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.

Influence of Iron Substitution and Solution Composition on Brucite Carbonation.

Carbon neutral or negative mining can potentially be achieved by integrating carbon mineralization processes into the mine design, operations, and closure plans. Brucite [Mg(OH)2] is a highly reactive mineral present in some ultramafic mine tailings with the potential to be rapidly carbonated and can contain significant amounts of ferrous iron [Fe(II)] substituted for Mg; however, the influence of this substitution on carbon mineralization reaction products and efficiency has not been thoroughly constrained. To better assess the efficiency of carbon storage in brucite-bearing tailings, we performed carbonation experiments using synthetic Fe(II)-substituted brucite (0, 6, 23, and 44 mol % Fe) slurries in oxic and anoxic conditions with 10% CO2. Additionally, the carbonation process was evaluated using different background electrolytes (NaCl, Na2SO4, and Na4SiO4). Our results indicate that carbonation efficiency decreases with increasing Fe(II) substitution. In oxic conditions, precipitation of ferrihydrite [Fe10IIIO14(OH)2] and layered double hydroxides {e.g., pyroaurite [Mg6Fe2III(OH)16CO3·4H2O]} limited carbonation efficiency. Carbonation in anoxic environments led to the formation of Fe(II)-substituted nesquehonite (MgCO3·3H2O) and dypingite [Mg5(CO3)4(OH)2·âˆ¼5H2O], as well as chukanovite [Fe2IICO3(OH)2] in the case of 23 and 44 mol % Fe(II)-brucite carbonation. Carbonation efficiencies were consistent between chloride- and sulfate-rich solutions but declined in the presence of dissolved Si due to the formation of amorphous SiO2·nH2O and Fe-Mg silicates. Overall, our results indicate that carbonation efficiency and the long-term fate of stored CO2 may depend on the amount of substituted Fe(II) in both feedstock minerals and carbonate products.

A Multicompartment Assessment of Microplastic Contamination in Semi-remote Boreal Lakes.

Microplastic contamination is ubiquitous across the globe, even in remote locations. Still, the sources and pathways of microplastics to such locations are largely unknown. To investigate microplastic contamination in a semi-remote location, we measured microplastic concentrations in nine oligotrophic lakes within and around the International Institute for Sustainable Development-Experimental Lakes Area in northwestern Ontario, Canada. Our first objective was to establish ambient concentrations of microplastics in bottom sediments, surface water, and atmospheric deposition in semi-remote boreal lakes. Across all lakes, mean shallow and deep sediment microplastic concentrations, near-surface water microplastic concentrations from in situ filtering, and dry atmospheric microplastic deposition rates were 551 ± 354 particles kg-1, 177 ± 103 particles kg-1, 0.2 ± 0.3 particles L-1, and 0.4 ± 0.2 particles m-2 day-1, respectively. Our second objective was to investigate whether microplastic contamination of these lakes is driven by point sources including local runoff and direct anthropogenic inputs or nonpoint sources such as atmospheric deposition. Lakes were selected based on three levels of anthropogenic activity-low, medium, and high-though activity levels were minimal across all study lakes compared with highly populated areas. Whereas a positive correlation would indicate that point sources were a likely pathway, we observed no relationship between the level of anthropogenic activity and microplastic contamination of surface water. Moreover, the composition of microplastics in surface water and atmospheric deposition were similar, comprising mostly polyester and acrylic fibers. Together, these results suggest that atmospheric deposition may be the main pathway of microplastics to these remote boreal lakes. Environ Toxicol Chem 2024;43:999-1011. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Contrasting copper concentrations and isotopic compositions in two Great Lakes watersheds.

Copper (Cu) stable isotopes can elucidate the biogeochemical controls and sources governing Cu dynamics in aquatic environments, but their application in larger rivers and catchments remains comparatively scarce. Here, we use major and trace element hydrogeochemical data, Cu isotope analyses, and mixing modeling, to assess Cu loads and sources in two major river systems in Ontario, Canada. In both the Spanish River and Trent River catchments, aqueous hydrochemical compositions appeared reasonably consistent, but Cu concentrations were more variable spatially. In the Spanish River, waters near (historic) industrial mining activities displayed positive Cu isotope compositions (δ65CuSRM-976 between +0.75 ‰ and +1.01 ‰), but these signatures were gradually attenuated downstream by mixing with natural background waters (δ65Cu -0.65 ‰ to -0.16 ‰). In contrast, Trent River waters exhibited more irregular in-stream Cu isotope patterns (δ65Cu from -0.75 ‰ to +0.21 ‰), beyond the variability in Cu isotope signatures observed for adjacent agricultural soils (δ65Cu between -0.26 ‰ and +0.30 ‰) and lacking spatial correlation, reflective of the more diffuse sourcing and entwined endmember contributions to Cu loads in this catchment. This work shows that metal stable isotopes may improve our understanding of the sources and baseline dynamics of metals, even in large river systems.

