Dimethyl Sulfide Measurements Research Articles

The determination of dimethyl sulfoxide in natural waters using electrochemical reduction

AbstractA highly specific electrochemical reduction method has been developed that enables the trace level measurement of dimethyl sulfoxide (DMSO) concentration in natural waters. Following the sparging of native dimethyl sulfide (DMS) from the sample, DMSO is reduced to DMS using a novel electrochemical workflow that relies upon CuSO4 as a redox mediator. The DMS produced through DMSO reduction is collected, concentrated, and detected using a previously described Purge & Trap‐Atmospheric Pressure Chemical Ionization‐Tandem Mass Spectrometry (P&T‐APCI‐MS/MS) analytical workflow. The method provides a 0.5 pM detection limit for the analysis of DMSO in 10 mL sample volumes, with a demonstrated method precision of 5.4% for the analysis of consecutive 10 nM aqueous standards. The method selectivity for DMSO was evaluated using a range of commonly observed marine organosulfur compounds, none of which were found to interfere with the analysis at a reduction potential of 4 V. Method intercomparison confirmed that the electrochemical reduction provides results that are equivalent (at the 95% confidence level) to an established TiCl3 reduction protocol for the analysis of both freshwater and seawater samples. Relative to established methods of DMSO reduction, the electrochemical method provides excellent selectivity and reproducibility, and offers the potential for automated, high‐throughput analysis. In addition, the new electrochemical method does not require expensive, difficult to procure enzymes or hazardous, corrosive chemical reagents. Depth profile measurements of DMSO, DMS, and dimethylsulfoniopropionate (DMSP) for unfiltered seawater samples collected in Saanich Inlet, a coastal fjord in British Columbia, demonstrate the effectiveness of the DMSO reduction method in an oceanographic context.

Observations of biogenic volatile organic compounds over a mixed temperate forest during the summer to autumn transition

Abstract. The exchange of trace gases between the biosphere and the atmosphere is an important process that controls both chemical and physical properties of the atmosphere with implications for air quality and climate change. The terrestrial biosphere is a major source of reactive biogenic volatile organic compounds (BVOCs) that govern atmospheric concentrations of the hydroxy radical (OH) and ozone (O3) and control the formation and growth of secondary organic aerosol (SOA). Common simulations of BVOC surface–atmosphere exchange in chemical transport models use parameterizations derived from the growing season and do not consider potential changes in emissions during seasonal transitions. Here, we use observations of BVOCs over a mixed temperate forest in northern Wisconsin during broadleaf senescence to better understand the effects of the seasonal changes in canopy conditions (e.g., temperature, sunlight, leaf area, and leaf stage) on net BVOC exchange. The BVOCs investigated here include the terpenoids isoprene (C5H8), monoterpenes (MTs; C10H16), a monoterpene oxide (C10H16O), and sesquiterpenes (SQTs; C15H24), as well as a subset of other monoterpene oxides and dimethyl sulfide (DMS). During this period, MTs were primarily composed of α-pinene, β-pinene, and camphene, with α-pinene and camphene dominant during the first half of September and β-pinene thereafter. We observed enhanced MT and monoterpene oxide emissions following the onset of leaf senescence and suggest that senescence has the potential to be a significant control on late-season MT emissions in this ecosystem. We show that common parameterizations of BVOC emissions cannot reproduce the fluxes of MT, C10H16O, and SQT during the onset and continuation of senescence but can correctly simulate isoprene flux. We also describe the impact of the MT emission enhancement on the potential to form highly oxygenated organic molecules (HOMs). The calculated production rates of HOMs and H2SO4, constrained by terpene and DMS concentrations, suggest that biogenic aerosol formation and growth in this region should be dominated by secondary organics rather than sulfate. Further, we show that models using parameterized MT emissions likely underestimate HOM production, and thus aerosol growth and formation, during early autumn in this region. Further measurements of forest–atmosphere BVOC exchange during seasonal transitions as well as measurements of DMS in temperate regions are needed to effectively predict the effects of canopy changes on reactive carbon cycling and aerosol production.

