An on-line method for S-isotope analysis is described. Samples are combusted in an elemental analyzer. SO2 is separated from other combustion gases by gas chromatography, and the gases enter the ion source of the mass spectrometer through a split interface. Integrated peak areas for 32S02+ and 34SC>2+ are compared to the response for a standard gas sample to determine the S^S value. 534S values of samples analyzed using the on-line method correspond linearly with those achieved from the same sample prepared off-line, where Kiba reduction followed by oxidation of the sulfur to SO2 is carried out prior to S-isotope analysis against a known standard. With the described on-line method, the amount of sulfur necessary for S-isotope analysis is reduced to about 10 #tg of S per analysis. The time needed for on-line preparation and measurement is less than one-third of the off-line procedure.Stable sulfur-isotope analysis is often associated with many problems concerning sample preparation and mass spectrometric determination. The 34S/32S ratios are most commonly determined after SO2 has been generated out of natural materials. Sample preparation always requires several chemical transformation steps to finally produce SO2 out of the S-containing compounds. The standard preparation techniques used for most sulfur-bearing samples start with conversion of all sulfur to BaSO*, which is then reduced to H2S by one of the following three procedures: graphite reduction at 1000 °C,' reduction with tin(II)-strong phosphoric acid (Kiba's reagent) at 300 °C in a stream of nitrogen,2 or application of a HI-H3PO4-HCI reduction solution.3 The generated H2S is converted to Ag2S, which is finally oxidized to SO2. One major disadvantage of these methods is that they all need relatively large amounts of the original material to obtain sufficient sulfur as the numerous chemical processes require rather high amounts of sulfur (3-7 mg of S). Although
[1] The recent decline in sea ice cover in the Arctic Ocean could affect the regional radiative forcing via changes in sea ice-atmosphere exchange of dimethyl sulfide (DMS) and biogenic aerosols formed from its atmospheric oxidation, such as methanesulfonic acid (MSA). This study examines relationships between changes in total sea ice extent north of 70 N and atmospheric MSA measurement at Alert, Nunavut, during 1980Nunavut, during -2009 at Barrow, Alaska, during 1997 and at Ny-Ålesund, Svalbard, for 1991. During the 1980-1989 and 1990 periods, summer (July-August) and June MSA concentrations at Alert decreased. In general, MSA concentrations increased at all locations since 2000 with respect to 1990 values, specifically during June and summer at Alert and in summer at Barrow and Ny-Ålesund. Our results show variability in MSA at all sites is related to changes in the source strengths of DMS, possibly linked to changes in sea ice extent as well as to changes in atmospheric transport patterns. Since 2000, a late spring increase in atmospheric MSA at the three sites coincides with the northward migration of the marginal ice edge zone where high DMS emissions from ocean to atmosphere have previously been reported. Significant negative correlations are found between sea ice extent and MSA concentrations at the three sites during the spring and June. These results suggest that a decrease in seasonal ice cover influencing other mechanisms of DMS production could lead to higher atmospheric MSA concentrations.
One year of aerosol particle observations from Alert, Nunavut shows that new particle formation (NPF) is common during clean periods of the summertime Arctic associated with attendant low condensation sinks and with the presence of methane sulfonic acid (MSA), a product of the atmospheric oxidation of dimethyl sulfide (DMS). The clean aerosol time periods, defined using the distribution of refractory black carbon number concentrations, increase in frequency from June through August as the anthropogenic influence dwindles. During the clean periods, the number concentrations of particles that can act as cloud condensation nuclei (CCN) increase from June through August suggesting that DMS, and possibly other oceanic organic precursors, exert significant control on the Arctic summertime submicron aerosol, a proposition supported by simulations from the GEOS-Chem-TOMAS global chemical transport model with particle microphysics. The CCN increase for the clean periods across the summer is estimated to be able to increase cloud droplet number concentrations (CDNC) by 23-44 cm -3 , comparable to the mean CDNC increase needed to yield the current global cloud albedo forcing from industrial aerosols. These results suggest that DMS may contribute significantly to modification of the Arctic summer shortwave cloud albedo, and they offer a reference for future changes in the Arctic summer aerosol.
