ABSTRACT
An automated device has been developed to measure aqueous dimethyl sulfide (DMSaq), its precursor dimethylsulfoniopropionate (DMSP), and atmospheric gaseous dimethyl sulfide (DMSg). In addition to having a role in the oceanic atmosphere, DMS and DMSP have recently gained substantial interest within the biosciences and are suspected as chemoattractants for predators searching for prey. To provide the spatial resolution relevant for biogeochemical functions, fast and on-site analysis of these compounds is an important technique. The system described measures the dimethyl sulfur compounds by sequential vaporization of DMSaq and DMSP to their gas phase, which is then analyzed by chemiluminescence detection (SVG-CL). The device has five analysis modes (full, DMS, water, gas, and DMSP mode) that can be selected by the user depending on the required analyte or desired sampling rate. Seawater analyses were performed by the developed SVG-CL system and, simultaneously, by an ion molecule reaction-mass spectrometer and a gas chromatograph-flame photometric detector to verify quantitative analysis results. Results obtained by the new method/device agreed well with those by the other methods. Detection limits of the SVG-CL system are 0.02 ppbv and 0.04 nM for DMSg and DMSaq/DMSP, respectively, which are much better than those of the mass spectrometer. The SVG-CL system can be easily installed and operated on a boat. Spatial variability in DMS and DMSP off the coast of Japan were obtained, showing significant changes in the concentrations of the components at the brackish/saline water interface and at the channel between the closed and open seas.
ABSTRACT
A small, simple device was developed for trace analysis of dimethyl sulfide (DMS) and dimethylsulfoniopropionate (DMSP) in natural waters. These compounds are known to be the major sources of cloud condensation nuclei in the oceanic atmosphere and ideally should be measured onsite because of their volatility and instability. First, chemical and physical vapor generations were examined, and simple pressurizing by injection of 30 mL of air using a syringe was adopted. Pressurized headspace air above a 10 mL water sample was introduced to a detection cell as a result of the pressure differential and mixed with ozone to induce chemiluminescence. Although the measurement procedure was simple, the method was very sensitive: sharp peaks appeared within seconds for nanomolar levels of DMS, and the limit of detection was 0.02 nmol L(-1) (1 ng L(-1)). Although interference from methanethiol was significant, this was successfully addressed by adding a small amount of Cd(2+) before DMS vapor generation. DMSP was also measured after hydrolysis to DMS, as previously reported. Pond water and seawater samples were analyzed, and DMS was found in both types of sample, whereas DMSP was observed only in seawater. The DMS/DMSP data obtained using the developed method were compared with data obtained by purge/trap and gas chromatography-mass spectrometry, and the data from the two methods agreed, with good correlation (R(2) = 0.9956). The developed device is inexpensive, light (5 kg), simple to use, can be applied in the field, and is sensitive enough for fresh- and seawater analysis.