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.

Experimental Evidence from the Field that Naturally Weathered Microplastics Accumulate Cyanobacterial Toxins in Eutrophic Lakes.

Freshwater ecosystems with recurring harmful algal blooms can also be polluted with plastics. Thus the two environmental problems may interact. To test whether microplastics influence the partitioning of microcystins in freshwater lakes, we examined the sorption of four microcystin congeners to different polymers of commercially available plastics (low-density polyethylene, polyethylene terephthalate, polyvinyl chloride, and polypropylene). We conducted three experiments: a batch sorption experiment in the laboratory with pristine microplastics of four different polymers, a second batch sorption experiment in the laboratory to compare pristine and naturally weathered microplastics of a single polymer, and a 2-month sorption experiment in the field with three different polymers experiencing natural weathering in a eutrophic lake. This series of experiments led to a surprising result: microcystins sorbed poorly to all polymers tested under laboratory conditions (<0.01% of the initial amount added), irrespective of weathering, yet in the field experiment, all polymers accumulated microcystins under ambient conditions in a eutrophic lake (range: 0-84.1 ng/g). Furthermore, we found that the sorption capacity for microcystins differed among polymers in the laboratory experiment yet were largely the same in the field. We also found that the affinity for plastic varied among microcystin congeners, namely, more polar congeners demonstrated a greater affinity for plastic than less polar congeners. Our study improves our understanding of the role of polymer and congener type in microplastic-microcystin sorption and provides novel evidence from the field, showing that naturally weathered microplastics in freshwater lakes can accumulate microcystins. Consequently, we caution that microplastics may alter the persistence, transport, and bioavailability of microcystins in freshwaters, which could have implications for human and wildlife health. Environ Toxicol Chem 2022;41:3017-3028. © 2022 SETAC.

Chemical identification of microplastics ingested by Red Phalaropes (Phalaropus fulicarius) using Fourier Transform Infrared spectroscopy.

Chemical characterization of plastics ingested by wildlife helps identify sources of plastic pollution in nature and informs assessments of exposure risk to contaminants. In 2016, Red Phalaropes (Phalaropus fulicarius) were found dead on the north coast of British Columbia, Canada, during their southward migration. Previously, ingested particles suspected to be plastics were reported upon gut examination in all carcasses collected, which likely contributed to mortality. Here, we provide chemical identification of the ingested particles using Fourier Transform Infrared (FTIR) spectroscopy. Polymer identification was successful for 41 of the 52 analysed particles (79%): 41 (79%) were confirmed as plastics, 6 (11%) were not plastics, and 5 (10%) could not be identified. The most commonly ingested plastics were polyethylene (42%) and polypropylene (23%), both of which are known to float in the marine environment. Our study highlights the vulnerability of surface foraging seabirds to plastic pollution in the marine environment.

Carbon Sequestration in Biogenic Magnesite and Other Magnesium Carbonate Minerals.

The stability and longevity of carbonate minerals make them an ideal sink for surplus atmospheric carbon dioxide. Biogenic magnesium carbonate mineral precipitation from the magnesium-rich tailings generated by many mining operations could offset net mining greenhouse gas emissions, while simultaneously giving value to mine waste products. In this investigation, cyanobacteria in a wetland bioreactor enabled the precipitation of magnesite (MgCO3), hydromagnesite [Mg5(CO3)4(OH)2·4H2O], and dypingite [Mg5(CO3)4(OH)2·5H2O] from a synthetic wastewater comparable in chemistry to what is produced by acid leaching of ultramafic mine tailings. These precipitates occurred as micrometer-scale mineral grains and microcrystalline carbonate coatings that entombed filamentous cyanobacteria. This provides the first laboratory demonstration of low temperature, biogenic magnesite precipitation for carbon sequestration purposes. These findings demonstrate the importance of extracellular polymeric substances in microbially enabled carbonate mineral nucleation. Fluid composition was monitored to determine carbon sequestration rates. The results demonstrate that up to 238 t of CO2 could be stored per hectare of wetland/year if this method of carbon dioxide sequestration was implemented at an ultramafic mine tailing storage facility. The abundance of tailings available for carbonation and the anticipated global implementation of carbon pricing make this method of mineral carbonation worth further investigation.

Geometric and dosimetric evaluation of atlas based auto-segmentation of cardiac structures in breast cancer patients.

