Browsing by Subject "Mercury"
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Item A comparison of factors affecting the small-scale distribution of mercury contamination in a Zimbabwean stream system(2017-04-18) Green, Corey S.; Thies, Monte L.; Lewis, Patrick J.; Wozniak, Jeffrey R.Artisanal small-scale mining (ASM) operations use mercury liberally in the gold extraction process, as compared to large scale industrial mining operations, and accounts for approximately one third of anthropogenic mercury consumption worldwide. These ASM operations are concentrated in many impoverished and poorly regulated countries such as Zimbabwe, resulting in a number of negative environmental and health impacts. There are three pathways by which mercury generally enters the environment from gold mining: 1) directly via private miners, 2) through stamp mill operations (also used by ASM miners), and 3) industrial-scale mining operations. To examine the levels of mercury contamination resulting in one such geographic locality, sediment and tailing samples in a single, heavily mined watershed in southern Zimbabwe were collected from May – June 2015. Samples were collected from the stream system, as well as six stamp mills and a single industrial mine in the watershed. GPS point location data were taken for mining operations and sampling sites to examine the spatial patterns of mercury concentration relative to each mining operation. Data were first analyzed using linear regression then a MARS model, followed by application of an ANCOVA model to assess the relationship between mercury concentrations and three factors; percent organic carbon, distance downstream, and distance from potential contamination source. Mercury concentrations within the study area ranged between 6-1,541 µg/kg dw (mean 142 µg/kg dw). Analyses of mercury concentrations indicated a positive relationship with percent organic carbon and a negative relationship with distance downstream and distance from potential contamination source. Results from this study will help to elucidate the relationship between gold production and the spatial scale of mercury contamination in aquatic ecosystems in Africa. These data may lead to a better understanding of the relationship between mercury use and community health, which may aid both the local and global communities in regulating mercury contamination of the environment, thereby reducing the suffering and early death of many people in impoverished countries where ASM is commonplace.Item A Meta-analysis of Mercury Levels in Lavaca Bay Texas(2014-05-07) Pillado, Maria C.Lavaca Bay is a secondary bay to Matagorda Bay on the central Texas Coast. In 1970 Texas Department of Health (TDH) closed parts of Lavaca Bay to the harvesting of oysters due to mercury contamination as a result of contaminated wastewater discharged into the bay by a chlor-alkali plant operated by Alcoa. In 1988 TDH closed the area around Dredge Island which is adjacent to the chlor-alkali plant to the taking of finfish and crabs due to elevated mercury levels. In 1994 it was proposed that the area around Dredge Island and area around the chlor-alkali plant were placed on the National Priorities List (NPL). In December of 2001 the Record of Decision (ROD) was signed to initiate the remediation process. The purpose of this study is to use a meta-analysis to determine if the mercury levels in secondary and tertiary trophic levels have changed between years 1992 and 2012, and if the levels in red drum (Sciaenops ocellatus) and oysters (Crassostrea virginica) have decreased over time. The meta-analysis used biota and sediment collected and analyzed for total mercury in 2012, historical data from Texas Department of Health (TDH), U.S. Environmental Protection Agency (EPA), and Woodward-Clyde (1992).Item Absorption of chlorine and mercury in sulfite solutions(2002-08) Roy, Sharmistha; Rochelle, Gary T.Item Advances in gamma-ray spectroscopy : compton suppression and gamma-gamma coincidence(2011-05) Horne, Steven Michael; Landsberger, Sheldon; Biegalski, StevenThis project aims to improve research in gamma-ray spectroscopy by using advanced detector systems. These systems are designed to reduce interference inherent in gamma-ray spectroscopy by rejecting Compton scattering events from high-energy gamma-rays, as well as look at cascading decays of gamma-rays through gamma-gamma coincidence counting. By combining these methods, one is able to lower detection limits for many elements than would otherwise be possible. This work also takes advantage of neutron activation analysis, which allows stable elements to be analyzed by