Resolving Uncertainties in the Quantification of Trace Elements within Organic-Rich Boreal Rivers for AF4-UV-ICP-MS Analysis.

Over the past few decades, asymmetric flow field-flow fractionation (AF4) has emerged as a robust technique for the separation of colloid-associated trace elements (TEs) in aqueous samples. Nevertheless, little is known about potential artifacts and how to control them when measuring the concentrations of colloid-associated elements at low (µg L-1) or ultralow concentrations (ng L-1) using AF4-UV-ICP-MS. Water from a boreal river was selected as a challenging test material due to its high concentrations of dissolved organic matter (DOM) and Fe-rich colloids. These colloids are expected to be significant contributors to artifact occurrence, even in a metal-free, ultraclean laboratory. The results show that the adsorption of Mn, Co, Ni, Cu, and Pb onto acid-cleaned, non-channel surfaces (such as connection tubing and autosampler) accounted for up to 48% of TE loss. These losses on non-channel surfaces also represent potential sources of cross-contamination for Co, Ni, Cu, and Pb. New, uncleaned poly(ether sulfone) membranes are also sources of contamination for Ni and Cu. Analytical bias may exist in the measured concentrations of TEs, primarily due to the potential carryover of weakly adsorbed TEs (e.g., Ni and Cu) on the system surfaces by colloids in the samples (e.g., DOM). On the other hand, colloids in the samples can also act to gradually remove contaminants from the surfaces. For these types of DOM-rich waters, preconditioning the AF4 system using 40 mg C L-1 of Suwannee River Natural Organic Matter (SRNOM, pH = 7) is recommended to mitigate the impact of membrane fouling and carryover. A comprehensive strategy for minimizing instrumental artifacts is presented and discussed.

Size-resolved distribution of trace elements in lysimeter soil solutions under contrasting long-term agricultural management to assess their bioavailability.

The chemical species of trace elements (TEs) in agricultural soils is highly variable under diverse conditions, requiring tools with clear resolution and minimal disturbance for exploration. A novel surgical (316L) stainless steel (SS) lysimeter with a 5 µm pore size was developed to collect field soil solutions. The size-resolved distribution of TEs were characterized into total (nitric acid digestion), particulate (0.45-5 µm), dissolved (<0.45 µm), colloidal (1 kDa to 0.45 µm), and mainly ionic (<1 kDa) fractions in the lysimeter soil solutions. Total concentrations of TEs (dry weight basis) in acid digested Gray Luvisolic soils were analyzed. Most TEs in lysimeter soil solutions were present in particulate phases, relevant to their geochemical affinities and occurrences in soil minerals. Among dissolved fractions, As, Ba, Co, Li, Mn, Tl, and V existed as mainly ionic species in the soil solutions. Copper, Pb, Al, Th, and U showed variable associations with dissolved organic matter (DOM) and/or inorganic colloids among agricultural treatments. Inorganic NPKS or NKS fertilizer applications with lower pH (5.25-5.74) enhanced mobility and potential bioavailability of Ba, Co, Li, Mn, and Pb present in mainly ionic species, compared with other locations (pH 5.82-6.37). Manure application exhibited a dual effect, potentially increasing bioavailability for As, Tl, and V due to probably enhanced cation exchange capacity (CEC), while also facilitating specific adsorption of Cu and U on DOM, potentially reducing their bioavailability depending on DOM molecular weight. Colloidal and ionic Al and Th concentrations were higher in forest soils than agricultural soils, with extremely low potential bioavailability of Th attributed to strong precipitation with inorganic colloids and adsorption on DOM. The lysimeter sampling and size fractionation method provided a clear insight into agricultural effects on TE distributions and enhancing understanding of agricultural soil health in terms of TE bioavailability in situ.

Spatio-temporal variations in dissolved trace elements in peat bog porewaters impacted by dust inputs from open-pit mining activities in the Athabasca Bituminous Sands (ABS) region.