Measurement report: Long-range transport and the fate of dimethyl sulfide oxidation products in the free troposphere derived from observations at the high-altitude research station Chacaltaya (5240 m a.s.l.) in the Bolivian Andes

Abstract. Dimethyl sulfide (DMS) is the primary natural contributor to the atmospheric sulfur burden. Observations concerning the fate of DMS oxidation products after long-range transport in the remote free troposphere are, however, sparse. Here we present quantitative chemical ionization mass spectrometric measurements of DMS and its oxidation products sulfuric acid (H2SO4), methanesulfonic acid (MSA), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), methanesulfinic acid (MSIA), methyl thioformate (MTF), methanesulfenic acid (MSEA, CH3SOH), and a compound of the likely structure CH3S(O)2OOH in the gas phase, as well as measurements of the sulfate and methanesulfonate aerosol mass fractions. The measurements were performed at the Global Atmosphere Watch (GAW) station Chacaltaya in the Bolivian Andes located at 5240 m above sea level (a.s.l.). DMS and DMS oxidation products are brought to the Andean high-altitude station by Pacific air masses during the dry season after convective lifting over the remote Pacific ocean to 6000–8000 m a.s.l. and subsequent long-range transport in the free troposphere (FT). Most of the DMS reaching the station is already converted to the rather unreactive sulfur reservoirs DMSO2 in the gas phase and methanesulfonate (MS−) in the particle phase, which carried nearly equal amounts of sulfur to the station. The particulate sulfate at Chacaltaya is however dominated by regional volcanic emissions during the time of the measurement and not significantly affected by the marine air masses. In one of the FT events, even some DMS was observed next to reactive intermediates such as methyl thioformate, dimethylsulfoxide, and methanesulfinic acid. Also for this event, back trajectory calculations show that the air masses came from above the ocean (distance >330 km) with no local surface contacts. This study demonstrates the potential impact of marine DMS emissions on the availability of sulfur-containing vapors in the remote free troposphere far away from the ocean.

Simulating the radiative forcing of oceanic dimethylsulfide (DMS) in Asia based on machine learning estimates

Abstract. Dimethylsulfide (DMS) emitted from seawater is a key precursor to new particle formation and acts as a regulator in Earth's warming climate system. However, DMS's effects are not well understood in various ocean regions. In this study, we estimated DMS emissions based on a machine learning method and used the GEOS-Chem global 3D chemical transport model coupled with the TwO Moment Aerosol Sectional (TOMAS) microphysics scheme to simulate the atmospheric chemistry and radiative effects of DMS. The contributions of DMS to atmospheric SO42- aerosol and cloud condensation nuclei (CCN) concentrations along with the radiative effects over the Asian region were evaluated for the first time. First, we constructed novel monthly resolved DMS emissions (0.5∘×0.5∘) for the year 2017 using a machine learning model; 4351 seawater DMS measurements (including the recent measurements made over the Chinese seas) and 12 relevant environment parameters were selected for model training. We found that the model could predict the observed DMS concentrations with a correlation coefficient of 0.75 and fill the values in regions lacking observations. Across the Asian seas, the highest seasonal mean DMS concentration occurred in March–April–May (MAM), and we estimate the annual DMS emission flux of 1.25 Tg (S), which is equivalent to 15.4 % of anthropogenic sulfur emissions over the entire simulation domain (which covered most of Asia) in 2017. The model estimates of DMS and methane sulfonic acid (MSA), using updated DMS emissions, were evaluated by comparing them with cruise survey experiments and long-term online measurement site data. The improvement in model performance can be observed compared with simulation results derived from the global-database DMS emissions. The relative contributions of DMS to SO42- and CCN were higher in remote oceanic areas, contributing 88 % and 42 % of all sources, respectively. Correspondingly, the sulfate direct radiative forcing (DRF) and indirect radiative forcing (IRF) contributed by DMS ranged from −200 to −20 mW m−2 and from −900 to −100 mW m−2, respectively, with levels varying by season. The strong negative IRF is mainly over remote ocean regions (−900 to −600 mW m−2). Generally, the magnitude of IRF derived by DMS was twice as large as its DRF. This work provides insights into the source strength of DMS and the impact of DMS on climate and addresses knowledge gaps related to factors controlling aerosols in the marine boundary layer and their climate impacts.