activating them with neutrons, causing them to become unstable and decay with radioactive signatures. By analyzing these signatures, one is able to detect trace levels of elements with relatively small samples sizes (< 1g) and in a nondestructive manner.Item Application of diffusive gradient in thin-film passive samplers to assess mercury availability and mobility in a fresh water river system(2015-12) Bireta, Paul Joseph Hardy; Katz, Lynn Ellen; Reible, Danny D.; Jackson, William A; Liljestrand, Howard M; Werth, Charles JThe accurate measurement of mercury in sediment porewater is a challenge using conventional sampling techniques which commonly require removal of sediment, transportation, and processing. Passive sampling is an alternative technique that measures sediment porewater concentrations in-situ and without significant sample disturbance. One passive sampling technique for mercury in sediment porewater is Diffusive Gradient in Thin-Films (DGT) samplers; a technique that has been employed since the 1990’s but is relatively new for mercury and has been primarily utilized in the laboratory. The approach estimates porewater concentrations of mercury species in-situ based upon the rate at which the species diffuses through a thin film of controlled thickness. The modification of this technique for field applications could significantly improve measurement of mercury porewater concentrations; however the technique lacks examples established quality assurance and control protocols, commercial availability, and examples of its successful implementation in a field setting. Sediment systems are important to mercury fate in aquatic systems due to their role as both a sink for inorganic mercury and source for methylmercury. Within the sediment, porewater chemistry is important to understanding mercury speciation and reactivity. The interaction between the solid and dissolved mercury species ranges greatly between systems and controls availability of mercury for methylation, direct exposure, and transport. This research uses DGT samplers in field applications to assess mercury speciation and mobility in sediment porewater. A representative site, the South River (Virginia, USA) was selected for evaluation of DGT sampling, development of sampling protocols and utilization of the technique for improving our ability to identify sources of mercury flux and evaluate of the biogeochemistry of a site. Through the use of DGT samplers, the river banks were identified as a potential source of mercury into the channel during flood events and the subsequent bank drainage. This behavior had not been identified using traditional sampling techniques and was not taken into account in the site conceptual model for mercury sources into the river. Using the DGT sampler data, a mercury flux budget was performed for a bank drainage event and it was determined that the river bank contributes significantly more mercury during large flood events than during baseline flow conditions. Laboratory studies were performed using South River bank sediment to better understand the biogeochemical behavior observed in the field.Item Bioaccumulation of mercury in pelagic fishes in NW Gulf of Mexico(Texas A&M University, 2006-08-16) Cai, YanTotal mercury (Hg) levels were determined in the tissues of ten taxa of pelagic fishes, with a special emphasis on apex predators (large vertebrates). Highest Hg levels were observed in blue marlin (Makaira nigricans), carcharhinid sharks (Genus Carcharhinus) and little tunny (Euthynnus alletteratus), ranging from 1.08 to 10.52 ppm. Moderate to low concentrations (<1.0 ppm) were observed in blackfin tuna (Thunnus atlanticus), cobia (Rachycentron canadum), dolphinfish (Coryphaena hippurus), greater amberjack (Seriola dumerili), king mackerel (Scomberomorus cavalla), wahoo (Acanthocybium solandri) and yellowfin tuna (Thunnus albacares). For the majority of species examined, Hg level did not vary significantly between locations (Texas and Louisiana) and years (2002 and 2003). The relationship between Hg level and fish size/weight was also explored and six taxa (blackfin tuna, carcharhinid sharks, dolphinfish, king mackerel, wahoo, yellowfin tuna) showed significant positive relationships between Hg level and body size and/or weight. Natural dietary tracers, stable isotopes (15N, 13C) and fatty acids were used to evaluate the relationship between Hg and trophic position and the relationship between Hg and dietary history. Stable nitrogen isotope analysis showed that Hg levels in fish tissues were positively associated with trophic position. Based on the 13C and 15N values of pelagic consumers