However, in that study the analytical sensitivity was not available to determine the isotopic composition of individual weekly aerosol samples during summer when aerosol concen-11,619
Abstract. Motivated by the need to predict how the Arctic atmosphere will change in a warming world, this article summarizes recent advances made by the research consortium NETCARE (Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments) that contribute to our fundamental understanding of Arctic aerosol particles as they relate to climate forcing. The overall goal of NETCARE research has been to use an interdisciplinary approach encompassing extensive field observations and a range of chemical transport, earth system, and biogeochemical models. Several major findings and advances have emerged from NETCARE since its formation in 2013. (1) Unexpectedly high summertime dimethyl sulfide (DMS) levels were identified in ocean water (up to 75 nM) and the overlying atmosphere (up to 1 ppbv) in the Canadian Arctic Archipelago (CAA). Furthermore, melt ponds, which are widely prevalent, were identified as an important DMS source (with DMS concentrations of up to 6 nM and a potential contribution to atmospheric DMS of 20 % in the study area). (2) Evidence of widespread particle nucleation and growth in the marine boundary layer was found in the CAA in the summertime, with these events observed on 41 % of days in a 2016 cruise. As well, at Alert, Nunavut, particles that are newly formed and grown under conditions of minimal anthropogenic influence during the months of July and August are estimated to contribute 20 % to 80 % of the 30–50 nm particle number density. DMS-oxidation-driven nucleation is facilitated by the presence of atmospheric ammonia arising from seabird-colony emissions, and potentially also from coastal regions, tundra, and biomass burning. Via accumulation of secondary organic aerosol (SOA), a significant fraction of the new particles grow to sizes that are active in cloud droplet formation. Although the gaseous precursors to Arctic marine SOA remain poorly defined, the measured levels of common continental SOA precursors (isoprene and monoterpenes) were low, whereas elevated mixing ratios of oxygenated volatile organic compounds (OVOCs) were inferred to arise via processes involving the sea surface microlayer. (3) The variability in the vertical distribution of black carbon (BC) under both springtime Arctic haze and more pristine summertime aerosol conditions was observed. Measured particle size distributions and mixing states were used to constrain, for the first time, calculations of aerosol–climate interactions under Arctic conditions. Aircraft- and ground-based measurements were used to better establish the BC source regions that supply the Arctic via long-range transport mechanisms, with evidence for a dominant springtime contribution from eastern and southern Asia to the middle troposphere, and a major contribution from northern Asia to the surface. (4) Measurements of ice nucleating particles (INPs) in the Arctic indicate that a major source of these particles is mineral dust, likely derived from local sources in the summer and long-range transport in the spring. In addition, INPs are abundant in the sea surface microlayer in the Arctic, and possibly play a role in ice nucleation in the atmosphere when mineral dust concentrations are low. (5) Amongst multiple aerosol components, BC was observed to have the smallest effective deposition velocities to high Arctic snow (0.03 cm s−1).
Dimethyl sulfide (DMS) and its oxidation products, which have been proposed to provide a climate feedback mechanism by affecting aerosol and cloud radiative properties, were measured on board the Canadian Coast Guard ship Amundsen in sampling campaigns in the Arctic in the fall of 2007 and 2008. DMS flux was calculated based on the surface water measurements and yielded 0.1–2.6 μmol m−2 d−1 along the Northwest Passage in 2007 and 0.2–1.3 μmol m−2 d−1 along Baffin Bay in 2008. DMS oxidation products, sulfur dioxide (SO2), methane sulfonic acid (MSA), and sulfate in aerosols were also measured. The amounts of biogenic SO2 and sulfate were approximated using stable isotope apportionment techniques. Calculating the threshold amount of SO2 needed for significant new particle formation from the formulation by Pirjola et al. (1999), the study suggests that instances of elevated biogenic SO2 concentrations (between 8 and 9 September 2008) derived using conservative assumptions may have been sufficient to form new aerosols in clean air conditions in the Arctic region.
Abstract. Size-segregated aerosol sulfate concentrations were measured on board the Canadian Coast Guard Ship (CCGS) Amundsen in the Arctic during July 2014. The objective of this study was to utilize the isotopic composition of sulfate to address the contribution of anthropogenic and biogenic sources of aerosols to the growth of the different aerosol size fractions in the Arctic atmosphere. Non-seasalt sulfate is divided into biogenic and anthropogenic sulfate using stable isotope apportionment techniques. A considerable amount of the average sulfate concentration in the fine aerosols with a diameter < 0.49 µm was from biogenic sources (> 63 %), which is higher than in previous Arctic studies measuring above the ocean during fall (< 15 %) (Rempillo et al., 2011) and total aerosol sulfate at higher latitudes at Alert in summer (> 30 %) (Norman et al., 1999). The anthropogenic sulfate concentration was less than that of biogenic sulfate, with potential sources being long-range transport and, more locally, the Amundsen's emissions. Despite attempts to minimize the influence of ship stack emissions, evidence from larger-sized particles demonstrates a contribution from local pollution.A comparison of δ 34 S values for SO 2 and fine aerosols was used to show that gas-to-particle conversion likely occurred during most sampling periods. δ 34 S values for SO 2 and fine aerosols were similar, suggesting the same source for SO 2 and aerosol sulfate, except for two samples with a relatively high anthropogenic fraction in particles < 0.49 µm in diameter (15)(16)(17). The high biogenic fraction of sulfate fine aerosol and similar isotope ratio values of these particles and SO 2 emphasize the role of marine organisms (e.g., phytoplankton, algae, bacteria) in the formation of fine particles above the Arctic Ocean during the productive summer months.
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