The determination of dimethyl sulfoxide in natural waters using electrochemical reduction

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.