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A 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. [ABSTRACT FROM AUTHOR]

We measured the concentration and turnover rates of dimethylsulfoxide (DMSO) across the northeast Subarctic Pacific (NESAP) to better understand the role of this compound in regional sulfur cycling and phytoplankton physiological ecology. Using ship‐track observations and Lagrangian drifter surveys, we examined the spatial and temporal components of DMS and DMSO variability, comparing rates of DMSO reduction with simultaneous measurements of dimethylsulfide (DMS) oxidation and dimethylsulfoniopropionate (DMSP) cleavage. Our results show high concentrations and rapid turnover of DMSO across much of our NESAP survey region. DMS and DMSO concentrations ranged from < 1 nM to maxima of 26 nM and 183 nM, respectively, and exhibited a nonlinear positive relationship. Rate constants for DMSO reduction to DMS ranged from < 1 to 6.5 d−1 and were correlated to bacterial production and phytoplankton taxonomic composition. DMSO reduction rates exceeded dissolved DMSP cleavage at nearly all stations, and exceeded DMS oxidation rates at four stations where DMSO reduction and DMS oxidation were measured simultaneously. At these stations, net DMS production from DMSO ranged from 0.50 to 7.18 nM d−1. During our Lagrangian survey, DMSO concentrations decreased during periods of peak mid‐day irradiance. A strong correlation between DMSO concentrations, non‐photochemical quenching and photochemical efficiency of photosystem II (Fv/Fm) suggest a potential role for DMSO in photo‐protection, supporting previous suggestions of an anti‐oxidant function for this molecule. Our findings highlight the potential contribution of DMSO to net DMS production in the NESAP, and suggest a role for this compound in phytoplankton physiological ecology. [ABSTRACT FROM AUTHOR]

RATIONALE: Atmospheric pressure photoionization (APPI) is considered a candidate ionization method suitable for a broad range of liquid chromatography/mass spectrometry (LC/MS) applications. Questions remain, however, regarding the ultimate potential of the technique. We propose that sensitivity and thus detection limits may be restricted by geometric source design, limiting widespread acceptance of the technique. METHODS: The relative performance of two geometrically distinct APPI source configurations was evaluated through comprehensive performance comparison upon a single MS platform. To facilitate a fair comparison, a prototype orthogonal geometry, field-free APPI source was developed and tested against two currently commercially available open-geometry APPI sources. The prototype device was engineered based upon the geometry and functionality of first-generation, co-axial field-free APPI sources. RESULTS: Initial characterization experiments were performed by flow injection analysis using a range of analyte standards exhibiting a variety of chemical properties. A standard panel of 16 polycyclic aromatic hydrocarbons (PAHs) identified as priority pollutants by the EPA was also analyzed, demonstrating relative performance using an LC/MS workflow. The prototype field-free APPI source demonstrated the potential for order-of-magnitude performance enhancement over open-geometry sources that lack a confined field-free reaction region. CONCLUSIONS: An APPI source configuration that includes an extended field-free reaction region was demonstrated to have the potential to provide enhanced sensitivity relative to commercially available open-geometry source designs. Improved performance will no doubt lead to increased acceptance and widespread application of the technique. [ABSTRACT FROM AUTHOR]