Academic literature on the topic 'Aqueous phase ethylation'

An analytical method for methylmercury (MeHg) using gas chromatography with atomic fluorescence detection is studied. The instrumental system is made based on a old gas chromatograph interfaced with an atomic fluorescence detector which is specific to Hg, currently available in our lab. Operating parameters for the GC-AFS system are optimised and analytical performances of the system are verified by quality control chart for stability. MeHg in sediment is leached and extracted to dichloromethane (DCM) in the presence of nitric acid, potassium chloride and copper sulfate. DCM in the extract is purged and MeHg is back extracted to aqueous phase followed by ethylation with sodium tetraethylborate in acetate buffer pH 5.3 containing potassium oxalate. The ethylated MeHg is then extracted to hexane and injected to GC-AFS for quantitation. The instrumental detection limit and method detection limit are 0.5 pg MeHg and 0.029 ppb MeHg (as Hg), respectively. The method can be applied for the determination of MeHg in soil, sludge and sediment samples.

A technique is presented, which allows the rapid and precise determination of methylmercury in aqueous samples. The sample is first reacted with sodium tetraethylborate, to convert the nonvolatile monomethyl mercury to gaseous methylethylmercury. The volatile adduct is then purged from solution, and recollected on a graphitic carbon column at room temperature. The methylethylmercury is then thermally desorbed from the column, and analyzed by cryogenic gas chromatography with cold vapour atomic fluorescence detection. The method allows the simultaneous determination of labile Hg(II) species, through the formation of diethylmercury, and of dimethylmercury, which is not ethylated. The methylmercury detection limit is about 0.6 pg Hg, or 0.003 ng∙L−1 for a 200-mL sample. The technique has been successfully applied directly to a wide variety of freshwater samples and alkaline tissue digestates. Seawater is analyzed following a simple extraction step to separate the methylmercury from the interfering chloride matrix. Analyses of natural surface waters have shown methylmercury levels typically in the range of 0.02–0.10 ng∙L−1, with values as high as 0.64 ng∙L−1 in a polluted urban lake. Waters collected from the anoxic bottom waters of a stratified remote lake have shown methylmercury levels as high as 4 ng∙L−1 as Hg.

A lignin-rich feedstock, soda-anthraquinone spent pulping liquor, was pyrolyzed in a kiln reactor. The liquor was prepared from mixed northern hardwood chips at a liquor-to-wood ratio of 3.5 L/kg, 16% effective alkali, and an H-factor of 1000 h. The spent liquor was pyrolyzed at 500°C as is, after oxygen oxidation, and with addition of sodium formate to determine the effect on bio-oil yield and product distribution. Contrary to bio-oil from sawdust, a clear phase separation of the liquid product into an aqueous layer and a denser organic layer is obtained. The predominant products found in the organic layer collected after pyrolysis are phenols with varying degrees of methylation and ethylation. The organic yield appears to go through a maximum (32 wt% on spent liquor organics) at around 25 wt% formate added on spent liquor dry solids and subsequently decreases at greater charges. Oxidation of the spent liquor prior to pyrolysis appears to have a detrimental effect on the organic yield.

Methods were developed for the determination of methylmercury in natural waters and sediments based on steam distillation and aqueous phase ethylation followed by gas chromatography-atomic fluorescence spectrometry. The methods were shown to be free from measurable artefactual methylation of inorganic mercury and offered improved sample throughput over existing methods. Improvements were made to existing methods for the determination of total mercury in biota, sediments and natural waters and dissolved mercury species in natural waters. These methods were applied to the study of mercury cycling in two remote field sites. The cycling of mercury species was studied in Lake Murray in Western Province, Papua New Guinea, which has been historically noted as a region of high mercury concentrations in fish. Concentrations of methylmercury and total mercury in the water column were found to be variable and consistent with non-contaminated lake systems. Concentrations of methylmercury and total mercury in the sediments were also found to be low, except for in the south of the lake, which was influenced by an intermittent supply of water and sediments with elevated mercury concentrations from the Strickland River. Methylmercury concentrations in the sediments were generally higher in the backwater areas due to littoral processes. The low concentrations of methylmercury in the sediments and waters were inconsistent with other systems previously studied in the northern hemisphere, showing a link between high mercury concentrations in fish and high concentrations of methylmercury in waters or sediments. Therefore, the biota of Lake Murray were studied in order to account for the differences between this and other systems. A study was conducted of the stable isotope ratios of carbon and nitrogen in biota from Lake Murray to elucidate key food-web interactions. This study revealed that the dominant carbon source for fish in the lake is plankton, although algae and macrophytes may also be involved in the food-web. The methylmercury bioaccumulation factors between trophic levels were similar to those measured in temperate systems of the northern hemisphere. The high concentrations of methylmercury, observed in piscivorous fish, were shown to be a consequence of the complex food-web and the number of trophic levels in the food-chains. The cycling of mercury species was studied in Lake Gordon and Lake Pedder in southwest Tasmania, which has recently been identified as being in a region of high mercury concentrations in trout and eels. The concentrations of total mercury were found to be reasonably uniform in the waters of both lakes, spatially and temporally. The concentrations of methylmercury in the waters were seasonally variable, and were consistently lower in Lake Pedder than in Lake Gordon. Dilution of methylmercury concentrations by precipitation direct to the lake surface, probably accounts for the most of the difference in methylmercury concentrations between the lakes. Owing to the long residence time of water in Lake Gordon, this reservoir mixes inputs of water with varying methylmercury concentrations. Concentrations of total mercury and methylmercury in submerged soils were low and depth profiles of mercury species in the water column did not show evidence of a gradient of mercury concentrations due to releases from the sediments. The concentrations of methylmercury observed in the water column are consistent with the concentrations observed in the fish. A budget of the mercury inputs and outputs to Lake Gordon showed that in-lake processes and sources in the catchment areas both contributed significantly to the concentrations of methylmercury in the lake. The methylation of mercury in Lake Gordon appeared to mainly occur in the surface waters (< 10 m) and was not consistent with processes leading to the methylation of mercury at the oxic/anoxic boundary observed in seepage lakes in Wisconsin. The concentrations of total mercury and methylmercury in bogs in the catchment areas of Lakes Gordon and Pedder, were high and governed by the concentration of organic matter in the sediments. The processes involved in the supply of mercury species from the Lake Gordon and Lake Pedder catchments appear to be similar to those in drainage lakes in the temperate and boreal regions of the northern hemisphere. The formation of the Lake Gordon and Lake Pedder reservoirs appears to have had little impact on the mean annual concentrations of methylmercury released to the downstream environment.