Nitrate concentrations in river waters ranged from 78 mmol L21 to 232 mmol L21; d15N varied from 8.2% to 16.2%, and the d18O values ranged from 20.1% to 3.2%. The nitrate concentrations in the German Bight were between 2 mmol L21 and 34 mmol L21, with d15N between 8.0% and 12.2% and d18O between 0.3% and 9.5%. Both riverine and marine end-member concentrations showed seasonal variations, with lower nitrate concentrations and more enriched isotope values during spring and summer compared to winter months. We found no indication in either concentrations or isotopic composition for a significant loss of nitrate within the estuary, but we found a significant increase of nitrate in the maximum turbidity zone in summer. We attribute this to nitrification reflected in a change in the oxygen isotopic composition. The entire riverine nitrate load is entrained into the North Sea by conservative mixing; this conflicts with both the presumed role of estuaries as effective N-sinks and with historical data from the Elbe estuary. Fundamental changes in the biogeochemical processes of the estuary have occurred over the past several decades due to extensive dredging and removal of sediment favorable for denitrification in the Elbe estuary that connects the port of Hamburg with the North Sea.

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.

Recent measurements at different locations suggest that the emission of mercury from soils may play a more pronounced role in the global mercury cycle as suggested by global emission inventories and global mercury cycling models. For up scaling and modelling of mercury emissions from soils a comprehensive assessment of the processes controlling the emission of mercury from soils is imperative. We have developed a laboratory flux measurement system (LFMS) to study the effect of major environmental variables on the emission of mercury under controlled conditions. We have investigated the effects of turbulent mixing, soil temperature and solar radiation on the emission of mercury from soils. The emission of mercury from soils is constant over time under constant experimental conditions. The response of the mercury emission flux to variations of the atmospheric transfer parameters such as turbulence requires a rapid adjustment of the equilibrium that controls the Hg degrees concentration in the soil air. It has been shown that the light-induced flux is independent of the soil temperature and shows a strong spectral response to UV-B. (c) 2006 Published by Elsevier Ltd.

Environmental context Once released to the atmosphere, halocarbons are involved in key chemical reactions. Stable carbon isotope measurements of halocarbons can provide valuable information on their sources and fate in the atmosphere. Here, we report δ13C values of 13 polyhalomethanes released from brown algae, which may provide a basis for inferring their sources and fate in future studies. Abstract Halocarbons are important vectors of reactive halogens to the atmosphere, where the latter participate in several key chemical processes. An improved understanding of the biogeochemical controls of the production–destruction equilibrium on halocarbons is of vital importance to address potential future changes in their fluxes to the atmosphere. Carbon stable isotope ratios of halocarbons could provide valuable additional information on their sources and fate that cannot be derived from mixing ratios alone. We determined the δ13C values of 13 polyhalomethanes from three brown algae species (Laminaria digitata, Fucus vesiculosus, Fucus serratus) and one seagrass species (Zostera noltii). The δ13C values were determined in laboratory incubations under variable environmental conditions of light, water levels (to simulate tidal events) and addition of hydrogen peroxide (H2O2). The δ13C values of the polyhalomethanes ranged from –42.2 ‰ (±3.5s.d.) for CHCl3 to 6.9 ‰ (±4.5) for CHI2Br and showed a systematic effect of the halogen substituents that could empirically be described in terms of linear free energy relationships. We further observed an enrichment in the δ13C of the polyhalomethanes with decreasing polyhalomethane yield that is attributed to the competing formation of halogenated ketones. Though variable, the isotopic composition of polyhalomethanes may provide useful additional information to discriminate between marine polyhalomethane sources.

International audience; Mercury (Hg) is a toxic pollutant and it can be strongly accumulated in the food chain, especially in Polar Regions. This paper presents a part of the work that has been on-going for 3-4 years in Ny-Alesund, Svalbard within the frame of an international collaboration. In Ny-Alesund in spring 2003, the atmospheric chemistry of mercury has been studied so as to better understand the formation of oxidized mercury species in the atmosphere that could be deposited onto snow surfaces. The role of snow as a potential source of mercury to the atmosphere or as a sink has also been approached to better understand the behavior of this metal. Chemical and biological processes seem to play a major role in Hg storage in snow. When melting, snow could be a major source of Hg into the various ecosystems and this toxin could therefore be accumulated into the food chain.