Hintelmann, Holger

This work presents a new online method using gas chromatography coupled to the multicollector-inductively coupled plasma-mass spectrometer for methylmercury (MMHg) isotope ratio measurement. An extraction method using distillation was developed that effectively extracted MMHg from up to 5 grams of sediment, imparting no isotope fractionation on MMHg during extraction. Isotope ratios from transient signals were calculated using three different data treatment approaches, facilitated by a data processing application, IsoCor. Peak Area Integration using 80% of the peak gave the most accurate and precise results. Using the proposed methodology, an external precision (2 SD) of ± 0.59‰ for NIST 3177 was measured. This method can be applied to samples with MMHg concentration as low as 0.1 ng/g and was successfully applied to real sediment samples however, additional research to improve the precision of the method is required for the detection of small differences between samples.

Author Keywords: compound specific isotopic ratios, isotope ratio measurement, MC-ICP-MS, methylmercury

The detection of ciguatoxins (CTXs) in biological samples is challenging due to their low concentrations, the presence of various congeners, and the absence of standardized methods. This study uses high resolution mass spectrometry (HRMS) with P-CTX-3B as a reference standard. The protonated molecules ([M+H]+) were most prevalent, especially when acetonitrile/water was utilized, providing enhanced sensitivity. Optimized collision energies of 15 eV for protonated molecules and flow rates of 10 µl/min enhance sensitivity and peak intensities, respectively. Acetonitrile/water (ACN/H2O) is recommended as the primary solvent for HRMS method, an aspect underexplored in existing literature. The detection of CTX-3B in fish tissue samples proved to be challenging, caused by variations in ion peak intensities and matrix effects, requiring a deeper exploration of the impact of complex matrices on CTX detection. The study emphasizes the need for a reliable internal standard to mitigate these effects and highlights the ongoing challenge of developing a rapid, simple, and sensitive detection method. The study's specific focus on the P-CTX-3B analogue significantly contributes to methodology development for this congener, serving as a foundational step in understanding and detecting CTX. Despite notable progress, the study acknowledges the absence of an ideal assay, outlining key challenges for future research on ciguatera analysis. It underscores the continuous necessity for method reevaluation, testing, and the broader goal of establishing a more clarified and rugged method for the identification of CTX in fish.

Author Keywords: Analytical Chemistry, Ciguatera Fish Poisoning, Ciguatoxin, High-Resolution Mass Spectrometry, Optimization, P-CTX-3B

The Wabigoon River is known for an historic mercury (Hg) pollution source, caused by a chlor-alkali facility operating in the 1960s. As legacy Hg contamination continues to cause serious adverse health effects to the local communities living in the Wabigoon River region, it is imperative to undertake additional research to understand the deposition and transport of historical mercury in this system and more importantly, its conversion into methylmercury (MMHg) which renders it bioavailable for ongoing bioaccumulation. The aim of this dissertation was to evaluate the transport and accumulation of Hg species by doing a spatial and temporal analysis of concentrations of mercury and methylmercury along the Wabigoon River, as well as assessing rates of methylation and demethylation, identifying areas of higher methylmercury production. Results show that locations downstream from the pollution source still show elevated mercury concentrations, with levels at least five times higher in water and up to 134 times higher in sediments compared to background levels. Among selected study sites, the Hydroelectric dam, the Wabigoon Rapids wetland and Clay Lake were identified to have high capacity for methylmercury production in the system, with notably Clay Lake presenting a higher potential for methylmercury accumulation due to the observed lower methylmercury demethylation rate. Furthermore, the impact of wetting and drying cycles on Hg methylation in riverbed and wetland locations within the Wabigoon River system was investigated through a laboratory simulation. Findings indicated increased susceptibility of riverbed locations to wetting and drying cycles.

