>Magister Scientiae - MSc / This project focuses on the simple, fast and highly sensitive adsorptive stripping voltammetry detection of Nickel and Cobalt complexed with DMG and Nioxime respectively at a Reduced Graphene Oxide modified pencil graphite electrode in water samples. This research as well demonstrates a novel electrochemically reduced graphene oxide (ERGO)/mercury film (MF) nanocomposite modified PGE, prepared through successive electrochemical reduction of graphene oxide (GO) sheets and in-situ plated mercury film. The GO and graphene were characterized using FT-IR, HR-SEM, HR-TEM, XRD and Raman spectroscopy. The FT-IR results supported by Xray diffraction analysis confirmed the inclusion of oxygen moieties within the graphitic structure during the chemical oxidation step. Microscopic and spectroscopic analysis was used to confirm the stackings of graphene on the pencil electrode. The ERGO-PG-MFE, in combination with a complexing agents of [dimethylglyoxime (DMG) and Nioxime] and square-wave cathodic stripping voltammetry (SW-CSV), was evaluated towards the individual determination of Ni2+ and Co2+ respectively and simultaneous determination of both metals from the combination of DMG and Nioxime mixture. A single-step electrode pre-concentration approach was employed for the in-situ Hg-film electroplating, metal-chelate complex formation and its non-electrolytic adsorption at – 0.7 V for the individual analysis of Ni2+ and Co2+. The current response due to metal-ligand(s) complex reduction were studied as a function of experimental variables; deposition/accumulation potential, deposition/accumulation time, rotation speed, frequency and amplitude and carefully optimized for the individual determination of Ni2+and Co2+ and simultaneous determination of Ni2+ and Co2+ at low concentration levels (μg L-1) in 0.1 M NH3- NH4Cl buffer solution (pH 9.4) solution. The recorded limit of detection for the individual analysis of Ni2+and Co2+ was found to be 0.120 μg L-1 and 0.220 μg L-1 respectively, at an accumulation time of 120 s for both metals. The recorded limit of detection of the simultaneous analysis of Ni2+ and Co2+ was found to be 6.1 μg L-1 and 1.8 μg L-1 respectively. The ERGO-PG-MFE further demonstrated a highly selective stripping response toward all trace metal analysis. The testing of the applicability of graphene-based sensor and method in laboratory tap water samples was evaluated. This electrode was found to be sensitive enough to detect metal ions in the tap water samples at the 0.2 μg L-1 level for individual analysis and 0.001 μg L-1 for simultaneous, well below WHO standards.

Infamous for “Mad hatter syndrome” and “Minamata disease”, mercury (Hg) is ranked high on the Agency for Toxic Substances and Disease Registry's priority list of hazardous substances for its potent neurologic, renal, and developmental toxicities. Most typical exposures are via contaminated water and food. Although regulations and advisories are exercised at various levels, Hg pollution from both natural and anthropogenic sources has remained a major public health and safety concern. Rapid detection of solvated aqueous Hg2+ ions at low levels is critical for immediate response and protection of those who are vulnerable (young children, pregnant and breast-feeding women) to acute and chronic exposures to Hg2+. Various types of sensors capable of detecting Hg in water have been developed. In particular, the novel use of engineered carbon nanotubes (CNTs) has garnered attention due to their specificity and sensitivity towards Hg2+ detection in solution. In this focused review, we describe the sensitivity, selectivity and mechanisms of Hg2+ ion sensing at trace levels by employing CNT-based various sensor designs, and appraise the open literature on the currently applied and “proof-of-concept” methods. Five different types of CNT-based sensor systems are described: potentiometric, DNA-based fluorescence, surface plasmon resonance (SPR), colorimetric, and stripping voltammetric assays. In addition, the recognized merits and shortcomings for each type of electrochemical sensors are discussed. The knowledge from this succinct review shall guide the development of the next generation CNT-based biochemical sensors for rapid Hg2+ detection in the environment, which is a significant first step towards human health risk analysis of this legacy toxicant.

Density Functional Theory (DFT) is a powerful tool for treating large organometallic structures efficiently and accurately. DFT calculations on the Hg-catalyzed oxidation of methane to methyl bisulfate in sulfuric acid suggest the lowest energy pathway involves a closed-shell electrophilic C–H activation mechanism coupled with metal alkyl reductive functionalization and oxidation by SO3. Comparison to Tl, Zn, and Cd suggests that Hg is unique in its ability to catalyze this set of reaction steps. Comparison to K2S2O8 highlights the selectivity of this C–H activation reaction as opposed to radical conditions. In contrast, DFT calculations indicate that CoIII(TFA)3 oxidizes methane through a radical TFA ligand decarboxylation pathway. A similar decarboxylation pathway is identified for MnIII(TFA)3, but the low spin ground state of TlIII(TFA)3 favors electrophilic C–H activation over this decarboxylation pathway. DFT calculations indicate that Cp(PPh2Me)Co=CF2 undergoes [2 + 2] cycloaddition with TFE by a unique open-shell singlet diradical mechanism. The significant stability of the perfluorometallacyclobutane reveals why catalytic metathesis with TFE is difficult.