examined in this study, three natural groups were identified with cluster analysis, and the same groupings were detected based on fatty acid profiles. This not only confirmed the existence of these natural groupings, but also indicated that the distinguishing factors for the grouping was likely connected with the dietary history of these fishes. The classification tree based on the fatty acid profiles of pelagic fishes readily separated fishes from different regions, suggesting that diets of pelagic taxa within the same region are similar or these consumers share a common source of organic matter in their food web. Findings from this study complement other Hg investigations conducted in the Gulf and also furthered our understanding of the link between feeding ecology and Hg accumulation. Moreover, the combined use of stable isotope and fatty acid techniques provided new insights on the dietary history of pelagic fishes in the Gulf of Mexico.Item Enhanced Land Subsidence and Seidment Dynamics in Galveston Bay- Implications for Geochemical Processes and Fate and Transport of Contaminants(2013-07-05) Almukaimi, Mohammad EGalveston Bay is the second largest estuary in the Gulf of Mexico. The bay?s watershed and shoreline contains one of the largest concentrations of petroleum and chemical industries in the world, with the greatest concentration within the lower 15 km of the San Jacinto River/Houston Ship Channel (SJR/HSC). Extensive groundwater has been withdrawn to support these industries and an expanding population has resulted elevated land subsidence, with the highest land subsidence in the lower SJR/HSC, of over 3 m (3 cm yr^-1) and has decreased seaward throughout the bay to 0.6 cm yr^-1 near Galveston Island. Mercury (Hg) contamination is well documented throughout the bay?s sediments. Sediment vibra-cores were collected throughout the bay systems. 210Pb and 137Cs geochronologies from these cores was used to determine sedimentation rates and correlated to Hg profiles to estimate input histories. Relative Sea Level Rise (RSLR) is the sum of eustatic sea level rise and land subsidence. The results show sedimentation rates are high in areas with high rates of RSLR and the rates are of the same order of magnitude, however, in general, sedimentation rates are as much as 50% of RSLR, indicating that sedimentation has not kept pace with land subsidence, although they have the same relative order. Hg core profiles were correlated with radioisotope geochronologies and show significant input of Hg beginning around 1940, with a peak around 1971, and a dramatic drop off in concentration afterwards, demonstrating it to be a valuable geochronology tool. Hg concentrations were found to be dramatically higher proximal to the SJR/HSC and progressively decreasing seaward and to distal parts of the bay.Item The interaction of benthic oligochaetes, T. tubifex with mercury impacted sediments: an assessment of bioaccumulation and biogeochemistry(2014-05) Offutt, Alyssa Jane; Reible, Danny D.Mercury is a pervasive environmental contaminant which is globally distributed in freshwater ecosystems. In order to assess the risk that mercury and methylmercury pose to public health through consumption and trophic level transfer, it is first necessary to understand the interactions and uptake that occurs between benthic organisms and mercury impacted sediments. Delineation of these interactions currently rely on correlating measurements of bulk sediment concentrations with bioaccumulation of either total mercury or methylmercury. However, it has been proposed that porewater concentrations, rather than sediment concentrations, should be used to predict uptake and bioavailability. Diffusive gradient in thin films (DGTs) have been proposed as a viable technique for porewater measurements to assess the bioavailable fractions of mercury. DGTs were compared to traditional bulk solid sampling to assess their capabilities for the prediction of total and methylmercury bioaccumulation in benthic oligochaetes, T. tubifex. DGTs performed similarly to the bulk solids sampling approach in respect to their correlation with mercury bioaccumulation in the sediment matrix studied. Bioturbation was shown to impact redox profiles in the sediment which led to a decrease in porewater methylmercury concentrations in the uppermost surficial sediment depths. These results indicate that monitoring tools such as DGTs are necessary to better understand the fate of mercury at field scale contaminated sites.Item Laboratory optimization and field demonstration of diffusive gradients in thin films for in-situ mercury measurements of river