Smartphone-based digital colorimetric measurement of dimethyl sulfide in wastewater

A simple and low-cost method for the measurement of dimethyl sulfide (DMS) in wastewater was developed using digital imaging colorimetry based on a smartphone. This method involved the generation of a pink color through the complexation reaction of DMS with sodium nitroprusside and subsequent acidification. A smartphone camera recorded the developed color through a digital image of the colored reaction mixture and color values in the red (R), green (G) and (B) blue color space were obtained through digital image analysis. The G value was found to provide a basis for the sensitive measurement of DMS. Light box parameters (position and distance of the light source relative to the camera) and reaction parameters (NaOH concentration, reaction time and HCl concentration) were optimized. This method exhibited linearity in the working range of 500–6000 μg kg−1 with a Pearson coefficient of 0.996. The sensitivity, which was based on the slope of the calibration line, was calculated to be −0.017 (μg kg−1)−1, and the limit of detection was 222 μgkg−1. Good precision (0.8 to 1.3% relative standard deviation) was obtained. The G value exhibited good correlation (Pearson correlation coefficient = 0.997) with the absorbance obtained from a spectrophotometer. Measurement of the DMS of a wastewater sample yielded a result which was in agreement (98 % recovery) with the results of a reference GC-FPD analysis, validating its capability for an accurate measurement.

Dimethyl Sulfide‐Induced Increase in Cloud Condensation Nuclei in the Arctic Atmosphere

AbstractOceanic dimethyl sulfide (DMS) emissions have been recognized as a biological regulator of climate by contributing to cloud formation. Despite decades of research, the climatic role of DMS remains ambiguous largely because of limited observational evidence for DMS‐induced cloud condensation nuclei (CCN) enhancement. Here, we report concurrent measurement of DMS, physiochemical properties of aerosol particles, and CCN in the Arctic atmosphere during the phytoplankton bloom period of 2010. We encountered multiple episodes of new particle formation (NPF) and particle growth when DMS mixing ratios were both low and high. The growth of particles to sizes at which they can act as CCN accelerated in response to an increase in atmospheric DMS. Explicitly, the sequential increase in all relevant parameters (including the source rate of condensable vapor, the growth rate of particles, Aitken mode particles, hygroscopicity, and CCN) was pronounced at the DMS‐derived NPF and particle growth events. This field study unequivocally demonstrates the previously unconfirmed roles of DMS in the growth of particles into climate‐relevant size and eventual CCN activation.

Unravelling Surface Seawater DMS Concentration and Sea‐To‐Air Flux Changes After Sea Ice Retreat in the Western Arctic Ocean

AbstractThe receding of the seasonal ice cover in the Arctic due to climate change has been predicted by models to increase climate‐active biogenic trace gas emissions, specifically those of dimethylsulfide (DMS). However, insufficient DMS measurements are currently available to either support or refute this hypothesis and to fully understand the various responses of oceanic DMS in a rapidly changing Arctic Ocean environment. Here, we present high‐resolution surface water DMS data collected in the summer of 2014 in combination with a suite of ancillary variables including sea ice cover, salinity, and nutrients. We show that surface seawater DMS concentrations, generally below 0.5 nmol L−1, remained unchanged in the Canada Basin after sea ice retreat probably due to insufficient nutrients supply to the upper mixed layer and resulting low primary production. Moreover, in the Chukchi shelf region, DMS concentrations decreased following a phytoplankton bloom due to the rapid depletion and slow resupply of nutrients. Although the DMS sea‐to‐air fluxes were not high from a global perspective, they increased by a factor of 4‐fold after sea ice retreat in the Arctic Ocean high latitudes. This increase in DMS flux was mainly driven by increased wind speed. This work provides unique observations and insights on how surface seawater DMS and flux to the atmosphere may change in the future Arctic Ocean.

