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.

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.

Radio- and stable carbon isotope analysis reveals minimal assimilation of petrogenic carbon into an oligotrophic freshwater food web after experimental spills of diluted bitumen.

Following an oil spill into water, bacteria can biodegrade petroleum hydrocarbons which could lead to petrogenic carbon assimilation by aquatic biota. We used changes in the isotope ratios of radio- (Δ14C) and stable (δ13C) carbon to examine the potential for assimilation of petrogenic carbon into a freshwater food web following experimental spills of diluted bitumen (dilbit) into a boreal lake in northwestern Ontario, Canada. Different volumes (1.5, 2.9, 5.5, 18, 42, 82, and 180 L) of Cold Lake Winter Blend (a heavy crude blend of bitumen and condensate) dilbit were applied to seven 10-m diameter littoral limnocorrals (approximate volume of 100 m3), and two additional limnocorrals had no added dilbit to serve as controls. Particulate organic matter (POM) and periphyton from oil-treated limnocorrals had lower δ13C (up to 3.2‰ and 2.1‰ for POM and periphyton, respectively) than the control at every sampled interval (3, 6 and 10 weeks for POM and 6, 8 and 10 weeks for periphyton). Dissolved organic and inorganic carbon (DOC and DIC, respectively) had lower Δ14C in the oil-treated limnocorrals relative to the control (up to 122‰ and 440‰ lower, respectively). Giant floater mussel (Pyganodon grandis) housed for 25 days in aquaria containing oil-contaminated water from the limnocorrals did not show significant changes in δ13C values of muscle tissue compared to mussels housed in control water. Overall, the changes in δ13C and Δ14C observed indicated small amounts (up to 11% in DIC) of oil carbon incorporation into the food web. The combined δ13C and Δ14C data provide evidence for minimal incorporation of dilbit into the food web of this oligotrophic lake, suggesting that microbial degradation and subsequent incorporation of oil C into the food web may play a relatively small role in the ultimate fate of oil in this type of ecosystem.

Application of quantitative mineralogy to determine sources of airborne particles at a European copper smelter.

Copper processing operations, such as smelters and refineries, can produce airborne particles that may impact the health of workers. At these operations, worker exposure to chemicals are regularly monitored to ensure that regulatory compliance with occupational exposure limit values (OELVs) are maintained. Determining the type of airborne particles present is important for characterizing the composition of dust exposures and better understanding the relationship between worker exposure and health. Routine methods of analysis (e.g., chemical assay) are unable to differentiate between phases containing the same elements and may result in ambiguity. A novel approach of a combination of Quantitative Evaluation of Materials by Scanning Electron Microscope (QEMSCAN) and chemical characterization was used here to evaluate airborne and settled dust collected at key locations throughout a copper smelter in Europe. The copper (Cu) phases present in the airborne dust are indicative of the activities performed at specific locations. In the batch preparation area where Cu concentrate is received, significant amounts of Cu were carried in sulfidic minerals (chalcocite, chalcopyrite/bornite, >40%), whereas near the anode and electric furnace, the majority of Cu in dust was carried in metallic and oxidic phases (60-70%). Particle size analysis of the settled dust indicates that the sulfidic and oxidic Cu minerals are more likely to become airborne over metallic Cu. Furthermore, overall Cu concentrations decreased with particle size where metallic and oxidic Cu dominate, which suggests that differences in the proportion of Cu forms present in the dust will impact how much Cu ends up in the respirable fraction. These results highlight the need to understand the characterization of Cu in dust in order to set better OELVs.

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.

Uranium: an overview of physicochemical properties, exposure assessment methodologies, and health effects of environmental and occupational exposure.

Uranium is chemo- and radiotoxic element which can cause multifactorial health hazards. Natural and anthropogenic uranium contamination raises concerns about potential public health problems. Natural contamination plays a significant role with regard to uranium exposure in the general population, whereas anthropogenic contamination leads to occupational uranium exposure, particularly in nuclear industry workers. In this review, we present a state-of-the-art status concerning uranium-induced health risks with a focus on epidemiological findings of uranium processing and enrichment plant workers. We provide a general overview of physicochemical properties of uranium and analytical methods for measuring or monitoring uranium, describe environmental and occupational exposure scenarios, and discuss the challenges for objectively investigating risks from uranium exposure.

Emerging applications of high-precision Cu isotopic analysis by MC-ICP-MS.