sediments(2010-08) Chess, Timothy William; Reible, Danny D.; Katz, Lynn E.Diffusive gradients in thin film (DGT) technique is applied to determine pore water mercury concentrations in river sediments. DGT devices have been a useful indicator of dissolved metals in aqueous systems, although it is not as well developed for measuring mercury. DGT devices were evaluated for three different ion exchange resins for adsorption of mercury. After a series of laboratory experiments, 3-Mercaptopropyl Functionalized Silica Gel (3M) was chosen as an effective resin layer. Laboratory experiments showed that the resin strongly associated with dissolved Hg²⁺. DGT probes were tested with sediments from the South River (Virginia, USA) in the laboratory and the time dependent deployment verified an uptake of mercury to the probes and established an effective diffusion coefficient for site specific utilization. Multiple piston and sediment probes were deployed in the South River in-situ to determine overlying water Hg concentrations and sediment pore water Hg concentration profiles. The DGT devices were successful in measuring Hg concentrations in-situ.Item Mercury emission control for coal fired power plants using coal and biomass(2009-05-15) Arcot Vijayasarathy, UdayasarathyMercury is a leading concern among the air toxic metals addressed in the 1990 Clean Air Act Amendments (CAAA) because of its volatility, persistence, and bioaccumulation as methylmercury in the environment and its neurological health impacts. The Environmental Protection Agency (EPA) reports for 2001 shows that total mercury emissions from all sources in USA is about 145 tons per annum, of which coal fired power plants contribute around 33% of it, about 48 tons per annum. Unlike other trace metals that are emitted in particulate form, mercury is released in vapor phase in elemental (Hg0) or oxidized (Hg2+, mainly HgCl2) form. To date, there is no post combustion treatment which can effectively capture elemental mercury vapor, but the oxidized form of mercury can be captured in traditional emission control devices such as wet flue gas defulrization (WFGD) units, since oxidized mercury (HgCl2) is soluble in water. The chlorine concentration present during coal combustion plays a major role in mercury oxidation, which is evident from the fact that plants burning coal having high chlorine content have less elemental mercury emissions. A novel method of co-firing blends of low chlorine content coal with high chlorine content cattle manure/biomass was used in order to study its effect on mercury oxidation. For Texas Lignite and Wyoming coal the concentrations of chlorine are 139 ppm and 309 ppm on dry ash free basis, while for Low Ash Partially Composted Dairy Biomass it is 2,691 ppm. Co-firing experiments were performed in a 100,000 BTU/hr (29.3 kWt) Boiler Burner facility located in the Coal and Biomass Energy laboratory (CBEL); coal and biomass blends in proportions of 80:20, 90:10, 95:5 and 100:0 were investigated as fuels. The percentage reduction of Hg with 95:5, 90:10 and 80:20 blends were measured to be 28- 50%, 42-62% and 71-75% respectively. Though cattle biomass serves as an additive to coal, to increase the chlorine concentration, it leads to higher ash loading. Low Ash and High Ash Partially Composted Dairy Biomass have 164% and 962% more ash than Wyoming coal respectively. As the fraction of cattle biomass in blend increases in proportion, ash loading problems increase simultaneously. An optimum blend ratio is arrived and suggested as 90:10 blend with good reduction in mercury emissions without any compromise on ash loading.Item Mercury specation during thermal remediation and in post-treatment environments(2011-12) Park, Chang Min; Liljestrand, Howard M. (Howard Michael); Katz, Lynn Ellen; Lawler, Desmond F.; Reible, Danny D.; Pope, Gary A.Mercury is a toxic metal that has been released to the environment through numerous industrial activities. It can exist in various solid, aqueous, and gaseous forms. Volatile Hg(0) is frequently present at the source of a spill where it behaves as a dense non-aqueous phase liquid (DNAPL) contaminant that can change oxidation state and speciation via chemical or biological reactions. Mercury speciation is a key factor determining the mobility, bioavailability, and toxicity of Hg in the environment. Previous research has demonstrated that In Situ Thermal Desorption (ISTD) can be used in various modes to treat soil contaminants including Hg(0). The application of ISTD and other remediation processes must incorporate potential speciation during remediation and assess mobility of any