Sohiko Kameyama

Equilibrator Inlet-Proton Transfer Reaction-Mass Spectrometry (EI-PTR-MS) for Sensitive, High-Resolution Measurement of Dimethyl Sulfide Dissolved in Seawater

We developed an equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) method for fast detection of dimethyl sulfide (DMS) dissolved in seawater. Dissolved DMS extracted by bubbling pure nitrogen through the sample was continuously directed to the PTR-MS instrument. The equilibration of DMS between seawater and the carrier gas, and the response time of the system, were evaluated in the laboratory. DMS reached equilibrium with an overall response time of 1 min. The detection limit (50 pmol L(-1) at 5 s integration) was sufficient for detection of DMS concentrations in the open ocean. The EI-PTR-MS instrument was deployed during a research cruise in the western North Pacific Ocean. Comparison of the EI-PTR-MS results with results obtained by means of membrane tube equilibrator-gas chromatography/mass spectrometry agreed reasonably well on average (R(2) = 0.99). EI-PTR-MS captured temporal variations of dissolved DMS concentrations, including elevated peaks associated with patches of high biogenic activity. These results demonstrate that the EI-PTR-MS technique was effective for highly time-resolved measurements of DMS in the open ocean. Further measurements will improve our understanding of the biogeochemical mechanisms of the production, consumption, and distribution of DMS on the ocean surface and, hence, the air-sea flux of DMS, which is a climatically important species.

Measurement of air-sea exchange of dimethyl sulfide and acetone by PTR-MS coupled with gradient flux technique.

We developed a new method for in situ measurement of air-sea fluxes of multiple volatile organic compounds (VOCs) by combining proton transfer reaction-mass spectrometry (PTR-MS) and gradient flux (GF) technique. The PTR-MS/GF system was first deployed to determine the air-sea flux of VOCs in the open ocean of the western Pacific, in addition to carbon dioxide and water vapor. Each profiling at seven heights from the ocean surface up to 14 m took 7 min. In total, 34 vertical profiles of VOCs in the marine atmosphere just above the ocean surface were obtained. The vertical gradient observed was significant for dimethyl sulfide (DMS) and acetone with the best-fit curves on quasi-logarithmic relationship. The mean fluxes of DMS and acetone were 5.5 ± 1.5 and 2.7 ± 1.3 μmol/m(2)/day, respectively. These fluxes are in general in accordance with those reported by previous expeditions.

Abundance and Distribution of Dimethylsulfoniopropionate Degradation Genes and the Corresponding Bacterial Community Structure at Dimethyl Sulfide Hot Spots in the Tropical and Subtropical Pacific Ocean

ABSTRACT Dimethylsulfoniopropionate (DMSP) is mainly produced by marine phytoplankton but is released into the microbial food web and degraded by marine bacteria to dimethyl sulfide (DMS) and other products. To reveal the abundance and distribution of bacterial DMSP degradation genes and the corresponding bacterial communities in relation to DMS and DMSP concentrations in seawater, we collected surface seawater samples from DMS hot spot sites during a cruise across the Pacific Ocean. We analyzed the genes encoding DMSP lyase (dddP) and DMSP demethylase (dmdA), which are responsible for the transformation of DMSP to DMS and DMSP assimilation, respectively. The averaged abundance (±standard deviation) of these DMSP degradation genes relative to that of the 16S rRNA genes was 33% ± 12%. The abundances of these genes showed large spatial variations. dddP genes showed more variation in abundances than dmdA genes. Multidimensional analysis based on the abundances of DMSP degradation genes and environmental factors revealed that the distribution pattern of these genes was influenced by chlorophyll a concentrations and temperatures. dddP genes, dmdA subclade C/2 genes, and dmdA subclade D genes exhibited significant correlations with the marine Roseobacter clade, SAR11 subgroup Ib, and SAR11 subgroup Ia, respectively. SAR11 subgroups Ia and Ib, which possessed dmdA genes, were suggested to be the main potential DMSP consumers. The Roseobacter clade members possessing dddP genes in oligotrophic subtropical regions were possible DMS producers. These results suggest that DMSP degradation genes are abundant and widely distributed in the surface seawater and that the marine bacteria possessing these genes influence the degradation of DMSP and regulate the emissions of DMS in subtropical gyres of the Pacific Ocean.

