Optimisation of a fast DMS sensor (FDS) for real time quantification of dimethyl sulfide production by algae

Abstract

Production of dimethyl sulfide (DMS) from marine samples is often quantified using gas chromatography techniques. Typically, these are labour intensive and have a slow sample turnover rate. Here we demonstrate the use of a portable fast DMS sensor (FDS) that utilises the chemiluminescent reaction of DMS and ozone to measure DMS production in aqueous samples, with a maximum frequency of 10 Hz. We have developed a protocol for quantifying DMS production that removes potential signal interference from other biogenic trace gases such as isoprene (2-methyl-1,3-butadiene) and hydrogen sulfide. The detection limit was 0.89 pM (0.02 ppbv) when using a DMS standard gas mixture. The lowest DMS production rates quantified with the FDS and verified using conventional gas chromatography with flame photometric detection (GC-FPD) were around 0.01 nmol min⁻¹. There was a strong correlation in DMS production when comparing the FDS and GC-FPD techniques with a range of marine samples (e.g., r ² = 0.94 for Emiliania huxleyi). However, the combined dataset showed the FDS measured 22% higher DMS production than the GC-FPD, with the differences in rates likely due to interfering gases, for example hydrogen sulfide and isoprene. This possible overestimation of DMS production is smaller than the two-fold difference in DMS production between day and night samples from a culture of E. huxleyi. The response time of the instrument to changes in DMS production is method dependent (e.g., geometry of incubation vessel, bubble size) and was approximately 4 min under our conditions when using a culture of E. huxleyi (800 ml) with aeration at 100 ml min⁻¹. We suggest the FDS can reduce sample handling, is suitable for short- and long-term measurements of DMS production in algal cultures, and will widen the range of DMS research in marine environments.