Natural dimethyl sulfide gradients would lead marine predators to higher prey biomass

Finding prey is essential to survival, with marine predators hypothesised to track chemicals such as dimethyl sulfide (DMS) while foraging. Many predators are attracted to artificially released DMS, and laboratory experiments have shown that zooplankton grazing on phytoplankton accelerates DMS release. However, whether natural DMS concentrations are useful for predators and correlated to areas of high prey biomass remains a fundamental knowledge gap. Here, we used concurrent hydroacoustic surveys and in situ DMS measurements to present evidence that zooplankton biomass is spatially correlated to natural DMS concentration in air and seawater. Using agent simulations, we also show that following gradients of DMS would lead zooplankton predators to areas of higher prey biomass than swimming randomly. Further understanding of the conditions and scales over which these gradients occur, and how they are used by predators, is essential to predicting the impact of future changes in the ocean on predator foraging success.

Predictability of Seawater DMS During the North Atlantic Aerosol and Marine Ecosystem Study (NAAMES)

This work presents an overview of a unique set of surface ocean dimethylsulfide (DMS) measurements from four shipboard field campaigns conducted during the North Atlantic Aerosol and Marine Ecosystem Study (NAAMES) project. Variations in surface seawater DMS are discussed in relation to biological and physical observations. Results are considered at a range of timescales (seasons to days) and spatial scales (regional to sub-mesoscale). Elevated DMS concentrations are generally associated with greater biological productivity, although chlorophyll a (Chl) only explains a small fraction of the DMS variability (15%). Physical factors that determine the location of oceanic temperature fronts and depth of vertical mixing have an important influence on seawater DMS concentrations during all seasons. The interplay of biomass and physics influences DMS concentrations at regional/seasonal scales and at smaller spatial and shorter temporal scales. Seawater DMS measurements are compared with the global seawater DMS climatology and predictions made using a recently published algorithm and by a neural network model. The climatology is successful at capturing the seasonal progression in average seawater DMS, but does not reproduce the shorter spatial/temporal scale variability. The input terms common to the algorithm and neural network approaches are biological (Chl) and physical (mixed layer depth, photosynthetically active radiation, seawater temperature). Both models predict the seasonal North Atlantic average seawater DMS trends better than the climatology. However, DMS concentrations tend to be under-predicted and the episodic occurrence of higher DMS concentrations is poorly predicted. The choice of climatological seawater DMS product makes a substantial impact on the estimated DMS flux into the North Atlantic atmosphere. These results suggest that additional input terms are needed to improve the predictive capability of current state-of-the-art approaches to estimating seawater DMS.

Global ocean dimethyl sulfide climatology estimated from observations and an artificial neural network

Abstract. Marine dimethyl sulfide (DMS) is important to climate due to the ability of DMS to alter Earth's radiation budget. Knowledge of the global-scale distribution, seasonal variability, and sea-to-air flux of DMS is needed in order to improve understanding of atmospheric sulfur, aerosol/cloud dynamics, and albedo. Here we examine the use of an artificial neural network (ANN) to extrapolate available DMS measurements to the global ocean and produce a global climatology with monthly temporal resolution. A global database of 82 996 ship-based DMS measurements in surface waters was used along with a suite of environmental parameters consisting of latitude–longitude coordinates, time of day, time of year, solar radiation, mixed layer depth, sea surface temperature, salinity, nitrate, phosphate, and silicate. Linear regressions of DMS against the environmental parameters show that on a global-scale mixed layer depth and solar radiation are the strongest predictors of DMS. These parameters capture ∼9 % and ∼7 % of the raw DMS data variance, respectively. Multilinear regression can capture more of the raw data variance (∼39 %) but strongly underestimates DMS in high-concentration regions. In contrast, the artificial neural network captures ∼66 % of the raw data variance in our database. Like prior climatologies our results show a strong seasonal cycle in surface ocean DMS with the highest concentrations and sea-to-air fluxes in the high-latitude summertime oceans. We estimate a lower global sea-to-air DMS flux (20.12±0.43 Tg S yr−1) than the prior estimate based on a map interpolation method when the same gas transfer velocity parameterization is used. Our sensitivity test results show that DMS concentration does not change unidirectionally with each of the environmental parameters, which emphasizes the interactions among these parameters. The ANN model suggests that the flux of DMS from the ocean to the atmosphere will increase with global warming. Given that larger DMS fluxes induce greater cloud albedo, this corresponds to a negative climate feedback.