mercury remaining in the soil post-remediation. However, research examining the impact of mercury speciation on ISTD processes is limited. The goals of this research are to investigate the fate and transport of mercury in soils from the source where concentrations are expected to be high to dilute solutions associated with down gradient groundwater, lakes, and rivers. For high concentrations of mercury, equilibrium speciation has been investigated to identify potential transformations at high temperatures consistent with those applied in ISTD processes. A model has been developed that describes mercury speciation over a range of environmental conditions. At low mercury concentrations, competitive Hg(II) adsorption on the soil minerals, goethite and gibbsite, has been evaluated over a range of experimental conditions. Models describing Hg(II) adsorption and aqueous speciation have been developed to provide a tool for predicting the fate and transport of residual mercury after thermal remediation applications. The results of these studies demonstrate that ISTD is feasible, but the off-gas speciation will depend on both the applied temperatures and the soil composition and redox conditions of the site. Pure phase mercury was predicted to be vaporized at temperatures well within the range of typical ISTD processes. The adsorption of trace levels of Hg(II) remaining after ISTD was successfully modeled on goethite and gibbsite using the 1-pK CD-MUSIC model.Item Pilot-Scale Demonstration of hZVI Process for Treating Flue Gas Desulfurization Wastewater at Plant Wansley, Carrollton, GA(2011-12-06) Peddi, Phani 1987-The hybrid Zero Valent Iron (hZVI) process is a novel chemical treatment platform that has shown great potential in our previous bench-scale tests for removing selenium, mercury and other pollutants from Flue Gas Desulfurization (FGD) wastewater. This integrated treatment system employs new iron chemistry to create highly reactive mixture of Fe^0, iron oxides (FeOx) and various forms of Fe (II) for the chemical transformation and mineralization of various heavy metals in water. To further evaluate and develop the hZVI technology, a pilot-scale demonstration had been conducted to continuously treat 1-2 gpm of the FGD wastewater for five months at Plant Wansley, a coal-fired power plant of Georgia Power. This demonstrated that the scaled-up system was capable of reducing the total selenium (of which most was selenate) in the FGD wastewater from over 2500 ppb to below 10 ppb and total mercury from over 100 ppb to below 0.01 ppb. This hZVI system reduced other toxic metals like Arsenic (III and V), Chromium (VI), Cadmium (II), Lead (II) and Copper (II) from ppm level to ppb level in a very short reaction time. The chemical consumption was estimated to be approximately 0.2-0.4 kg of ZVI per 1 m^3 of FGD water treated, which suggested the process economics could be very competitive. The success of the pilot test shows that the system is scalable for commercial application. The operational experience and knowledge gained from this field test could provide guidance to further improvement of technology for full scale applications. The hZVI technology can be commercialized to provide a cost-effective and reliable solution to the FGD wastewater and other metal-contaminated waste streams in various industries. This technology has the potential to help industries meet the most stringent environmental regulations for heavy metals and nutrients in wastewater treatment.Item Sorption of Arsenic, Mercury, Selenium onto Nanostructured Adsorbent Media and Stabilization via Surface Reactions(2011-02-22) Han, Dong SukThe overall goal of this study is to evaluate the ability of novel nanostructured adsorbent media (NTAs, iron sulfides (FeS2 and FeS)) to remove arsenic, selenium and mercury from ash and scrubber pond effluents. The NTAs aim to enhance arsenic removal from solution compared to conventional adsorbents. The iron sulfides are expected to produce stable residuals for ultimate disposal after removing As, Se and Hg from solution, so that removal of these compounds from wastewaters will not result in contamination of soils and groundwaters. Methods for reliably and economically producing these materials were developed. The synthesized NTAs and iron sulfides were characterized by surface analysis techniques such as XRD, FT-IR, SEM-EDS, TEM, XPS, AFM and N2-adsorption. These analyses indicated that Ti(25)-SBA-15 has highly ordered hexagonal mesopores, MT has interparticle mesopores, pyrite (FeS2) forms crystalline, nonporous rectangular nanoparticles (<500 nm), and mackinawite (FeS) forms