Since the Industrial Revolution at the end of the 18th century, anthropogenic changes in the environment have shifted from the local to the global scale. Even remote environments such as the high Arctic are vulnerable to the effects of climate change. Similarly, anthropogenic mercury (Hg) has had a global reach because of atmospheric transport and deposition far from emission point sources. Whereas some effects of climate change are visible through melting permafrost, or toxic effects of Hg at higher trophic levels, the often-invisible changes in microbial community structures and functions have received much less attention. With recent and drastic warming-related changes in Arctic watersheds, previously uncharacterized phylogenetic and functional diversity in the sediment communities might be lost forever. The main objectives of my thesis were to uncover how microbial community structure, functional potential and the evolution of mercury specific functions in lake sediments in northern latitudes (>54ºN) are affected by increasing temperatures and Hg deposition. To address these questions, I examined environmental DNA from sediment core samples and high-throughput sequencing to reconstruct the community composition, functional potential, and evolutionary responses to historical Hg loading. In my thesis I show that the microbial community in Lake Hazen (NU, Canada) sediments is structured by redox gradients and pH. Furthermore, the microbes in this phylogenetically diverse community contain genomic features which might represent adaptations to the cold and oligotrophic conditions. Finally, historical Hg pollution from anthropogenic sources has likely affected the evolution of microbial Hg resistance and this deposition can be tracked using sediment DNA on the Northern Hemisphere. My thesis underscores the importance of using culture-independent methods to reconstruct the structure, functional potential and evolution of environmental microbial communities.

No description available.

Master of Dental Surgery / The safety of amalgam restorations has been challenged, claims having been made that health risks are associated with the constituent mercury. There are assertions that mercury released from amalgam produces mercury poisoning, and is thus responsible for diverse symptoms of impaired health as well as disease states such as Multiple Sclerosis. This study examines the various forms of mercury and their effects and attempts particularly to delineate the significance of dental amalgam as a factor in hypersensitivity reactions and in the human body burden of mercury. Dental personnel are evaluated as a potentially high-risk group for mercury exposure. Dental amalgam and alternative restorative materials are considered, the removal of amalgam being evaluated as a therapeutic modality. The “anti-amalgam” perspective is scrutinised and the validity of the claims assessed. A review of the scientific literature, and the statements of national and international dental and scientific literature, and the statements of national and international dental and scientific organisations reflect the general support for the safety of dental amalgam. There is no evidence that health risks are associated with the use of dental amalgam other than rare local allergic reactions and oral lichenoid lesions. Notwithstanding the usefulness and safety of dental amalgam certain recommendations and conclusions are made in respect of future approaches to the utilisation of this material and for mercury in general. Further objective scientific research is necessary to determine the effects on human health of chronic exposure to low levels of mercury. There is the need for accurate general population threshold levels to be established for mercury vapour with special consideration for the vulnerable members of the community. The health professions have a significant role to play in providing informed opinion and advice for their patients and the public, in countering the more eccentric claims of the anti-amalgamists and assuaging the anxiety and confusion which accompanies this subject.

H.B. Huntington. / "July, 1948." "Reprinted from The Journal of the Acoustical Society of America, Vol. 20, No. 4, 424-432, July, 1948." / Army Signal Corps Contract No. W-36-039 sc-32037.

We have developed a regional mass balance model for the St. Lawrence River near Cornwall, Ontario that describes the fate and transport of mercury in three forms, elemental mercury (Hg0), divalent mercury (Hg2+), and methyl mercury (MeHg), in a five compartment environment (air, water, sediments, periphyton, and benthos). Our first objective was to construct a steady-state mass balance model to determine the dominant sources and sinks of mercury in this environment. Our second objective was to construct a dynamic mass balance model to predict and hindcast mercury concentrations in this environment. We compiled mercury concentrations, fluxes, and transformation rates from previous studies completed in this section of the river to develop the model in STELLA®. The inflow of mercury was the major source to this system, accounting for 0.42 mol month-1, or 95.5% of all mercury inputs, whereas outflow was 0.28 mol month-1, or 63.6% of all losses, and sediment deposition was 0.12 mol month-1, or 27.3% of all losses. The dynamic mass balance model provides estimated results that are consistent with measured data and predicts historical local industrial emissions to be approximately 400 kg year-1. Uncertainty estimates were greatest for advective fluxes in surface water, porewater, periphyton, and benthic invertebrates. This model is useful for predicting and hindcasting mercury concentrations in other aquatic environments because it contains the three main environmental compartments, all forms of mercury, and compartments (e.g. periphyton) not included in previous mercury multi-media models.