Considerable volumes of dust are generated from open-pit bitumen mining operations in northern Alberta, Canada. The reactive mineral phases of these dust particles can potentially dissolve in acidic (pH < 4) bog waters. Their dissolution could release trace elements (TEs), which could eventually alter these bog ecosystems. The impact of dust dissolution on the abundance of TEs in the dissolved (<0.45 µm) fraction of porewaters from excavated pits (30-40 cm deep) in the ombrogenic zone of five peatlands was evaluated. Porewaters were collected from four bogs situated within 70 km of mines and upgraders in the Athabasca Bituminous Sands (ABS) region, Alberta, Canada, and from a reference bog situated 264 km away. Over two consecutive years, the dissolved concentrations of some conservative (Al, Th, Y) and mobile lithophile elements (Fe, Li, Mn, Sr), as well as the metals enriched in bitumen (V, Ni, Mo), all increased with proximity to the mining area, in the ABS region. These trends reflect the observed increase in dust deposition with proximity to the mining area from independent studies of snow, lichens, and Sphagnum moss. Contrarily, the impact of dust dissolution on the concentration of potentially toxic TEs (As, Cd, Pb, Sb, and Tl) was negligible. Thus, the elements which are more abundant in the porewaters near industry are either ecologically benign (e.g. Li and Sr) or essential micronutrients (e.g. Fe, Mn, Ni, and Mo). Manganese was the only element which was enriched by more than 10x at all sites near the mining area, compared to its concentration at the reference site. The enrichments of all other elements were <10x, indicating that anthropogenic dust emissions from mining areas have had only a modest effect on the TEs abundance in peat porewaters.

Metal-free sampling methods for dust, rainwater, surface water, plants, and sediments: A selection of unique tools from the SWAMP laboratory.

Contamination control remains one of the greatest challenges for the reliable determination of many trace elements in environmental samples. Here we describe a series of metal-free sampling devices and tools designed and constructed specifically to minimize the risk of contamination by trace elements during sampling of dust, rainwater, surface water, plants, and sediments. Plastic components fabricated using 3-D printing include polylactic acid (PLA), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polypropylene (PP), polycarbonate (PC) and PC with carbon fibre. When additional strength is needed (e.g. supporting structural components), carbon fibre, aluminum (Al), or 316 stainless steel (SS) is used. Other plastics employed include acrylic and vinyl. Epoxy glue or SS may be used for joining components, but do not come into contact with the samples. Ceramic (zirconium dioxide) cutting blades are used where needed. Each plastic material was evaluated for contaminant trace elements by leaching with high purity nitric acid in the metal-free, ultraclean SWAMP laboratory. The devices were tested in the field to evaluate their performance and durability. When combined with appropriate cleaning procedures, the equipment enables ultraclean collection for trace element analysis of environmental media.•Plastic sampling devices were designed and constructed using 3D printing of PLA, PET, PETG or PP.•Leaching characteristics of plastic components were evaluated using high purity nitric acid in a metal-free, ultraclean laboratory.•Each sampling device was successfully field-tested in industrial settings (near open pit bitumen mines and upgraders), and in remote locations of northern Alberta, Canada.

Comparison of trace elements in tissue of beaver (Castor canadensis) and local vegetation from a rural region of southern Ontario, Canada.

Beavers have been analyzed in several studies examining trace elements (TEs) in wildlife; however, most of these studies were undertaken in areas with known environmental pollutants. To understand and quantify natural enrichments of TEs in beaver tissue, samples of kidney, liver, muscle from 28 animals were compared with bark from 40 species of trees and shrubs, from the same, uncontaminated watershed. Pearson correlation and factor analysis show that conservative, lithophile elements such as Al, Ga, Th, and Y, all surrogates for mineral dust particles, explain 61% of the variation in the bark data. In contrast, Cd, Co, Cu, Mn, Mo, Ni, Rb, Se, Sr, and Tl in bark are independent of Al, and therefore most likely occur in non-mineral forms. Comparing tissue concentrations of beaver and bark, the organs are enriched in micronutrients such as Cu, Fe, Mo, Se, and Zn, but also non-essential, benign elements such as Cs and Rb, and potentially toxic elements such as Cd and Tl. Thus, the elements most enriched in beaver organs are those that apparently occur in biological form in the plant tissue. The elements enriched in these animals, relative to bark, appear to offer the most promise for monitoring environmental contamination by TEs using beavers. The majority of TEs of environmental relevance are most abundant in beaver kidney. However, monitoring studies must consider the variation in TE concentrations in beaver tissue, including those due to sex and age. Also, due consideration must be given to background concentrations of TEs in the vegetation composing the diet of the animals. The natural enrichment in the case of elements such as Cd, in beaver tissue relative to bark, is profound. These data establish critical baseline values for TEs in beavers in an unpolluted environment, thereby allowing for their use as model organisms in tracking how heavy metal pollutants may affect wildlife.

