High dimethylsulfide photolysis rates in nitrate-rich Antarctic waters

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 31 (2004): L11307, doi:10.1029/2004GL019863.The photochemistry of dimethylsulfide (DMS) was examined in the Southern Ocean to assess its impact on the biogeochemical dynamics of DMS in Antarctic waters. Very high DMS photolysis rate constants (0.16–0.23 h−1) were observed in surface waters exposed to full sunlight. DMS photolysis rates increased linearly with added nitrate concentrations, and 35% of the DMS loss in unamended samples was attributed to the photochemistry of ambient nitrate (29 μM). Experiments with optical filters showed that the UV-A band of sunlight (320–400 nm) accounted for ~65% of DMS photolysis suggesting that dissolved organic matter was the main photosensitizer for DMS photolysis. During the austral spring, DMS photolysis was the dominant loss mechanism under non-bloom and non-ice cover conditions owing to the high doses and deep penetration of UV radiation in the water column, low observed microbial consumption rates, and high in situ nitrate concentrations.This work was supported by NSF (OPP- 0230499, DJK; OPP-0230497, RPK)

The sulfur cycle

Author Posting. © Oceanography Society, 2007. This article is posted here by permission of Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 20, 2 (2007): 117-123.The ocean represents a major reservoir of sulfur on Earth, with large quantities in the form of dissolved sulfate and sedimentary minerals (e.g., gypsum and pyrite). Sulfur occurs in a variety of valence states, ranging from –2 (as in sulfide and reduced organic sulfur) to +6 (as in sulfate). Sulfate is the most stable form of sulfur on today’s oxic Earth; weathering and leaching of rocks and sediments are its main sources to the ocean. In addition, the reduced inorganic forms of sulfur, with oxidation states of –2 and 0 (as in elemental sulfur) are quite common in anoxic environments, with sulfur compounds of mixed valence states (e.g., thiosulfate and polythionates) produced transiently. The natural release of volatile organic sulfur compounds from the ocean, mainly as dimethyl sulfide (DMS), transports sulfur from the ocean to terrestrial regions, and it also affects atmospheric chemistry and the climate system. While they remain very important, natural sulfur emissions have currently been overtaken by anthropogenic emissions, primarily from the burning of fossil fuels.Preparation of this manuscript was partially supported by National Science Foundation grant OCE-0452333 and a fellowship from the Hanse- Wissenschaftskolleg (http://www. h-w-k.de) to SMS, National Science Foundation grants OPP-0230497 and OPP-0083078 to RPK, as well as the Research Center Ocean Margins (RCOM) of the University of Bremen (Germany) to HNSV (RCOM-Nr. 0476)

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

© The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution 4.0 License. The definitive version was published in Biogeosciences 16(8), (2019):1729-1754, doi:10.5194/bg-16-1729-2019.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.We dedicate this article to the memory of Ronald P. Kiene, a wonderful scientist, mentor and friend. His contributions to DMS and DMSP research have shaped our field over the past 3 decades, and he will be missed by many around the world. We also wish to thank many individuals involved in data collection and logistical aspects of the cruises presented here, including scientists from the Institute of Ocean Sciences, the captain and crew of the R/V Oceanus and the CCGS John P. Tully, and members of the Tortell, Kiene, Levine and Hatton laboratory groups. We also thank Theodore Ahlvin for GIS support and both reviewers for their insightful comments. Support for this work was provided from the US National Science Foundation (grant no. 1436344) and from the Natural Sciences and Engineering Research Council of Canada

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

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&thinsp;&lt;&thinsp;1–10&thinsp;nM, mean 3.9&thinsp;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&thinsp;&lt;&thinsp;1–24&thinsp;nM, mean 6.1&thinsp;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&thinsp;Tg of DMS-derived sulfur to the atmosphere during the summer season.</p

The abundant marine bacterium Pelagibacter simultaneously catabolizes dimethylsulfoniopropionate to the gases dimethyl sulfide and methanethiol

Marine phytoplankton produce ~109 tons of dimethylsulfoniopropionate (DMSP) per year1,2, an estimated 10% of which is catabolized by bacteria through the DMSP cleavage pathway to the climatically active gas dimethyl sulfide (DMS)3,4. SAR11 Alphaproteobacteria (order Pelagibacterales), the most abundant chemoorganotrophic bacteria in the oceans, have been shown to assimilate DMSP into biomass, thereby supplying this cell’s unusual requirement for reduced sulfur5,6. Here we report that Pelagibacter HTCC1062 produces the gas methanethiol (MeSH) and that simultaneously a second DMSP catabolic pathway, mediated by a cupin-like DMSP lyase, DddK, shunts as much as 59% of DMSP uptake to DMS production. We propose a model in which the allocation of DMSP between these pathways is kinetically controlled to release increasing amounts of DMS as the supply of DMSP exceeds cellular sulfur demands for biosynthesis

Missed Opportunities for HIV Testing and Late-Stage Diagnosis among HIV-Infected Patients in Uganda