Automated, high frequency, on-line dimethyl sulfide measurements in natural waters using a novel “microslug” gas-liquid segmented flow method with chemiluminescence detection

Dimethyl sulfide (DMS) is the major biogenic volatile sulfur compound in surface seawater. Good quality DMS data with high temporal and spatial resolution are desirable for understanding reduced sulfur biogeochemistry. Here we present a fully automated and novel “microslug” gas-liquid segmented flow-chemiluminescence (MSSF-CL) based method for the continuous in-situ measurement of DMS in natural waters. Samples were collected into a flow tank and DMS transferred from the aqueous phase to the gas phase using a vario-directional coiled flow, in which microvolume liquid and gas slugs were interspersed. The separated DMS was reacted with ozone in a reaction cell for CL detection. The analytical process was automated, with a sample throughput of 6.6 h−1. Using MSSF for DMS separation was more effective and easily integrated with CL detection compared with the commonly used bubbling approach. Key parameters of the proposed method were investigated. The linear range for the method was 0.05–500 nM (R2 = 0.9984) and the limit of detection (3 x S/N) was 0.015 nM, which is comparable to the commonly used gas chromatography (GC) method and sensitive enough for direct DMS measurement in typical aquatic environments. Reproducibility and recovery were assessed by spiking natural water samples (river, lake, reservoir and pond) with different concentrations of DMS (10, 20 and 50 nM), giving relative standard deviations (RSDs) ≤1.75% (n = 5) and recoveries of 94.4–107.8%. This fully automated system is reagent free, easy to assemble, simple to use, portable (weight ~5.1 kg) and can be left in the field for several hours of unattended operation. The instrumentation can provide high quality DMS data for natural waters with an environmentally relevant temporal resolution of ~9 min.

Regional and Urban-Scale Environmental Influences of Oceanic DMS Emissions over Coastal China Seas.

Marine biogenic dimethyl sulfide (DMS) is an important natural source of sulfur in the atmosphere, which may play an important role in air quality. In this study, the WRF-CMAQ model is employed to assess the impact of DMS on the atmospheric environment at the regional scale of eastern coastal China and urban scale of Shanghai in 2017. A national scale database of DMS concentration in seawater is established based on the historical DMS measurements in the Yellow Sea, the Bohai Sea and the East China Sea in different seasons during 2009~2017. Results indicate that the sea-to-air emission flux of DMS varies greatly in different seasons, with the highest in summer, followed by spring and autumn, and the lowest in winter. The annual DMS emissions from the Yellow Sea, the Bohai Sea and the East China Sea are 0.008, 0.059, and 0.15 Tg S a−1, respectively. At the regional scale, DMS emissions increase atmospheric sulfur dioxide (SO2) and sulfate concentrations over the East China seas by a maximum of 8% in summer and a minimum of 2% in winter, respectively. At the urban scale, the addition of DMS emissions increase the SO2 and levels by 2% and 5%, respectively, and reduce ozone (O3) in the air of Shanghai by 1.5%~2.5%. DMS emissions increase fine-mode ammonium particle concentration distribution by 4% and 5%, and fine-mode nss- concentration distributions by 4% and 9% in the urban and marine air, respectively. Our results indicate that although anthropogenic sources are still the dominant contributor of atmospheric sulfur burden in China, biogenic DMS emissions source cannot be ignored.