Effects of Acute and Subchronic Waterborne Thallium Exposure on Ionoregulatory Enzyme Activity and Oxidative Stress in Rainbow Trout (Oncorhynchus mykiss).

The mechanisms of acute (96-hour) and subchronic (28-day) toxicity of the waterborne trace metal thallium (Tl) to rainbow trout (Oncorhynchus mykiss) were investigated. Specifically, effects on branchial and renal ionoregulatory enzymes (sodium/potassium adenosine triphosphatase [ATPase; NKA] and proton ATPase) and hepatic oxidative stress endpoints (protein carbonylation, glutathione content, and activities of catalase and glutathione peroxidase) were examined. Fish (19-55 g) were acutely exposed to 0 (control), 0.9 (regulatory limit), 2004 (half the acute median lethal concentration), or 4200 (acute median lethal concentration) µg Tl L-1 or subchronically exposed to 0, 0.9, or 141 (an elevated environmental concentration) µg Tl L-1 . The only effect following acute exposure was a stimulation of renal H+ -ATPase activity at the highest Tl exposure concentration. Similarly, the only significant effect of subchronic Tl exposure was an inhibition of branchial NKA activity at 141 µg Tl L-1 , an effect that may reflect the interaction of Tl with potassium ion handling. Despite significant literature evidence for effects of Tl on oxidative stress, there were no effects of Tl on any such endpoint in rainbow trout, regardless of exposure duration or exposure concentration. Elevated basal levels of antioxidant defenses may explain this finding. These data suggest that ionoregulatory perturbance is a more likely mechanism of Tl toxicity than oxidative stress in rainbow trout but is an endpoint of relevance only at elevated environmental Tl concentrations. Environ Toxicol Chem 2024;43:87-96. © 2023 SETAC.

Spatial variation and chemical reactivity of dusts from open-pit bitumen mining using trace elements in snow.

The chemical reactivity of trace elements (TEs) in dusts from bitumen mining, upgrading and related industrial activities in the Athabasca Bituminous Sands region (ABS), Alberta, Canada, was evaluated using the acid-soluble fraction of snow. Samples were collected at 14 sites along the Athabasca River (AR) and its tributaries, and at 3 remote locations. Following metal-free, ultra-clean procedures for processing and analysis, samples were leached with nitric acid (pH < 1), filtered (<0.45 µm), and analyzed using ICP-MS. Insoluble particles (>0.45 µm) were examined using SEM-EDS. Along the river, acid-soluble concentrations of TEs varied by 6 orders of magnitude, from 1 mg/L (Al) to less than 1 ng/L (Tl). Conservative (Al, Y, La, Th) and mobile (Li, Be, Cs, Sr) lithophile elements, those enriched in bitumen (V, Ni, Mo), and potentially toxic chalcophile elements (As, Cd, Pb, Sb, Tl) showed considerable spatial variation. Normalizing the concentrations of TEs in samples collected near industry to the corresponding concentrations in snow from the reference site (UTK), resulted in enrichments of V and most of the lithophile elements. Dust reactivity, quantified as the ratio of acid-soluble to total concentrations, was less than 50% suggesting limited bioaccessibility. The large differences in behaviour between Cd and Pb versus Ni and V could be due to the occurrence of the former pair in carbonate or sulfide minerals, versus acid-insoluble petcoke particles for the latter couple. Spatial variations in the reactivity of TEs most likely reflect the range in diversity and chemical stability of dust particles, and variations in their abundance in primary source areas. The leaching conditions employed here are extreme (pH < 1) and intended to identify an upper limit of chemical reactivity, with far less dust dissolution expected when these dusts encounter natural waters of the area which range in pH from 4 to 8.

