Spatiotemporal and multi-isotope assessment of metal sedimentation in the Great Lakes.

This study investigates spatiotemporal dynamics in metal sedimentation in the North American Great Lakes and their underlying biogeochemical controls. Bulk geochemical and isotope analyses of n = 72 surface and core sediment samples show that metal (Cu, Zn, Pb) concentrations and their isotopic compositions vary spatially across oligotrophic to mesotrophic settings, with intra-lake heterogeneity being similar or higher than inter-lake (basin-scale) variability. Concentrations of Cu, Zn, and Pb in sediments from Lake Huron and Lake Erie vary from 5 to 73 mg/kg, 18-580 mg/kg, and 5-168 mg/kg, respectively, but metal enrichment factors were small (<2) across the surface- and core sediments. The isotopic signatures of surface sediment Cu (δ65Cu between -1.19‰ and +0.96‰), Zn (δ66Zn between -0.09‰ and +0.41‰) and Pb (206/207Pb from 1.200 to 1.263) indicate predominantly lithogenic metal sourcing. In addition, temporal trends in sediment cores from Lake Huron and Lake Erie show uniform metal concentrations, minor enrichment, and Zn and Pb isotopic signatures suggestive of negligible in-lake biogeochemical fractionation. In contrast, Cu isotopic signatures and correlation to chlorophyll and macronutrient levels suggest more differentiation from source variability and/or redox-dependent fractionation, likely related to biological scavenging. Our results are used to derive baseline metal sedimentation fluxes and will help optimize water quality management and strategies for reducing metal loads and enrichment in the Great Lakes and beyond.

Occurrence and mobility of thiolated arsenic in legacy mine tailings.

We studied the occurrence of dissolved thiolated Arsenic (As) in legacy tailings systems in Ontario and Nova Scotia, Canada, and used aqueous and mineralogical speciation analyses to assess its governing geochemical controls. Surface-accessible and inundated tailings in Cobalt, Ontario, contained ∼1 wt-% As mainly hosted in secondary arsenate minerals (erythrite, yukonite, and others) and traces of primary sulfide minerals (cobaltite, gersdorffite and others). Significant fractions of thiolated As (up to 5.9 % of total dissolved As) were detected in aqueous porewater and surface water samples from these sites, comprising mostly monothioarsenate, and smaller amounts of di- and tri-thioarsenates as well as methylated thioarsenates. Tailings at the Goldenville and Montague sites in Nova Scotia contained less (<0.5 wt-%) As, hosted mostly in arsenopyrite and As-bearing pyrite, than the Cobalt sites, but exhibited higher proportions of dissolved thiolated As (up to 17.3 % of total dissolved As, mostly mono- and di-thioarsenate and traces of tri-thioarsenate). Dissolved thiolated As was most abundant in sub-oxic porewaters and inundated tailings samples across the studied sites, and its concentrations were strongly related to the prevailing redox conditions and porewater hydrochemistry, and to a lesser extent, the As-bearing mineralogy. Our novel results demonstrate that thiolated As species play an important role in the cycling of As in mine waste systems and surrounding environments, and should be considered in mine waste management strategies for high-As sites.

Dissolved thiolated arsenic formed by weathering of mine wastes.

Aqueous thiolated arsenic (As) species play an important role in the biogeochemical cycling of As in wetlands and hydrothermal systems. Although mine wastes such as tailings ponds and waste rock piles may harbor similarly sub-oxic and neutral to alkaline conditions that favor the formation and mobility of thio-As species, quantitative data on their existence in these systems is lacking. We conducted laboratory column experiments under contrasting redox conditions with waste rock from the Antamina mine, Peru, and processed tailings from Montague, Nova Scotia, Canada. Dissolved As concentrations between 1 and 7000 µg/L were recorded in drainages across these mine waste types, with up to 13 µg/L As present in thiolated form, predominantly monothioarsenate. Higher percentages of thio-As species (up to 5%) were observed in drainages from enargite-rich materials compared to arsenopyrite-bearing materials (<0.5%). The lower abundance of dissolved thio-As in the arsenopyrite-rich mine waste samples is attributed to their partially oxidized nature and reduced mineral reactivity under the experimental circumneutral drainage pH, the difference in S [-II/0]-to-As molar ratios compared to the enargite-rich mine waste samples, as well as the oxidation of di- and tri-thiolated As species by dissolved Fe. Overall, our results demonstrate that aqueous thiolated As species may occur in mine wastes with different As-bearing minerals and could play an important role in governing the mobility and fate of As in these systems.