Atmospheric dimethyl sulfide and its significant influence on the sea-to-air flux calculation over the Southern Ocean

Our understanding about the atmospheric dimethyl sulfide (DMS) and its influence to sea-to-air flux calculation in the Southern Ocean is still limited due to insufficient investigations. Herein, high-resolution shipboard underway simultaneous surface seawater and atmospheric DMS measurements were conducted in the Southern Ocean from February 23 to March 31, 2018. A larger variation of DMS levels was found in atmosphere compared with that in seawater. Remarkably, a large-scale area with high seawater and atmospheric DMS concentrations up to 27.9 nM and 3.92 ppbv, respectively, was investigated outside of Ross Sea sector. Atmospheric DMS levels were strongly impacted by wind speed and air mass convection. The relationship between atmospheric DMS and air mass exposure to oceanic chlorophyll varied greatly depending on the area of investigation. Some other regions with high DMS production capacity were examined as well beside those along the cruise tracks based on the results of positive correlations with high slopes and back trajectories. Moreover, significant uncertainty of sea-to-air DMS flux over the Southern Ocean could be caused by follows: (1) the selecting of different gas transfer coefficients; (2) the negative flux values calculated under high atmospheric DMS levels together with low seawater DMS concentrations; and (3) the greatly overestimated flux, approximately 47.1–76.9%, without considering the atmospheric DMS. This study highlights the urgent demand of high-resolution observations of atmospheric DMS over the Southern Ocean to estimate DMS emission with high accuracy.

Patterns and drivers of dimethylsulfide concentration in the northeast subarctic Pacific across multiple spatial and temporal scales

Abstract. The northeast subarctic Pacific (NESAP) is a globally important source of the climate-active gas dimethylsulfide (DMS), yet the processes driving DMS variability across this region are poorly understood. Here we examine the spatial distribution of DMS at various spatial scales in contrasting oceanographic regimes of the NESAP. We present new high-spatial-resolution measurements of DMS across hydrographic frontal zones along the British Columbia continental shelf, together with key environmental variables and biological rate measurements. We combine these new data with existing observations to produce a revised summertime DMS climatology for the NESAP, yielding a broader context for our sub-mesoscale process studies. Our results demonstrate sharp DMS concentration gradients across hydrographic frontal zones and suggest the presence of two distinct DMS cycling regimes in the NESAP, corresponding to microphytoplankton-dominated waters along the continental shelf and nanoplankton-dominated waters in the cross-shelf transitional zone. DMS concentrations across the continental shelf transition (range < 1–10 nM, mean 3.9 nM) exhibited positive correlations to salinity (r=0.80), sea surface height anomaly (SSHA; r=0.51), and the relative abundance of prymnesiophyte and dinoflagellates (r=0.89). In contrast, DMS concentrations in nearshore coastal transects (range < 1–24 nM, mean 6.1 nM) showed a negative correlation with salinity (r=-0.69; r=-0.78) and SSHA (r=-0.81; r=-0.75) and a positive correlation to relative diatom abundance (r=0.88; r=0.86). These results highlight the importance of bloom-driven DMS production in continental shelf waters of this region and the role of prymnesiophytes and dinoflagellates in DMS cycling further offshore. In all areas, the rate of DMS consumption appeared to be an important control on observed concentration gradients, with higher DMS consumption rate constants associated with lower DMS concentrations. We compiled a data set of all available summertime DMS observations for the NESAP (including previously unpublished results) to examine the performance of several existing algorithms for predicting regional DMS concentrations. None of these existing algorithms was able to accurately reproduce observed DMS distributions across the NESAP, although performance was improved by the use of regionally tuned coefficients. Based on our compiled observations, we derived an average summertime distribution map for DMS concentrations and sea–air fluxes across the NESAP, estimating a mean regional flux of 0.30 Tg of DMS-derived sulfur to the atmosphere during the summer season.