Sea‐to‐air flux of dimethyl sulfide in the South and North Pacific Ocean as measured by proton transfer reaction‐mass spectrometry coupled with the gradient flux technique

Exchange of dimethylsulfide (DMS) between the surface ocean and the lower atmosphere was examined by using Proton Transfer Reaction-Mass Spectrometry coupled with the Gradient Flux (PTR-MS/GF) system. We deployed the PTR-MS/GF system and observed vertical gradients of atmospheric DMS just above the sea surface in the subtropical and transitional South Pacific Ocean and the subarctic North Pacific Ocean. In total, we obtained 370 in situ profiles, and of these we used 46 data sets to calculate the sea-to-air flux of DMS. The DMS flux determined was in the range from 1.9 to 31 μmol m–2 d–1 and increased with wind speed and biological activity, in reasonable accordance with previous observations in the open ocean. The gas transfer velocity of DMS derived from the PTR-MS/GF measurements was similar to either that of DMS determined by the eddy covariance technique or that of insoluble gases derived from the dual tracer experiments, depending on the observation sites located in different geographic regions. When atmospheric conditions were strongly stable during the daytime in the subtropical ocean, the PTR-MS/GF observations captured a daytime vs. nighttime difference in DMS mixing ratios in the surface air overlying the ocean surface. The difference was mainly due to the sea-to-air DMS emissions and stable atmospheric conditions, thus affecting the gradient of DMS. This indicates that the DMS gradient is strongly controlled by diurnal variations in the vertical structure of the lower atmosphere above the ocean surface.

Estimates of methane emissions from the Southern Ocean from quasi-continuous underway measurements of the partial pressure of methane in surface seawater during the 2012/13 austral summer

Abstract We used a new underway measurement system to investigate the partial pressure of methane (CH4) in surface seawater and overlying air in the Southern Ocean from late November 2012 to mid-February 2013. The underway system consisted of a cavity ring-down spectroscopy analyser and a shower-head type equilibrator. The monthly mean atmospheric CH4 mixing ratios obtained agreed well (within 5 ppb) with those recorded at onshore baseline stations. CH4 saturation ratios (SR, %), defined as CH4 concentration in seawater divided by CH4 concentration equilibrated with atmospheric CH4, varied between 85 and 185%; most of the ratios we calculated indicated supersaturation, except for those from south of the Southern limit of Upper Circumpolar Deep Water. SR was higher at the lower latitudes, including coastal areas north of the Sub-Antarctic Front, but decreased gradually and monotonously between the Sub-Antarctic Front and the Upper Circumpolar Deep Water. At high latitudes south of the Polar Front, SR decreased to below 100% due to the effects of upwelling and vertical mixing. We found a strong linear correlation between SR and apparent oxygen utilisation (AOU) south of the Polar Front. Observed SR decreased with increasing AOU and reached 85% at high AOU (41 µmol kg−1) and low temperature (–1.8 °C). On the basis of the linear relationship between SR and AOU, we evaluated the climatological sea–air flux of CH4 from December to February for the entire Southern Ocean south of 50°S: Sea–air CH4 emission was estimated to be 0.027 Tg yr−1 in December, 0.04 Tg yr−1 in January, and 0.019 Tg yr−1 in February.

Technical Note: Determination of formaldehyde mixing ratios in polluted air with PTR-MS: laboratory experiments and field measurements

1 National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba, Ibaraki 305-8506, Japan 2 JSPS Research Fellow, Japan 3 Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan 4 Frontier Research Center for Global Change, Japan Agency for Marine-Earth Science and Technology, 3173-25, Showa-machi, Yokohama, Kanagawa 236-0001, Japan 5 LAPC/NZC, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 10029, China