Mercury is an environmental contaminant of global concern. The distribution of mercury in freshwater systems is poorly characterized in Mexico, despite widespread contamination from industrial and urban effluents. The land use, geology, and hydrology of the Lake Zapotlán basin, Mexico are conducive to the delivery of elevated mercury in water to the lake due to untreated wastewater discharge, deforestation, and local volcanic history. To assess a mercury exposure risk to fish consumers, the concentrations of total Hg (THg) in water inputs, surface waters, sediments, and the commercial catch of tilapia and carp were investigated. Results indicate that despite high particle-bound inputs of THg to the lake in runoff and wastewater, THg in sediments and surface waters were low. Dense Typha latifolia dominated wetlands are believed to retain THg inflow from water inputs. Concentrations of THg in tilapia and carp were low, suggesting low mercury bioavailability in this system.

Ingestion exposure estimates typically use a default bioavailability of 100%, thereby assuming that the entirety of an ingested dose is absorbed into systemic circulation. However, the actual bioavailability of ingested contaminants is oftentimes lower than 100%. The research described herein investigates the use of the Simulator of the Human Intestinal Microbial Ecosystem (SHIME) for the calculation of <i>in vitro</i> bioaccessibility (IVBA), a conservative predictor of bioavailability, of mercury (Hg) from traditional northern foods and arsenic (As) from soils. The primary objective of the research described herein is to address data-gaps which have hindered attempts to incorporate IVBA into risk assessment on more than a case-by-case basis. The hypotheses of this thesis are that (1) the bioaccessibility of contaminants is dependent upon concentration due to kinetic limitations on dissolution, (2) gastrointestinal (GI) microbes in the ileum and colon alter contaminant bioaccessibility and/or speciation, (3) the GI microbial effect on bioaccessibility is toxicologically relevant, and (4) metal bioaccessibility is predictable according to dissolution kinetics.<p> Mercury bioaccessibility from country food samples was independent of total Hg concentration (F=0.5726, P=0.578) whereas As bioaccessibility was inversely related to total As concentration for Nova Scotia mine tailings, synthesized ferrihydrite with adsorbed AsV, and synthesized amorphous scorodite (P=2 x 10-10). Isotherm analysis indicated that, at high soil As concentrations, saturation of simulated GI fluids limited As bioaccessibility under gastric conditions whereas kinetic limitations constrained As bioaccessibility under intestinal conditions. Additionally, we demonstrated that GI microbes may affect Hg bioaccessibility, either increasing or decreasing bioaccessibility depending upon the type of food. For example, the bioaccessibility of HgT decreased in the presence of GI microbial activity for caribou kidney, caribou tongue, seal blood, seal brain, seal liver, and walrus flesh. In contrast, HgT bioaccessibility from Arctic char and seal intestine increased in the presence of GI microbial activity. Similarly, colon microbial activity increased (Fishers Protected LSD, P<0.05) As bioaccessibility from synthesized amorphous scorodite (56 110%), Nova Scotia mine tailings (140 300%), an agricultural soil (53%) and an ironstone soil (350%) containing elevated arsenic concentrations. However, under small intestinal conditions, this microbial effect was transient and demonstrated a small effect size. The toxicological relevance of microbial effects upon As bioaccessibility was assessed using a juvenile swine model with co-administration of oral antibiotics (neomycin and metronidazole). This study research indicated that microbial effects on As bioaccessibility are not reflected in the juvenile swine model. For example, the microbial communities present in the pigs proximal colon clustered according to antibiotic treatment (e.g. microbial communities of antibiotic treated pigs differed from non-treated pigs). Despite this, the urinary arsenic excretion (and hence arsenic bioavailability) of antibiotic-treated juvenile swine orally exposed to soil-borne arsenic was equivalent (Holm-Sidak, P=0.930) to the urinary arsenic excretion of juvenile swine not treated with antibiotics. Therefore, in vitro GI models may not need to include a microbially active intestinal stage when measuring As IVBA.<p> Metal bioaccessibility from soils appears predictable according to fundamental chemical properties of the metal-of-concern. Specifically, metal bioaccessibility of 7 of the 13 metals (V, Ni, Zn, Cu, U, Cd, & Ba but not Tl, Pb, As, Se, Cr, and Hg) regulated according to Canadian Council of Ministers of the Environment Soil Quality Guidelines (CCME SQG) were strongly dependent (R2 = 0.7) on water exchange rate constants of metal cations (kH20) indicating that desorption kinetics may serve as the foundation of a predictive model of metal bioaccessibility.