An integrated sampler for shipboard underway measurement of dimethyl sulfide in surface seawater and air

Dimethyl sulfide (DMS), a marine-derived trace gas, can influence atmospheric compositions and has an impact on the global climate. To date, obtaining continuous and coupled shipboard underway measurements of DMS in seawater and air has been challenging. To address this issue, we report a custom-made sampling device based on the purge-and-trap technique. This sampler, in combination with a time-of-flight mass spectrometer (TOF-MS), was successfully utilized to perform coupled shipboard underway measurements of DMS in surface seawater and air around western Antarctica during the 34th Chinese Antarctic Research Expedition from February 2018 to April 2018. The seawater and air streams were continuously introduced into the sampler unit and subsampled every 10 min. The limits of detection (LODs) of DMS in seawater and air were found to be 0.07 nM and 32 pptv, respectively. The variability in the DMS levels in the surface seawater and air can be distinguished and evaluated based on the variations in the DMS peaks. These results demonstrated that the sampling device was effective for consistent, sensitive underway measurements of DMS.

Characteristics of the surface water DMS and pCO2 distributions and their relationships in the Southern Ocean, southeast Indian Ocean, and northwest Pacific Ocean

AbstractOceanic dimethyl sulfide (DMS) is of interest due to its critical influence on atmospheric sulfur compounds in the marine atmosphere and its hypothesized significant role in global climate. High‐resolution shipboard underway measurements of surface seawater DMS and the partial pressure of carbon dioxide (pCO2) were conducted in the Atlantic Ocean and Indian Ocean sectors of the Southern Ocean (SO), the southeast Indian Ocean, and the northwest Pacific Ocean from February to April 2014 during the 30th Chinese Antarctic Research Expedition. The SO, particularly in the region south of 58°S, had the highest mean surface seawater DMS concentration of 4.1 ± 8.3 nM (ranged from 0.1 to 73.2 nM) and lowest mean seawater pCO2 level of 337 ± 50 μatm (ranged from 221 to 411 μatm) over the entire cruise. Significant variations of surface seawater DMS and pCO2 in the seasonal ice zone (SIZ) of SO were observed, which are mainly controlled by biological process and sea ice activity. We found a significant negative relationship between DMS and pCO2 in the SO SIZ using 0.1° resolution, [DMS] seawater = −0.160 [pCO2] seawater + 61.3 (r2 = 0.594, n = 924, p < 0.001). We anticipate that the relationship may possibly be utilized to reconstruct the surface seawater DMS climatology in the SO SIZ. Further studies are necessary to improve the universality of this approach.

Assessing the potential for dimethylsulfide enrichment at the sea surface and its influence on air–sea flux

Abstract. The flux of dimethylsulfide (DMS) to the atmosphere is generally inferred using water sampled at or below 2 m depth, thereby excluding any concentration anomalies at the air–sea interface. Two independent techniques were used to assess the potential for near-surface DMS enrichment to influence DMS emissions and also identify the factors influencing enrichment. DMS measurements in productive frontal waters over the Chatham Rise, east of New Zealand, did not identify any significant gradients between 0.01 and 6 m in sub-surface seawater, whereas DMS enrichment in the sea-surface microlayer was variable, with a mean enrichment factor (EF; the concentration ratio between DMS in the sea-surface microlayer and in sub-surface water) of 1.7. Physical and biological factors influenced sea-surface microlayer DMS concentration, with high enrichment (EF > 1.3) only recorded in a dinoflagellate-dominated bloom, and associated with low to medium wind speeds and near-surface temperature gradients. On occasion, high DMS enrichment preceded periods when the air–sea DMS flux, measured by eddy covariance, exceeded the flux calculated using National Oceanic and Atmospheric Administration (NOAA) Coupled-Ocean Atmospheric Response Experiment (COARE) parameterized gas transfer velocities and measured sub-surface seawater DMS concentrations. The results of these two independent approaches suggest that air–sea emissions may be influenced by near-surface DMS production under certain conditions, and highlight the need for further study to constrain the magnitude and mechanisms of DMS production in the sea-surface microlayer.