amorphous, nonporous nanoparticles (<100 nm). Kinetic and equilibrium tests for As(III, V) removal were conducted with NTAs over a range of pH (4, 7, 9.5). The rates of arsenic uptake were very fast and followed a bi-phasic sorption pattern, where sorption was fast for the first 10 minutes, and then slowed and was almost completed within 200 minutes. Distinct sorption maxima for As(III) removal were observed between pH 7 and pH 9.5 for MT and between pH 4 and pH 7 for Ti(25)-SBA-15. The amount of As(V) adsorbed generally decreased as pH increased. In addition, a surface complexation model (SCM) based on the diffuse layer model (DLM) was used to predict arsenic adsorption envelopes by NTAs under various environmental conditions. The SCM for As(III, V) adsorption by NTAs demonstrated the role of mono- and bidentate surface complexes in arsenic adsorption. A batch reactor system was employed in an anaerobic chamber to conduct experiments to characterize both the removal of As, Se, Hg from solution and their subsequent reactions with iron sulfides. Experiment variables for removal experiments included: contaminant valence state (As(V), As(III), Se(VI), Se(IV), Hg(II)); adsorbent/reactant type (FeS, FeS2); adsorbent/reactant concentration; pH (7, 8, 9, 10); and competing ion (SO42-) concentration (0, 1, 10 mM). Experimental variables for reaction experiments were reaction time (up to 30 days) at pH 8 and oxidation states of contaminants. In addition, the stability of iron sulfides (FeS2, FeS) combined with target compounds was investigated by measuring the ability of the target compounds to resist release to the aqueous phase after removal. These experiments showed that iron sulfides were good adsorbent/reactants for target contaminants in spite of the presence of sulfate. This was particularly true at intermediate concentrations of target compounds. The experiments also demonstrated that iron sulfides interacted with target contaminants in such a way to improve their resistance to being released back to solution as pH was changed. Therefore, this study demonstrates the ability of novel nanostructured adsorbent media to remove arsenic, selenium and mercury from ash and scrubber pond effluents and the ability of iron sulfides to produce residuals that are stable when disposed in landfills.Item Trimeric perfluoro-ortho-phenylene mercury as a building block for supramolecular materials(Texas A&M University, 2006-04-12) Haneline, Mason ReamesTrimeric perfluoro-ortho-phenylene mercury (1) constitutes one of the simplest trifunctional Lewis acidic hosts. Cooperative effects arising from the proximity of the mercury(II) centers, the electron-withdrawing properties of the backbone and the accessibility of the electrophilic sites leads to the facile complexation of neutral and electron rich substrates. The planarity of the structure as well as its overall polarizability compounded with relativistic effects at mercury also permits the occurrence of non-covalent interactions. The main objective of this dissertation was to explore the potential of 1 as a building block for supramolecular materials. Compound 1 was investigated using single crystal x-ray diffraction and was found to display a rich polymorphism. The electronic structure, probed by DFT methods, shows that the LUMO of 1 has a large contribution from the mercury 6p orbitals and features a large lobe protruding above and below the center of the trinuclear mercury core. Complexes in which two nitronyl nitroxide radicals (NIT-Ph = 2-(phenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) coordinate to the trinuclear core of 1 above and below the Hg3 plane reveal that 1 does not significantly mediate magnetic interactions. The ability of 1 to complex π-basic molecules such as tetrathiafulvalene (TTF), toluene, o-xylene, m-xylene, p-xylene, mesitylene, biphenyl, naphthalene, acenaphthalene, anthracene, pyrene, triphenylene, perylene, and coronene was also investigated and show that 1 and arenes form extended binary stacks in which the two components alternate. The photoluminescence observed in some of these supramolecular complexes corresponds to the phosphorescence of the arene indicating a mercury heavy atom effect. Complexation of 1 in solution was observed with hexaalkoxytriphenylenes (HATn, n = 1, 6) by fluorescence and NMR spectroscopy. Finally, compound 1 forms electrophilic double sandwich structures with ferrocene and nickelocene in which a molecule of 1 caps each of the Cp ligands. The nickelocene adduct is stabilized towards oxidation, and the photophysical and magnetic properties indicate the occurrence of a mercury heavy atom effect.