Author Keywords: Demethylation, Mercury, Methylation, Methylmercury, Wabigoon River

A meta-analysis revealed that while there is often a greater degree of contamination of soils and sediments with metals, contamination by mercury (Hg) is a large concern owing to its toxicity at low concentrations. The case study in Guyana characterized Hg and concentrations of other metals (As, Cd, Co, Cu, Mn, Ni, Pb, and Zn) in soil and sediment within gold mined areas. Metal concentrations were low in soil and sediment of sampled gold mines, while the concentrations of Hg were much higher in soil and sediment and contamination was not localized to the mine site. Moss bags and Hg passive air samplers (MerPAS) were deployed to measure atmospheric Hg around a gold mine in Mahdia, Guyana over a 90-day period as well as a 2-day period that encompassed a periodic burn (typically 2-hr). Mercury in moss and MerPAS were positively correlated over both deployment periods, but Hg concentrations measured during the 2-day event were several-fold higher in both moss and MerPAS compared with the 90-day exposure demonstrating that most of the Hg sorbed to both moss and passive samplers is lost during periods of inactivity. Using the 2-day deployment as a conservative estimate of atmospheric Hg exposure, Hg air concentrations around the burning station exceeded 100,000 ng m-3 averaged over a 48-hr period, and moss Hg concentrations were greater than 250,000 ng g-1 around the burning station, although Hg concentrations in both media decreased rapidly with distance. Mercury concentration in soil and sediment was strongly related to organic matter content, which tended to be higher away from the mine site. These controls of organic matter (carbon; C) cycling on Hg distribution and movement are clear at sites exposed to high atmospheric Hg and exist at the global scale, although Hg:C ratios in environmental media are greatly elevated at the gold mine site compared with the global average. Locally sourced biochar did not sufficiently improve physical properties (porosity) in overburden soil, which showed the worse plant response, possibly due to the high clay content that contributes to the "baked" condition of these soils and restrict root growth.

Author Keywords: Biochar, Environmental contamination, Gold mining, Mercury, Metals, Organic matter

The ᐃᓕᓕᐗᔅᑭᔾ | Ililiwaskiy (Moose Cree First Nation Territory) in Ontario's James Bay region has long faced industrial impacts on its ecosystems. Community concerns about mercury in culturally important fish prompted an interdisciplinary study bringing together chemical analysis and community knowledge. Researchers partnered with Moose Cree members through workshops, training, and interviews, while sampling over 180 fish across six sites. Walleye showed the highest mercury levels, often exceeding Health Canada's 0.5 ppm guideline for large fish and the 0.2 ppm guideline for subsistence consumers, women, and children. Community input highlighted fish as both a cultural cornerstone and food source, while noting how land-based changes have impacted fishing practices. Findings reveal elevated mercury in traditional foods and broader impacts on land-based practices and food security. The project underscores the importance of rethinking risk assessments, mitigating risks from resource extraction, water management, and supporting Moose Cree leadership in stewardship.

Author Keywords: Consumption, Cumulative effects, Fish, Indigenous knowledge, Mercury, Risk

A significant portion (15-20%) of mercury (Hg) in the Arctic Ocean is believed to originate from Arctic rivers, such as the Mackenzie River watershed in the NWT. Recent (2005- 2020) Hg monitoring data of freshwater and fish tissue and environmental model outputs were compiled and used to develop a Bayesian Network Relative Risk model (BN-RRM), a probabilistic model capable of analyzing causal relationships. The objectives of the model were to estimate the risk posed to fish health and the subsequent dietary Hg-exposure to humans; to compare the relative risks between regions of the watershed; and to identify the influential Hg sources. The output of the BN-RRMs differed significantly throughout the watershed, with atmospheric Hg deposition and soil erosion Hg release consistently flagged as important explanatory variables. Analysis of the endpoint uncertainties revealed gaps in knowledge and in Hg datasets, which should be the focus of study for future monitoring programs.

Author Keywords: Aquatic Ecosystems, Arctic, Bayesian Network, Mercury, Risk Assessment, Toxicology