Sources, spatial-distributions and fluxes of PAH-contaminated dusts in the Athabasca oil sands region.

Atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) has increased in northern Alberta, Canada, due to industrial development in the Athabasca oil sands region (AOSR). However, the sources, summertime deposition fluxes and associated spatial patterns are poorly characterized, and the magnitude of contamination has not been directly contrasted with comparable measurements around large Canadian cities. PAHs were measured in Sphagnum moss collected from 30 bogs in the AOSR and compared with reference moss collected from various remote, rural and near-urban sites in Alberta and Ontario. At all 39 locations, strong correlations between depositional fluxes of PAHs and accumulation rates of ash (n = 117, r = 0.877, p < 0.001) implied that the main source of PAHs to moss was atmospheric deposition of particles. Average PAH concentrations at near-field AOSR sites (mean [SD], 62.4 [24.3] ng/g) were significantly higher than at far-field AOSR sites (44.9 [20.8] ng/g; p = 0.038) or the 7 reference sites in Alberta (20.6 [3.5] ng/g; p < 0.001). In fact, average PAH concentrations across the entire AOSR (7,850 km2) were approximately twice as high as in London, Ontario, or near petroleum upgrading and major traffic corridors in Edmonton, Alberta. A chemical mass balance model estimated that both delayed petcoke (33 % of PAHs) and fine tailings (38 % of PAHs) were the major sources of PAHs in the AOSR. Over the 2015 summer growing season, we estimate that 101-110 kg of PAHs (on 14,300-17,300 tonnes of PAH-containing dusts) were deposited to the AOSR within a 50 km radius of surface mining. Given that the highest PAH deposition was to the northern quadrant of the AOSR, which includes the First Nations community of Fort MacKay, further dust control measures should be considered to protect human and environmental health in the region.

Natural enrichment of Cd and Tl in the bark of trees from a rural watershed devoid of point sources of metal contamination.

To help understand the bioaccumulation of Cd and Tl in beaver tissue, we examined the enrichment of these metals in vegetation available to the animals. Bark was collected from 40 species of trees and shrubs, along with a complete soil weathering profile, within a small watershed devoid of trace metal contamination. Weathering resulted in a 5x enrichment of Cd in the soils relative to the underlying sediments, and a 6x Tl depletion: while Cd was lost from calcite and accumulates in the organic matter and oxyhydroxide fractions, Tl occurred only in the residual fraction. Soil processes alone, however, cannot explain the anomalous concentrations and enrichments of Cd in willow and poplar which contain up to 8.5 mg/kg Cd. The concentrations of Cd and Tl in the dissolved fraction (<0.45 µm) of the Wye River are similar (1.2 ± 0.4 and 1.6 ± 0.1 ng/L, respectively), and are taken to estimate their bioavailability in soil solutions. Normalizing the Cd/metal ratios in bark to the corresponding ratios in water yields the Stream Enrichment Factor: this novel approach shows that all plant species are enriched in Cd relative to Ni; 33 relative to Cu, 13 relative to Zn, and 7 relative to Mn. Thus, many plants preferentially accumulate Cd, especially willow and poplar, over these essential micronutrients. Clearly, the enrichment of Cd over Tl in bark is not a reflection of differences in bioavailability, but rather on the preferential uptake of Cd by the plants. The profound natural bioaccumulation of Cd in the bark of willow and poplar, the two favourite foods of the beaver, has ramifications for the use of these aquatic mammals as biomonitors of environmental contamination, as well as for the direct and indirect consumption of bark for traditional food and medicine.

Mechanistic examination of thallium and potassium interactions in Daphnia magna.

