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Bubbles rising through the water column are known to scavenge organic material and microorganisms, and transport them through the air–sea interface after bursting. This mechanism has important implications for air–sea exchange processes. However, little is known about how bubbles influence the chemical and biological properties of the sea-surface microlayer (SML), a gelatinous film at the air–sea interface. We used floating mesocosms in the coastal Baltic Sea and a laboratory tank filled with seawater from the North Sea to study the effect of bubbling on the gelatinous nature of the SML. Bubbling was found to always increase concentrations of transparent exopolymer particles (TEP) in the SML. In the field, TEP in the SML already increased after 2 min (53% ± 63%) and 10 min (19% ± 12%) bubbling, respectively. During the tank experiment, TEP enriched in the SML by 312% (± 244%) after > 3 h of bubbling. Therefore, bubbling is a highly efficient mechanism for TEP enrichment in the SML. Bubbling caused enrichment and depletion of microbial abundances (prokaryotes, flagellates, eukaryotes) in the SML. However, the incorporation of ³H-thymidine (i.e., bacterial carbon production) was consistently stimulated after 10 min of bubbling in the field experiment, indicating a bubble-induced import of unstressed bacteria and fresh organic substrates into the SML. Overall, our results suggest that the gelatinous matrix of the SML is re-formed within min after disruption by bursting bubbles, and, thus, highlights the importance of biogeochemical interactions within the air–sea interface.

Transparent exopolymer particles (TEPs) exhibit the properties of gels and are ubiquitously found in the world oceans. TEPs may enter the atmosphere as part of sea-spray aerosol. Here, we report number concentrations of TEPs with a diameter > 4.5 µm, hence covering a part of the supermicron particle range, 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 seawater. The ambient TEP concentrations ranged between 7×102 and 3×104 #TEP m−3 in the aerosol particles and correlations with 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 and, according to the measured cloud liquid water content, corresponding to equivalent air concentrations of 2–4×103 #TEP m−3. Based on Na+ concentrations in seawater and in the atmosphere, the enrichment factors for TEPs in the atmosphere were calculated. The tank-generated TEPs were enriched by a factor of 50 compared with seawater and, therefore, in-line with published enrichment factors for supermicron organic matter in general and TEPs 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 a secondary 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, whereas 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 TEPs likely possess good properties to act as INPs, in future experiments it is worth studying if a certain part of TEPs contributes a fraction of the biogenic INP population.

To elucidate the fate of river-borne nitrate in the estuarine environment, we measured nitrate concentrations and δ¹⁵N and δ¹⁸O 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 micromol L⁻¹ to 232 micromol L⁻¹; δ¹⁵N varied from 8.2‰ to 16.2‰, and the δ¹⁸O values ranged from -0.1‰ to 3.2‰. The nitrate concentrations in the German Bight were between 2 micromol L⁻¹ and 34 micromol L⁻¹, with δ¹⁵N between 8.0‰ and 12.2‰ and δ¹⁸O 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.

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 cm3 volume) for preserving the OCS amount and δ34S(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 (1σ) of δ34S(OCS) values as 0.4 ‰ for overall procedures during measurements for atmospheric samples. Additionally, this report presents diurnal variation of δ34S(OCS) values collected from ambient air at the Suzukakedai campus of the Tokyo Institute of Technology located in Yokohama, Japan. The observed OCS concentrations andδ34S(OCS) values were, respectively, 447–520 pmol mol-1 and from 10.4 ‰ to 10.7 ‰ with a lack of diurnal variation. The observed δ34S(OCS) values in ambient air differed greatly from previously reported values of δ34S(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 δ34S(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 δ34S(OCS) values is expected due to a link between anthropogenic activities and OCS cycles. The system presented herein is useful for application of δ34S(OCS) for investigation of OCS sources and sinks in the troposphere to elucidate its cycle.

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.

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.sup.+ 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.sup.-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.sup.-1 ; (ii) portability of adsorption tubes (1/4 in. (0.64 cm) outer diameter, 17.5 cm length, approximately 1.4 cm.sup.3 volume) for preserving the OCS amount and [delta].sup.34 S(OCS) values at -80 .sup.∘ C for up to 90 days and 14 days; and (iii) purification OCS from other compounds such as CO.sub.2 . We tested the OCS collection efficiency of the systems and sulfur isotopic fractionation during sampling. Results show precision (1σ) of [delta].sup.34 S(OCS) values as 0.4 0/00 for overall procedures during measurements for atmospheric samples. Additionally, this report presents diurnal variation of [delta].sup.34 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 [delta].sup.34 S(OCS) values were, respectively, 447-520 pmol mol.sup.-1 and from 10.4 0/00 to 10.7 0/00 with a lack of diurnal variation. The observed [delta].sup.34 S(OCS) values in ambient air differed greatly from previously reported values of [delta].sup.34 S(OCS) = (4.9±0.3) 0/00 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 [delta].sup.34 S(OCS) values between 10.5 0/00 in Japan (this study) and ∼13 0/00 recently reported in Israel or the Canary Islands indicates that spatial and temporal variation of [delta].sup.34 S(OCS) values is expected due to a link between anthropogenic activities and OCS cycles. The system presented herein is useful for application of [delta].sup.34 S(OCS) for investigation of OCS sources and sinks in the troposphere to elucidate its cycle.

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 cm3 volume) for preserving the OCS amount and δ34S(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 (1σ) of δ34S(OCS) values as 0.4 ‰ for overall procedures during measurements for atmospheric samples. Additionally, this report presents diurnal variation of δ34S(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 δ34S(OCS) values were, respectively, 447–520 pmol mol−1 and from 10.4 ‰ to 10.7 ‰ with a lack of diurnal variation. The observed δ34S(OCS) values in ambient air differed greatly from previously reported values of δ34S(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 δ34S(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 δ34S(OCS) values is expected due to a link between anthropogenic activities and OCS cycles. The system presented herein is useful for application of δ34S(OCS) for investigation of OCS sources and sinks in the troposphere to elucidate its cycle.

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.

Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially 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 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 -264±45 and -280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of -205±6 ‰ 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.

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.