Determination of Mustard Gas Hydrolysis Products Thiodiglycol and Thiodiglycol Sulfoxide by Gas Chromatography-Tandem Mass Spectrometry after Trifluoroacetylation
ANALYTICAL CHEMISTRY
Authors: Popiel, Stanislaw; Nawala, Jakub; Dziedzic, Daniel; Soderstrom, Martin; Vanninen, Paula
Abstract
A method for detecting mustard gas degradation products thiodiglycol (TDG) and thiodiglycol sulfoxide (TDGO) in water and sediment samples using gas chromatography-tandem mass spectrometry (GC-MS/MS) after derivatization with 1-(trifluoroacetyl)imidazole (TFAI) was described. Selected reaction monitoring mode (SRM) of tandem mass spectrometry was developed for analysis of TDG and TDGO derivatives while analysis by gas chromatography-atomic emission detector (GC-AED) was performed using the 181 nm sulfur canal. TFAI derivatization conditions were optimized and the method validated. Two derivatization agents were compared, TFAI and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA), where derivatization using TFAI occurred quicker and under milder conditions than using BSTFA. Water samples containing TDG and TDGO were evaporated to dryness under nitrogen, dissolved in organic solvent followed by reaction with TFAL The limit of detection (LOD) for TDG and TDGO were 0.01 and S ng/mL, respectively. The limit of detection for TDG was decreased by two orders of magnitude if TFAI is used for derivatization rather than silyl derivatizing agents (e.g., BSTFA). TFAI has three major advantages in comparison to BSTFA, the first is much higher sensitvity, the second is a very clean background of chromatograms, and the last one is very mild conditions of derivatization. Moreover, by-products are not formed during derivatization of TDGO by TFAI in comparison to derivatization by silylating agents.
Effects of Total Dissolved Gas Supersaturation in Fish of Different Sizes and Species
INTERNATIONAL JOURNAL OF ENVIRONMENTAL RESEARCH AND PUBLIC HEALTH
Authors: Xue, Shudan; Wang, Yuanming; Liang, Ruifeng; Li, Kefeng; Li, Ran
Abstract
Two endemic fish in the upper Yangtze River, the Rock Carp (Procypris rabaudi) and Prenant's Schizothoracin (Schizothorax prenanti), were used as research objects in this study to assess the effects of total dissolved gas (TDG) supersaturation on fish of varying sizes. Fish were exposed to TDG-supersaturated water at the levels of 145, 140, 135, 130, and 125%. The results showed that fish swam slowly, responded clumsily, and then exhibited spiral swimming performance after a period of exposure to TDG-supersaturated water. Fish exhibited exophthalmos, body swelling, gill bleeding, and caudal fin bleeding when they died in the TDG-supersaturated water. With the increase in TDG supersaturation, the tolerance capacity of fish to supersaturated TDG significantly reduced. At high supersaturation, the difference in survival time between species was not significant, while fish with smaller sizes showed greater tolerance capacity. At low supersaturation, the tolerance capacity of fish was mainly affected by species, and the influence of size was relatively small. With the decrease in TDG supersaturation, the catalase (CAT) activity first increased and then decreased. Rock Carp displayed significantly less activity than Prenant's Schizothoracin on exposure to TDG-supersaturated water. At high supersaturation levels, the CAT activity of Prenant's Schizothoracin of small size was greater than that of large Prenant's Schizothoracin. In contrast, small Prenant's Schizothoracin showed less CAT activity at low TDG levels than did large individuals.