The trace element thallium (Tl) exerts its toxic effects, at least in part, through its mimicry of potassium (K+) and subsequent impairment of K+ homeostasis. However, the specific nature of this effect remains poorly understood, especially in aquatic biota that are threatened by elevated concentrations of Tl associated with mining and refining effluents. In this study experiments were conducted to mechanistically examine the relationship between Tl and K+ in terms of uptake and toxicity in the regulatory model species Daphnia magna. In one set of experiments the effects of K+, the K+ analog rubidium (Rb+), and generalized K+ channel blocker cesium (Cs+) on Tl-induced acute toxicity were examined. The presence of increasing concentrations of K+ and Rb+ in exposure water reduced waterborne Tl toxicity, indicating that the actions of Tl were mediated at least in part through interactions with K+. However, in the presence of elevated water Cs+, the toxicity of Tl paradoxically increased. Pharmaceuticals with putative blocking actions on K+ channels failed to alter whole-body K+ of control organisms, but in the case of clozapine and chlorpropamide, whole-body K+ status was significantly elevated relative to exposures with Tl alone, which tended to reduce this metric. These data identify inwardly rectifying and voltage gated K+ channels as potential loci of Tl toxicity. Experiments using rubidium (Rb+) as a tracer of K+, showed that waterborne Tl affects the uptake of K+, but the magnitude of inhibition by Tl was not sufficient to explain the effect on whole-body K+. While these data indicate interactions between Tl and K occur at K+ transporters in D magna, they also indicate that environmental levels of K+ are likely to ameliorate toxicity in most natural waters.

Accumulation of Thallium in Rainbow Trout (Oncorhynchus mykiss) Following Acute and Subchronic Waterborne Exposure.

The accumulation and tissue distribution of toxicants in aquatic biota can be determinative of their toxic impact to both exposed organisms and their potential human consumers. In the present study, accumulation of the trace metal thallium (Tl) in gill, muscle, plasma, and otoliths of rainbow trout (Oncorhynchus mykiss) following acute (96-h) and subchronic (28-day) waterborne exposures was investigated. Owing to known interactions between Tl and potassium ions (K+ ), plasma and muscle K+ concentrations were also determined. Branchial Tl accumulated in a dose-dependent manner in both acute and subchronic exposures, while plasma Tl was rapidly mobilized to tissues and accumulated only at exposure concentrations of 141 µg L-1 or higher. For muscle tissue, Tl concentrations at 28 days were markedly lower than those at 96 h at comparable exposure concentrations (0.9 µg L-1 ), indicating the presence of mechanisms that act to reduce Tl accumulation over time. However, after acute exposure, muscle Tl reached concentrations that, if consumed, would exceed acceptable daily intake values for this element, indicating some risk to human health from the consumption of fish from waters heavily contaminated with Tl. Otoliths showed Tl concentrations that reflected exposure concentration and length, confirming their capacity to provide insight into fish exposure history. No changes in tissue K+ concentrations were observed, suggesting that accumulation of Tl in rainbow trout plasma and muscle does not occur at the expense of K+ homeostasis. In addition to highlighting the capacity of rainbow trout to accumulate Tl to levels that exceed recommended dietary doses to human consumers, the present study provides the first data of tissue-specific Tl accumulation in an important regulatory species. Environ Toxicol Chem 2023;42:1553-1563. © 2023 SETAC.

Recent climate change has driven divergent hydrological shifts in high-latitude peatlands.

High-latitude peatlands are changing rapidly in response to climate change, including permafrost thaw. Here, we reconstruct hydrological conditions since the seventeenth century using testate amoeba data from 103 high-latitude peat archives. We show that 54% of the peatlands have been drying and 32% have been wetting over this period, illustrating the complex ecohydrological dynamics of high latitude peatlands and their highly uncertain responses to a warming climate.

Environmental significance of trace elements in the Athabasca Bituminous Sands: facts and misconceptions.