As a component of many minerals and an essential trace element in most aerobic organisms, the transition metal element Cu is important for studying reduction-oxidation (redox) interactions and metal cycling in the total environment (lithosphere, atmosphere, biosphere, hydrosphere, and anthroposphere). The "fractionation" or relative partitioning of the naturally occurring "heavy" (65Cu) and "light" (63Cu) isotope between two coexisting phases in a system occurs according to bonding environment and/or as a result of a slight difference in the rate at which these isotopes take part in physical processes and chemical reactions (in absence of equilibrium). Due to this behaviour, Cu isotopic analysis can be used to study a range of geochemical and biological processes that cannot be elucidated with Cu concentrations alone. The shift between Cu+ and Cu2+ is accompanied by a large degree of Cu isotope fractionation, enabling the Cu isotope to be applied as a vector in mineral exploration, tracer of origin, transport, and fate of metal contaminants in the environment, biomonitor, and diagnostic/prognostic marker of disease, among other applications. In this contribution, we (1) discuss the analytical protocols that are currently available to perform Cu isotopic analysis, (2) provide a compilation of published δ65Cu values for matrix reference materials, (3) review Cu isotope fractionation mechanisms, (4) highlight emerging applications of Cu isotopic analysis, and (5) discuss future research avenues.

Zinc stable isotope analysis reveals Zn dyshomeostasis in benign tumours, breast cancer, and adjacent histologically normal tissue.

The disruption of Zn homeostasis has been linked with breast cancer development and progression. To enhance our understanding of changes in Zn homeostasis both inside and around the tumour microenvironment, Zn concentrations and isotopic compositions (δ66Zn) were determined in benign (BT) and malignant (MT) tumours, healthy tissue from reduction mammoplasty (HT), and histologically normal tissue adjacent to benign (NAT(BT)) and malignant tumours (NAT(MT)). Mean Zn concentrations in NAT(BT) are 5.5 µg g-1 greater than in NAT(MT) (p = 0.00056) and 5.1 µg g-1 greater than in HT (p = 0.0026). Zinc concentrations in MT are 12.9 µg g-1 greater than in HT (p = 0.00012) and 13.3 µg g-1 greater than in NAT(MT) (p < 0.0001), whereas δ66Zn is 0.17‰ lower in MT than HT (p = 0.017). Benign tumour Zn concentrations are also elevated compared to HT (p = 0.00013), but are not significantly elevated compared to NAT(BT) (p = 0.32). The δ66Zn of BT is 0.15‰ lower than in NAT(BT) (p = 0.045). The similar light δ66Zn of BT and MT compared to HT and NAT may be related to the isotopic compensation of increased metallothionein (64Zn-rich) expression by activated matrix metalloproteinase (66Zn-rich) in MT, and indicates a resultant 66Zn-rich reservoir may exist in patients with breast tumours. Zinc isotopic compositions thus show promise as a potential diagnostic tool for the detection of breast tumours. The revealed differences of Zn accumulation in healthy and tumour-adjacent tissues require additional investigation.

Chromite chemistry of a massive chromitite seam in the northern limb of the Bushveld Igneous Complex, South Africa: correlation with the UG-2 in the eastern and western limbs and evidence of variable assimilation of footwall rocks.

The Bushveld Igneous Complex (BIC) is known for its laterally extensive platinum group element-bearing layers, the most famous being the Merensky Reef and the UG-2 chromitite in the eastern and western limbs of the complex. In the northern limb, the Platreef mineralization and a thick chromitite seam below it (referred to as the "UG-2 equivalent" or UG-2E) have been proposed to be the stratigraphic equivalents of the Merensky Reef and the UG-2, respectively. In this study, we compare a suite of UG-2E samples from the Turfspruit project with a UG-2 reference suite from the western limb using petrography, electron probe microanalysis, laser ablation-inductively coupled plasma-mass spectrometry, and Mössbauer spectroscopy. The results show that (a) in Mg# vs. Cr# diagrams, UG-2E chromites have a distinct compositional field; however, when samples of similar chromite modal abundance (≥ 80%) are used, the UG-2E chromites overlap the field that characterizes UG-2 chromites; (b) the UG-2E is more variable in chromite modal abundance than the UG-2; and (c) variations in Mg# and Fe3+/ΣFe in the UG-2E indicate contamination of the magma by metasedimentary rocks of the Duitschland Formation (Transvaal Supergroup) during emplacement, followed by partial re-equilibration of chromite grains with a trapped melt. Thus, we conclude that for chromite modes higher than 80%, the chromite composition retains enough information to allow correlation and that the UG-2E in the northern limb is very likely the UG-2 chromitite.