BACKGROUND: Late diagnosis of HIV infection is a major challenge to the scale-up of HIV prevention and treatment. In 2005 Uganda adopted provider-initiated HIV testing in the health care setting to ensure earlier HIV diagnosis and linkage to care. We provided HIV testing to patients at Mulago hospital in Uganda, and performed CD4 tests to assess disease stage at diagnosis. METHODS: Patients who had never tested for HIV or tested negative over one year prior to recruitment were enrolled between May 2008 and March 2010. Participants who tested HIV positive had a blood draw for CD4. Late HIV diagnosis was defined as CD4≤250 cells/mm. Predictors of late HIV diagnosis were analyzed using multi-variable logistic regression. RESULTS: Of 1966 participants, 616 (31.3%) were HIV infected; 47.6% of these (291) had CD4 counts ≤250. Overall, 66.7% (408) of the HIV infected participants had never received care in a medical clinic. Receiving care in a non-medical setting (home, traditional healer and drug stores) had a threefold increase in the odds of late diagnosis (OR = 3.2; 95%CI: 2.1-4.9) compared to receiving no health care. CONCLUSIONS: Late HIV diagnosis remains prevalent five years after introducing provider-initiated HIV testing in Uganda. Many individuals diagnosed with advanced HIV did not have prior exposure to medical clinics and could not have benefitted from the expansion of provider initiated HIV testing within health facilities. In addition to provider-initiated testing, approaches that reach individuals using non-hospital based encounters should be expanded to ensure early HIV diagnosis

Assessing the order of magnitude of outcomes in single-arm cohorts through systematic comparison with corresponding cohorts: An example from the AMOS study

<p>Abstract</p> <p>Background</p> <p>When a therapy has been evaluated in the first clinical study, the outcome is often compared descriptively to outcomes in corresponding cohorts receiving other treatments. Such comparisons are often limited to selected studies, and often mix different outcomes and follow-up periods. Here we give an example of a systematic comparison to all cohorts with identical outcomes and follow-up periods.</p> <p>Methods</p> <p>The therapy to be compared (anthroposophic medicine, a complementary therapy system) had been evaluated in one single-arm cohort study: the Anthroposophic Medicine Outcomes Study (AMOS). The five largest AMOS diagnosis groups (A-cohorts: asthma, depression, low back pain, migraine, neck pain) were compared to all retrievable corresponding cohorts (C-cohorts) receiving other therapies with identical outcomes (SF-36 scales or summary measures) and identical follow-up periods (3, 6 or 12 months). Between-group differences (pre-post difference in an A-cohort minus pre-post difference in the respective C-cohort) were divided with the standard deviation (SD) of the baseline score of the A-cohort.</p> <p>Results</p> <p>A-cohorts (5 cohorts with 392 patients) were similar to C-cohorts (84 cohorts with 16,167 patients) regarding age, disease duration, baseline affection and follow-up rates. A-cohorts had ≥ 0.50 SD larger improvements than C-cohorts in 13.5% (70/517) of comparisons; improvements of the same order of magnitude (small or minimal differences: -0.49 to 0.49 SD) were found in 80.1% of comparisons; and C-cohorts had ≥ 0.50 SD larger improvements than A-cohorts in 6.4% of comparisons. Analyses stratified by diagnosis had similar results. Sensitivity analyses, restricting the comparisons to C-cohorts with similar study design (observational studies), setting (primary care) or interventions (drugs, physical therapies, mixed), or restricting comparisons to SF-36 scales with small baseline differences between A- and C-cohorts (-0.49 to 0.49 SD) also had similar results.</p> <p>Conclusion</p> <p>In this descriptive analysis, anthroposophic therapy was associated with SF-36 improvements largely of the same order of magnitude as improvements following other treatments. Although these non-concurrent comparisons cannot assess comparative effectiveness, they suggest that improvements in health status following anthroposophic therapy can be clinically meaningful. The analysis also demonstrates the value of a systematic approach when comparing a therapy cohort to corresponding therapy cohorts.</p

A global database of sea surface dimethylsulfide (DMS) measurements and a procedure to predict sea surface DMS as a function of latitude, longitude, and month

47 pages, 13 figures, 7 tablesA database of 15,617 point measurements of dimethylsulfide (DMS) in surface waters along with lesser amounts of data for aqueous and particulate dimethylsulfoniopropionate concentration, chlorophyll concentration, sea surface salinity and temperature, and wind speed has been assembled. The database was processed to create a series of climatological annual and monthly 1°x1°latitude-longitude squares of data. The results were compared to published fields of geophysical and biological parameters. No significant correlation was found between DMS and these parameters, and no simple algorithm could be found to create monthly fields of sea surface DMS concentration based on these parameters. Instead, an annual map of sea surface DMS was produced using an algorithm similar to that employed by Conkright et al. [1994]. In this approach, a first-guess field of DMS sea surface concentration measurements is created and then a correction to this field is generated based on actual measurements. Monthly sea surface grids of DMS were obtained using a similar scheme, but the sparsity of DMS measurements made the method difficult to implement. A scheme was used which projected actual data into months of the year where no data were otherwise presen