The bituminous sands of Alberta, Canada, represent the second largest reserves of hydrocarbons on earth. Open pit bitumen mining and upgrading of the Athabasca Bituminous Sands (ABS), the largest of the deposits, began in 1967. Concerns about fugitive release of trace elements (TEs) to the environment began with studies of V, as this is the most abundant trace metal in bitumen. Recent studies, however, have extended to Ag, As, Be, Cd, Cr, Cu, Pb, Sb, and Tl, and this has led to considerable confusion about which TEs are relevant to ecosystem health. While V along with Ni, Mo, Se and Re are enriched in bitumen, Ag, As, Be, Cd, Cr, Cu, Pb, Sb and Tl are found almost exclusively in the mineral (i.e. sand) fraction of the ABS, with limited opportunity to become bioaccessible, much less bioavailable. Here, a summary is given of ten misunderstandings that have arisen regarding TEs in the environment of the ABS region. To help illustrate the significance of the misconceptions that have arisen regarding (a) air and (b) water resources, published and unpublished TE data obtained from the metal-free, ultraclean SWAMP lab is presented for: (a) snow, moss, and peat cores from bogs, and (b) the dissolved, particulate, and colloidal fractions of water from the Athabasca River (AR), as well as pristine groundwater. Natural enrichments of Ni in plants such as Rat Root (Acorus calamus) and pine (Pinus banksiana), Tl in fish (Percopsis omiscomaycus) and Cd in cranberries (Vaccinium oxycoccus), Labrador Tea (Rhododendron groenlandicum) and beaver (Castor canadensis), are also presented.

Exploring Nanogeochemical Environments: New Insights from Single Particle ICP-TOFMS and AF4-ICPMS.

Nanogeochemistry is an emerging focus area recognizing the role of nanoparticles in Earth systems. Engineered nanotechnology has cultivated advanced analytical techniques that are also applicable to nanogeochemistry. Single particle inductively coupled plasma ICP-time-of-flight-mass spectrometry (ICP-TOF-MS) promises a significant step forward, as time-of-flight mass analyzers enable simultaneous quantification of the entire atomic mass spectrum (∼7-250 m/z +). To demonstrate the utility of this approach, samples were collected and analyzed from a large, boreal river, and its surrounding tributaries. These samples provided us with a diversity of particle compositions and morphologies, while their interconnected nature allowed for an examination of the various nanogeochemical processes present in this system. To further expand on this effort, we combined this high-throughput technique with AF4-ICPMS, focusing on major carriers of trace elements. Using spICP-TOF-MS, Al, Si, and Fe were grouped into classes having all combinations of one or more of these elements. Particle-by-particle ICP-TOF-MS analysis found chemically heterogeneous populations, indicating the predominance of diverse mineralogy or heteroaggregates. The importance of suspended Fe and Mn for the speciation of Pb was observed by single particle ICP-TOF-MS and complemented by AF4-ICPMS analysis of dissolved organic matter and nanoparticulate Fe/Mn. Our study exploits the combination of spICP-TOF-MS and AF4-ICP-MS for studying isotopic and elemental ratios (mineralogy) of individual nanoparticles, which opens the door to further explore the mechanisms of colloid facilitated transport of trace elements.

Impact of the 2016 Fort McMurray wildfires on atmospheric deposition of polycyclic aromatic hydrocarbons and trace elements to surrounding ombrotrophic bogs.

Fort McMurray and the Athabasca oil sands region (AOSR) experienced major wildfires in 2016, but the impact of these on regional deposition of polycyclic aromatic hydrocarbons (PAHs) and trace elements has not been reported nor compared to industrial sources of these pollutants in the region. Living moss (Sphagnum fuscum) was collected in triplicate from five ombrotrophic bogs in the AOSR after the wildfires, and analyzed for PAHs and trace elements. These post-wildfire data were compared to data from previous years at the same sites, and also to remote reference bogs in Alberta and Ontario. Elevated post-wildfire concentrations and flux of naphthalene and fluorene were observed at all five bogs in the AOSR, but no consistent trend was evident for higher molecular weight PAHs or the sum of priority PAHs (∑13PAH). Trace elements at most AOSR bogs were not elevated post-wildfire, except at one bog in the burned area (MIL), but even here the elements that were increased (1.7-5.6 × ) were likely of bitumen-origin (i.e., V, Ni, Se, Mo and Re). Significant post-wildfire correlations between PAHs and most trace elements suggested a common source, and few significant correlations were observed with retene, suggesting that wildfires were not the dominant source of most contaminants detected. Mass balance receptor models were used to apportion sources, indicating that the major sources of trace elements among five AOSR bogs post-wildfire were oil sands ore (mean 42%), haul road dust (17%), and petcoke (11%), whereas wildfire was always a minor source (3-4%). For PAHs at the most contaminated site (MIL), delayed petcoke (27%) and wildfire (25%) were the major sources, but the contribution of wildfire to PAHs at other sites was less or not discernable. Impacts of the 2016 wildfires on regional atmospheric deposition of major pollutants was less than from ongoing deposition of anthropogenic dust from oil sands activities.

