RESUMO
Analysis of mercury (Hg) in natural water samples has routinely been impractical in many environments, for example, artisanal and small-scale gold mines (ASGM), where difficult conditions make monitoring of harmful elements and chemicals used in the processes highly challenging. Current sampling methods require the use of hazardous or expensive materials, and so difficulties in sample collection and transport are elevated. To solve this problem, a solid-phase extraction-based method was developed for the sampling and preservation of dissolved Hg in natural water samples, particularly those found around ASGM sites. Recoveries of 85% ± 10% total Hg were obtained during 4 weeks of storage in refrigerated (4 °C, dark) and unrefrigerated (16 °C, dark) conditions, and from a representative river water spiked to 1 µg L-1 Hg2+, 94% ± 1% Hg recovery was obtained. Solid-phase extraction loading flow rates were tested at 2, 5, and 10 mL min-1 with no breakthrough of Hg, and sorbent stability showed no breakthrough of Hg up to 2 weeks after functionalisation. The method was deployed across five artisanal gold mines in Kakamega gold belt, Kenya, to assess Hg concentrations in mine shaft water, ore washing ponds, and river and stream water, including drinking water sources. In all waters, Hg concentrations were below the WHO guideline limit value of 6 µg L-1, but drinking water sources contained trace concentrations of up to 0.35 µg L-1 total Hg, which may result in negative health effects from long-term exposure. The SPE method developed and deployed here is a robust sampling method that can therefore be applied in future Hg monitoring, toxicology, and environmental work to provide improved data that is representative of total dissolved Hg in water samples.
RESUMO
Mercury is considered to be one of the most toxic elements to humans. Due to pollution from industry and artisanal gold mining, mercury species are present globally in waters used for agriculture, aquaculture, and drinking water. This review summarises methods reported for preserving mercury species in water samples and highlights the associated hazards and issues with each. This includes the handling of acids in an uncontrolled environment, breakage of sample containers, and the collection and transport of sample volumes in excess of 1 L, all of which pose difficulties for both in situ collection and transportation. Literature related to aqueous mercury preservation from 2000-2021 was reviewed, as well as any commonly cited and relevant references. Amongst others, solid-phase extraction techniques were explored for preservation and preconcentration of total and speciated mercury in water samples. Additionally, the potential as a safe, in situ preservation and storage method for mercury species were summarised. The review highlighted that the stability of mercury is increased when adsorbed on a solid-phase and therefore the metal and its species can be preserved without the need for hazardous reagents or materials in the field. The mercury species can then be eluted upon return to a laboratory, where sensitive analytical detection and speciation methods can be better applied. Developments in solid phase extraction as a preservation method for unstable metals such as mercury will improve the quality of representative environmental data, and further improve toxicology and environmental monitoring studies.