Dimethyl sulfide in the summertime Arctic atmosphere: measurements and source sensitivity simulations

Abstract. Dimethyl sulfide (DMS) plays a major role in the global sulfur cycle. In addition, its atmospheric oxidation products contribute to the formation and growth of atmospheric aerosol particles, thereby influencing cloud condensation nuclei (CCN) populations and thus cloud formation. The pristine summertime Arctic atmosphere is strongly influenced by DMS. However, atmospheric DMS mixing ratios have only rarely been measured in the summertime Arctic. During July–August, 2014, we conducted the first high time resolution (10 Hz) DMS mixing ratio measurements for the eastern Canadian Archipelago and Baffin Bay as one component of the Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments (NETCARE). DMS mixing ratios ranged from below the detection limit of 4 to 1155 pptv (median 186 pptv) during the 21-day shipboard campaign. A transfer velocity parameterization from the literature coupled with coincident atmospheric and seawater DMS measurements yielded air–sea DMS flux estimates ranging from 0.02 to 12 µmol m−2 d−1. Air-mass trajectory analysis using FLEXPART-WRF and sensitivity simulations with the GEOS-Chem chemical transport model indicated that local sources (Lancaster Sound and Baffin Bay) were the dominant contributors to the DMS measured along the 21-day ship track, with episodic transport from the Hudson Bay System. After adjusting GEOS-Chem oceanic DMS values in the region to match measurements, GEOS-Chem reproduced the major features of the measured time series but was biased low overall (2–1006 pptv, median 72 pptv), although within the range of uncertainty of the seawater DMS source. However, during some 1–2 day periods the model underpredicted the measurements by more than an order of magnitude. Sensitivity tests indicated that non-marine sources (lakes, biomass burning, melt ponds, and coastal tundra) could make additional episodic contributions to atmospheric DMS in the study region, although local marine sources of DMS dominated. Our results highlight the need for both atmospheric and seawater DMS data sets with greater spatial and temporal resolution, combined with further investigation of non-marine DMS sources for the Arctic.

Discussion of Wort Homogeneity

Constant wort boiling leads to a homogenous wort and is a major quality criterion during beer production. The topic of this article is the determination of wort boiling constancy, and of wort homogeneity, via measurement of dimethyl sulfide (DMS) residue curves. Three states of wort homogeneity are introduced and calculated procedurally in terms of the evaporation of DMS. As an example, evaporation of DMS from water is measured for a falling-film evaporator operating as an external boiler on a technical scale during defined trials. Measurement results are further compared with results of (pre-)calculated states of wort homogeneity. It can be stated that the postulated states were precalculated and simulated within the trials successfully. The current article thus conveys a tool enabling any practitioner to investigate and evaluate wort homogeneity of its particular brewery.

Air‐sea exchange of methanol and acetone during HiWinGS: Estimation of air phase, water phase gas transfer velocities

AbstractThe air‐sea fluxes of methanol and acetone were measured concurrently using a proton‐transfer‐reaction mass spectrometer (PTR‐MS) with the eddy covariance (EC) technique during the High Wind Gas Exchange Study (HiWinGS) in 2013. The seawater concentrations of these compounds were also measured twice daily with the same PTR‐MS coupled to a membrane inlet. Dissolved concentrations near the surface ranged from 7 to 28 nM for methanol and from 3 to 9 nM for acetone. Both gases were consistently transported from the atmosphere to the ocean as a result of their low sea surface saturations. The largest influxes were observed in regions of high atmospheric concentrations and strong winds (up to 25 m s−1). Comparison of the total air‐sea transfer velocity of these two gases (Ka), along with the in situ sensible heat transfer rate, allows us to constrain the individual gas transfer velocity in the air phase (ka) and water phase (kw). Among existing parameterizations, the scaling of ka from the COARE model is the most consistent with our observations. The kw we estimated is comparable to the tangential (shear driven) transfer velocity previously determined from measurements of dimethyl sulfide. Lastly, we estimate the wet deposition of methanol and acetone in our study region and evaluate the lifetimes of these compounds in the surface ocean and lower atmosphere with respect to total (dry plus wet) atmospheric deposition.