Chronic toxicity of waterborne thallium to Daphnia magna.

There is limited information regarding the toxicity of the trace element thallium (Tl) to aquatic biota, most of which assesses acute toxicity and bioaccumulation. The relative lack of chronic Tl toxicity data compromises the establishment of water quality criteria for this trace metal. In the presented work, chronic toxicity endpoints (final body weight (a proxy measure of growth), survival, and reproduction) and Tl body burden were measured in the freshwater crustacean Daphnia magna during a 21-day exposure to dissolved Tl. Thallium caused complete mortality in daphnids between exposure concentrations of 424 and 702 µg L-1. In contrast with previously published work examining acute Tl toxicity, exposure to Tl for 21 days was not associated with changes in whole-body potassium concentration. This was despite a 710-fold increase in Tl body burden in animals exposed to 424 µg L-1 relative to the control. Median effect concentrations (EC50's) for growth and reproduction (total neonates produced), were 1.6 (95% confidence interval: 1.0-3.1) and 11.1 (95% confidence interval: 5.5-21.8) µg Tl L-1, respectively. A no observable effect concentration (NOEC) of 0.9 µg Tl L-1 for growth, and a NOEC range of 0.9-83 µg Tl L-1 for a variety of reproductive metrics, was measured. A lowest observable effect concentration (LOEC) of 8.8 µg Tl L-1 was determined for the effects of Tl on growth and most of the reproductive endpoints examined. These data indicate that under controlled laboratory conditions D. magna is significantly less sensitive to Tl than the species on which the current Canadian Council of Ministers of the Environment regulatory guideline value of 0.8 µg L-1 is based.

Trace elements in Labrador Tea (Rhododendron groenlandicum): How predominant sources to the plants impact the chemical composition of hot water extracts.

Labrador Tea (Rhododendron groenlandicum) has been an important food and medicinal plant to First Nations communities in North America for millenia, but little is known of its geochemical properties. Using plants from 10 sites in 4 provinces, including pristine and industrial regions, and employing the metal-free, ultraclean SWAMP laboratory facilities and procedures, we provide an estimate of the natural abundance of trace elements in the leaves, and the extent of their release during hot water extraction. Elements decrease in abundance in the order Mn > Al > Fe > Zn > Cu > Ni > V > Pb > La > Mo > Y > La > Tl > Cd > Th > Ag. The greatest concentrations of conservative, lithophile elements such as Al, La, Th and Y, are found in samples collected on lands reclaimed from open pit bitumen mines in northern Alberta, reflecting elevated inputs of atmospheric dusts. In contrast, micronutrients such as Cu and Zn are remarkably uniform which suggests that these are supplied almost exclusively by plant uptake via roots. Deionized, reverse osmosis water is more effective in removing some elements (e.g. Al, La, Y, Fe, Zn, Cd) whereas others are more readily extracted using groundwater (e.g. Cu, Ni, Pb); V behaves independently of water composition. In both types of water, the elements most readily extracted are plant micronutrients (Mn, Ni, Cu, and Zn) whereas those supplied primarily by dust exhibit much lower yields; Al shows behaviour intermediate between these two extremes. While element concentrations in the infusions increase with increasing concentrations in the leaves, the abundance of potentially toxic chalcophile elements such as Cd, Pb, Sb and Tl in the infusions are extremely low (ng/l). Plants from British Columbia, Ontario and Quebec provide evidence of atmospheric Pb contamination, yielding greater ratios of Pb/La compared to the samples from Alberta where crustal values are found. Given that this plant is common and found across the northern half of the continent, it shows great promise as a tool for biomonitoring of air quality. For consumers, Labrador Tea may represent an important dietary source of Mn.