BACKGROUND AND PURPOSE: Auto-segmentation represents an efficient tool to segment organs on CT imaging. Primarily used in clinical setting, auto-segmentation plays an increasing role in research, particularly when analyzing thousands of images in the "big data" era. In this study we evaluate the accuracy of cardiac dosimetric endpoints derived from atlas based auto-segmentation compared to gold standard manual segmentation. MATERIAL AND METHODS: Heart and cardiac substructures were manually delineated on 54 breast cancer patients. Twenty-seven patients were used to build the auto-segmentation atlas, the other 27 to validate performance. We evaluated accuracy of the auto-segmented contours with standard geometric indices and assessed dosimetric endpoints. RESULTS: Auto-segmented contours overlapped geometrically with manual contours of the heart and chambers with Dice-similarity coefficients of 0.93 ±â€¯0.02 (mean ±â€¯standard deviation) and 0.79 ±â€¯0.07 respectively. Similarly, there was a strong link between dosimetric parameters derived from auto-segmented and manual contours (R2 = 0.955-1.000). On the other hand, the left anterior descending artery had little geometric overlap (Dice-similarity coefficient 0.09 ±â€¯0.07), though acceptable representation of dosimetric parameters (R2 = 0.646-0.992). CONCLUSIONS: The atlas based auto-segmentation approach delineates heart structures with sufficient accuracy for research purposes. Our results indicate that quality of auto-segmented contours cannot be determined by geometric values only.

Accelerating Mineral Carbonation Using Carbonic Anhydrase.

Carbonic anhydrase (CA) enzymes have gained considerable attention for their potential use in carbon dioxide (CO2) capture technologies because they are able to catalyze rapidly the interconversion of aqueous CO2 and bicarbonate. However, there are challenges for widespread implementation including the need to develop mineralization process routes for permanent carbon storage. Mineral carbonation of highly reactive feedstocks may be limited by the supply rate of CO2. This rate limitation can be directly addressed by incorporating enzyme-catalyzed CO2 hydration. This study examined the effects of bovine carbonic anhydrase (BCA) and CO2-rich gas streams on the carbonation rate of brucite [Mg(OH)2], a highly reactive mineral. Alkaline brucite slurries were amended with BCA and supplied with 10% CO2 gas while aqueous chemistry and solids were monitored throughout the experiments (hours to days). In comparison to controls, brucite carbonation using BCA was accelerated by up to 240%. Nesquehonite [MgCO3·3H2O] precipitation limited the accumulation of hydrated CO2 species, apparently preventing BCA from catalyzing the dehydration reaction. Geochemical models reproduce observed reaction progress in all experiments, revealing a linear correlation between CO2 uptake and carbonation rate. Data demonstrates that carbonation in BCA-amended reactors remained limited by CO2 supply, implying further acceleration is possible.

A greenhouse-scale photosynthetic microbial bioreactor for carbon sequestration in magnesium carbonate minerals.

A cyanobacteria dominated consortium collected from an alkaline wetland located near Atlin, British Columbia, Canada accelerated the precipitation of platy hydromagnesite [Mg5(CO3)4(OH)2·4H2O] in a linear flow-through experimental model wetland. The concentration of magnesium decreased rapidly within 2 m of the inflow point of the 10-m-long (∼1.5 m(2)) bioreactor. The change in water chemistry was monitored over two months along the length of the channel. Carbonate mineralization was associated with extra-cellular polymeric substances in the nutrient-rich upstream portion of the bioreactor, while the lower part of the system, which lacked essential nutrients, did not exhibit any hydromagnesite precipitation. A mass balance calculation using the water chemistry data produced a carbon sequestration rate of 33.34 t of C/ha per year. Amendment of the nutrient deficiency would intuitively allow for increased carbonation activity. Optimization of this process will have application as a sustainable mining practice by mediating magnesium carbonate precipitation in ultramafic mine tailings storage facilities.

Accelerated carbonation of brucite in mine tailings for carbon sequestration.

Atmospheric CO(2) is sequestered within ultramafic mine tailings via carbonation of Mg-bearing minerals. The rate of carbon sequestration at some mine sites appears to be limited by the rate of CO(2) supply. If carbonation of bulk tailings were accelerated, large mines may have the capacity to sequester millions of tonnes of CO(2) annually, offsetting mine emissions. The effect of supplying elevated partial pressures of CO(2) (pCO(2)) at 1 atm total pressure, on the carbonation rate of brucite [Mg(OH)(2)], a tailings mineral, was investigated experimentally with conditions emulating those at Mount Keith Nickel Mine (MKM), Western Australia. Brucite was carbonated to form nesquehonite [MgCO(3) · 3H(2)O] at a rate that increased linearly with pCO(2). Geochemical modeling indicated that HCO(3)(-) promoted dissolution accelerated brucite carbonation. Isotopic and aqueous chemistry data indicated that equilibrium between CO(2) in the gas and aqueous phases was not attained during carbonation, yet nesquehonite precipitation occurred at equilibrium. This implies CO(2) uptake into solution remains rate-limiting for brucite carbonation at elevated pCO(2), providing potential for further acceleration. Accelerated brucite carbonation at MKM offers the potential to offset annual mine emissions by ~22-57%. Recognition of mechanisms for brucite carbonation will guide ongoing work to accelerate Mg-silicate carbonation in tailings.