The detection of ciguatoxins (CTXs) in biological samples is challenging due to their low concentrations, the presence of various congeners, and the absence of standardized methods. This study uses high resolution mass spectrometry (HRMS) with P-CTX-3B as a reference standard. The protonated molecules ([M+H]+) were most prevalent, especially when acetonitrile/water was utilized, providing enhanced sensitivity. Optimized collision energies of 15 eV for protonated molecules and flow rates of 10 µl/min enhance sensitivity and peak intensities, respectively. Acetonitrile/water (ACN/H2O) is recommended as the primary solvent for HRMS method, an aspect underexplored in existing literature. The detection of CTX-3B in fish tissue samples proved to be challenging, caused by variations in ion peak intensities and matrix effects, requiring a deeper exploration of the impact of complex matrices on CTX detection. The study emphasizes the need for a reliable internal standard to mitigate these effects and highlights the ongoing challenge of developing a rapid, simple, and sensitive detection method. The study's specific focus on the P-CTX-3B analogue significantly contributes to methodology development for this congener, serving as a foundational step in understanding and detecting CTX. Despite notable progress, the study acknowledges the absence of an ideal assay, outlining key challenges for future research on ciguatera analysis. It underscores the continuous necessity for method reevaluation, testing, and the broader goal of establishing a more clarified and rugged method for the identification of CTX in fish.

Author Keywords: Analytical Chemistry, Ciguatera Fish Poisoning, Ciguatoxin, High-Resolution Mass Spectrometry, Optimization, P-CTX-3B

The Wabigoon River is known for an historic mercury (Hg) pollution source, caused by a chlor-alkali facility operating in the 1960s. As legacy Hg contamination continues to cause serious adverse health effects to the local communities living in the Wabigoon River region, it is imperative to undertake additional research to understand the deposition and transport of historical mercury in this system and more importantly, its conversion into methylmercury (MMHg) which renders it bioavailable for ongoing bioaccumulation. The aim of this dissertation was to evaluate the transport and accumulation of Hg species by doing a spatial and temporal analysis of concentrations of mercury and methylmercury along the Wabigoon River, as well as assessing rates of methylation and demethylation, identifying areas of higher methylmercury production. Results show that locations downstream from the pollution source still show elevated mercury concentrations, with levels at least five times higher in water and up to 134 times higher in sediments compared to background levels. Among selected study sites, the Hydroelectric dam, the Wabigoon Rapids wetland and Clay Lake were identified to have high capacity for methylmercury production in the system, with notably Clay Lake presenting a higher potential for methylmercury accumulation due to the observed lower methylmercury demethylation rate. Furthermore, the impact of wetting and drying cycles on Hg methylation in riverbed and wetland locations within the Wabigoon River system was investigated through a laboratory simulation. Findings indicated increased susceptibility of riverbed locations to wetting and drying cycles.

Author Keywords: Demethylation, Mercury, Methylation, Methylmercury, Wabigoon River

The following study measured dissolved organic carbon (DOC) and total mercury (THg) concentrations in acid sensitive lakes in the Republic of Ireland. Sixty-eight upland lakes and 48 lowland lakes were sampled for DOC; the upland lakes were additionally sampled for THg. Spatial variability of DOC was explained by regional precipitation and soil organic matter. A subset of lakes was tested for long-term trends and in contrast to reports of rising DOC in European surface waters, changes in DOC were minor. Spatial variability in THg was explained by DOC and organic matter aromaticity. Long-term THg concentrations increased, likely caused by inputs of terrestrial THg. A subset of lakes was sampled for sediment and soil and the results suggested soils drove THg variation in lake water and sediment. Lake water and sediment THg was low and consistent with background regions, while soil THg was relatively high due to high organic content.

Author Keywords: Dissolved Organic Carbon, Lakes, Organic Matter, Soil, Total Mercury, Water

A novel passive sampler for mercury monitoring was prepared using organosilica sol-gel materials. It comprises a binding layer with thiol groups for mercury complexation and a porous diffusive layer through which mercury can diffuse and arrive at the binding layer. Our study demonstrated that this new sampler follows the principle of passive sampling. The mass of mercury accumulated in the binding layer depends linearly on the mercury concentration in solution, the sampling rate and the exposure time. A typical sol-gel sampler is characterized by a diffusive layer of 1.2 &mum, in which mercury ions diffuse with a coefficient of D = 0.09~10-6 cm2/s. The capacity for mercury uptake is approximately 0.64 &mug/cm2. Mercury diffusion and binding in the passive sampler are independent of the type of mercury-chloride complex. Its sampling rate increases with increasing water turbulence and decreases with increasing DOM amount. The field trial of sol-gel sampler in Miller Creek shows the concentration gained from the sol-gel passive sampler is slightly lower than that from the spot sampling.