Strontium isotope stratigraphy through the Flatreef PGE-Ni-Cu mineralization at Turfspruit, northern limb of the Bushveld Igneous Complex: evidence of correlation with the Merensky Unit of the eastern and western limbs.

The origin of PGE-Ni-Cu mineralization in the Platreef, northern limb of the Bushveld Igneous Complex (BIC), and the possible correlation with the Merensky Reef in the eastern and western limbs has been long debated. The Platreef and Merensky Reef share the same stratigraphic position in the uppermost part of the Upper Critical Zone (UCZ), near the transition to the overlaying Main Zone (MZ). However, discrepancies in interpretations have been difficult to resolve due to the effects of intense magma-country rock interaction throughout most of the northern limb succession. To address this problem, we generated a detailed stratigraphic profile of the initial strontium isotopic ratio [Sri = (87Sr/86Sr)i] in plagioclase across a Flatreef interval lacking macroscopic evidence of country rock assimilation. The in situ Sr isotopic ratios in plagioclase were determined using LA-MC-ICP-MS analysis on 37 samples from a drill core (UMT094) at the Turfspruit project. Strontium isotope stratigraphy is useful because of a well-documented shift in Sri near the base of the Merensky Unit in the eastern and western limbs. The results show the existence of a significant shift (from Sri = 0.7060 to Sri = 0.7090) that matches the isotopic shift documented through the Merensky Unit in the eastern and western limbs. Thus, this new Sr isotope data indicates that the main mineralized interval of the Flatreef can be stratigraphically correlated to the Merensky Reef in the remainder of the BIC. In addition, we interpret these results as compelling evidence to suggest that the main mineralization processes in the Flatreef were likely similar to those operating in the eastern and western limbs and that interaction with local country rocks was not a necessary condition.

Postprandial zinc stable isotope response in human blood serum.

In recent years, considerable advances have been made in the field of medical isotope metallomics, but numerous fundamental physiological processes remain to be investigated. Past studies report that blood serum Zn concentrations decrease by between about 10 and 25%, depending on the size of meal, approximately three hours postprandially (i.e. after eating), before returning to baseline values if no meals are consumed over the following four to five hours. Nine participants were recruited for this study to investigate whether this postprandial Zn concentration decrease is accompanied by a stable isotope response. A baseline serum sample was collected from participants in the morning after overnight fasting. A 576 kcal meal was then provided and additional serum samples were taken 90 and 180 minutes post-meal to coincide with the postprandial response. Serum Zn concentrations decreased postprandially by an average of 21 ± 9% (1SD), but this was not accompanied by a change in stable Zn isotope composition (mean Δ66Zn180-minute-baseline = 0.01 ± 0.09‰, 2SD). We propose that hemodilution and the rapid, efficient postprandial transfer of albumin-bound Zn from serum to the liver and pancreas is responsible for the lack of postprandial serum Zn isotopic response. These results indicate that studies examining solely the distribution of Zn isotopes in serum may obtain samples without considering timing of the most recent meal. However, future studies seeking to compare serum Zn concentrations with δ66Zn values should draw blood samples in the morning after overnight fasting.

Louisville seamount subduction and its implication on mantle flow beneath the central Tonga-Kermadec arc.

Subduction of intraplate seamounts beneath a geochemically depleted mantle wedge provides a seldom opportunity to trace element recycling and mantle flow in subduction zones. Here we present trace element and Sr, Nd and Pb isotopic compositions of lavas from the central Tonga-Kermadec arc, west of the contemporary Louisville-Tonga trench intersection, to provide new insights into the effects of Louisville seamount subduction. Elevated (206)Pb/(204)Pb, (208)Pb/(204)Pb, (86)Sr/(87)Sr in lavas from the central Tonga-Kermadec arc front are consistent with localized input of subducted alkaline Louisville material (lavas and volcaniclastics) into sub-arc partial melts. Furthermore, absolute Pacific Plate motion models indicate an anticlockwise rotation in the subducted Louisville seamount chain that, combined with estimates of the timing of fluid release from the subducting slab, suggests primarily trench-normal mantle flow beneath the central Tonga-Kermadec arc system.