Lead immobilization processes in soils subjected to freeze-thaw cycles.

Soil freeze-thaw cycles (FTCs) change the physical and chemical properties of soils; however, information is limited about the consequences for heavy metal sorption and desorption. Lead (Pb) sorption isotherms and successive desorption tests were measured for three soils from North China (Chestnut, Lou and Black), following multiple freeze-thaw cycles (0, 1, 3, 6 and 9 FTCs) of -5 °C for 12 h and then +5 °C for 12 h. Lead adsorption dominated the sorption processes for all soils, and sorption capacity increased with additional FTCs. The Freundlich affinity parameter of soils for Pb sorption (i.e. A; Lß mmol1-ß kg-1), was linearly correlated with carbonate content for soils with multiple FTCs. The effects of FTCs on lead adsorption may be more dependent on carbonate and clay contents than organic matter (OM), cation exchange capacity (CEC) and amorphous iron content. Repeated FTCs increased the pH of soil solutions at applied Pb concentrations >1.4 mmol L-1, which could facilitate formation of inner-sphere complexes of Pb in studied soils. Cation exchange, a weak association, could occupy specific adsorption sites with increasing Pb doses in soils and it can also be facilitated by FTCs. Our results demonstrate the great potential for increasing Pb immobilization with repeated FTCs, by facilitating the formation of both inner-sphere and outer-sphere complexes. Hence, these findings provide useful information on Pb immobilization in contaminated soils that undergo frequent FTCs and offer an additional insight into predicting Pb behavior in cold and freezing environments like the polar regions.

Contemporary and Historical Atmospheric Deposition of Arsenic and Selenium in the Athabasca Bituminous Sands Region.

Selenium (Se) is one of the trace elements that is enriched in bitumen. To assess the importance of atmospheric Se deposition from mining and upgrading of bituminous sands in northern Alberta, Canada, Sphagnum moss was obtained from 25 bogs near industrial operations. The average Se concentration in moss near industries (58 ± 13 µg/kg; n = 75) was greater than in remote sites in Alberta (29-50 µg/kg), but comparable to bogs in central regions of the province and lower than bogs in southern Ontario (121-244 µg/kg) or the west and east coasts (230-285 µg/kg). In bog vegetation and peat, arsenic (As) concentrations and accumulation rates are 10 times greater at the industrial site (MIL) compared to the control site (UTK), but this is proportional to the differences in scandium (a surrogate for mineral matter concentrations), which points to dust as the predominant As source. An age-dated peat core collected near industries revealed that both Se and As deposition have declined in recent years. A peat core from UTK provided a record of atmospheric deposition dating back over 2700 years, indicating that As and Se deposition in northern Alberta increased considerably in the early 19th century and then went into decline during ∼1950-1970.

The Effect of Major Ions and Dissolved Organic Matter on Complexation and Toxicity of Dissolved Thallium to Daphnia magna.

Thallium (Tl) is a trace element associated with base metal mining and processing, but little is known regarding how its toxicity is influenced by water chemistry. In the present study, the 48-h median lethal concentration (LC50) of Tl to Daphnia magna was determined in a standard laboratory water, and toxicity was reassessed under conditions of varying cation (Ca2+ , K+ , Na+ ), anion (Cl- , HCO-3 ), and dissolved organic matter (DOM) concentrations. The calculated 48-h LC50 of 1.86 mg Tl/L was consistent with previous work on Tl toxicity to D. magna. At the 48-h LC50 concentration, changes in water chemistry had no statistically significant effect on mortality, although there was a trend toward lower Tl toxicity with elevated water K+ . Test waters containing 10 mM CaCl2 did not support control survival. The measurement of Tl complexation with DOM using asymmetric flow field flow fractionation confirmed the outcomes of biogeochemical speciation modeling: Tl speciation was relatively unaffected by water chemistry, and the majority of Tl remained in the ionic form across all treatments. These data indicate that Tl toxicity is largely independent of speciation, a property that will greatly simplify risk assessments for this metal in freshwaters. Environ Toxicol Chem 2019;38:2472-2479. © 2019 SETAC.