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.

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.

AF4-ICPMS with the 300 Da Membrane To Resolve Metal-Bearing "Colloids" < 1 kDa: Optimization, Fractogram Deconvolution, and Advanced Quality Control.

The smallest colloids exert a disproportionately large influence on colloidal systems owing to their greater surface area; however, the challenges of working in the smaller size range have limited most field-flow fractionation-ICPMS analyses to sizes > ca. 1 kDa. We discuss considerations and present solutions for overcoming these challenges, including high pressures associated with using the 300-Da membrane, calibration in this small size range, accounting for drifting LODs and separation conditions during membrane aging, and optimizing the compromise between resolution and recovery. Necessary flow program ranges for observing pressure limits are discussed, and calibration is conducted using a combination of bromophenol blue and polystyrene size standards. The impact of membrane drift on size is demonstrated and effectively corrected by routine calibration. Separation conditions are optimized by monitoring the recovery and resolution of several trace metals. A precise, high-resolution separation is achieved using fractogram deconvolution to fully resolve overlapping peaks. Method effectiveness and precision are demonstrated through triplicate analyses of three natural water samples: Mp = 2.89 ± 0.04, 3.20 ± 0.03 and 3.50 ± 0.12 kDa for DOM-associated Fe in the three samples (±95% CI). A primarily inorganic Fe fraction with Mp = 14.7 ± 0.5 kDa was also resolved from the DOM-associated fraction. Quality control methods and considerations for optimizing flow conditions are detailed in the Supporting Information as a guide for researchers seeking to analyze colloids in this smallest size range using AF4-ICPMS with the 300-Da membrane.

Peat Bogs Document Decades of Declining Atmospheric Contamination by Trace Metals in the Athabasca Bituminous Sands Region.

Peat cores were collected from five bogs in the vicinity of open pit mines and upgraders of the Athabasca Bituminous Sands, the largest reservoir of bitumen in the world. Frozen cores were sectioned into 1 cm slices, and trace metals determined in the ultraclean SWAMP lab using ICP-QMS. The uppermost sections of the cores were age-dated with 210Pb using ultralow background gamma spectrometry, and selected plant macrofossils dated using 14C. At each site, trace metal concentrations as well as enrichment factors (calculated relative to the corresponding element/Th ratio of the Upper Continental Crust) reveal maximum values 10 to 40 cm below the surface which shows that the zenith of atmospheric contamination occurred in the past. The age-depth relationships show that atmospheric contamination by trace metals (Ag, Cd, Sb, Tl, but also V, Ni, and Mo which are enriched in bitumen) has been declining in northern Alberta for decades. In fact, the greatest contemporary enrichments of Ag, Cd, Sb, and Tl (in the top layers of the peat cores) are found at the control site (Utikuma) which is 264 km SW, suggesting that long-range atmospheric transport from other sources must be duly considered in any source assessment.

Cadmium exposure and the risk of prostate cancer among Nigerian men: Effect modification by zinc status.

BACKGROUND: Prostate cancer (PCa) may result from an interplay between many factors including exposure to trace elements. This study examined the association between cadmium exposure and PCa among Nigerian men and evaluated possible modification of this effect by zinc status. METHODS: This case-control study involved men with histologically confirmed PCa (n = 82), benign prostatic hyperplasia (BPH; n = 93) and controls (n = 98), aged between 40 and 80 years. Study participants were recruited from the main teaching hospital that draws clients from the entire Anambra State in South-Eastern Nigeria. Blood and urine samples were collected from these participants and were analyzed for trace elements using ICP-MS. Statistical models were used to assess the exposure risk for cadmium exposure as well as the mediating effect of zinc status. RESULTS: Among men with prostatic disorders (case-case analysis), every 10-fold increase in urinary cadmium was associated with increased risk of PCa (adjusted odds ratios: 2.526; 95% CI: 1.096-5.821). Men in the highest blood zinc quartile had lower odds of PCa compared to the lowest quartile (AOR: 0.19; 95% CI, 0.06-0.54; p-for trend = 0.001). Zinc-specific effect was observed in this group: every 10-fold increase in urinary cadmium was associated with increased risk of PCa among men with creatinine-adjusted urinary zinc levels below the median value (AOR: 8.46; 95% CI: 1.97 -36.39) but not in those above the median value (AOR: 1.55; 95% CI: 0.45 - 5.39). CONCLUSION: Higher exposure to cadmium may be associated with increased risk of PCa in Nigeria and probably other countries with high prevalence of Zn deficiency. These results point to the need to consider co-occurring trace metals in any effort to mitigate the toxicity of Cd in the environment.

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.

A geochemical perspective on the natural abundance and predominant sources of trace elements in cranberries (Vaccinium oxycoccus) from remote bogs in the Boreal region of northern Alberta, Canada.

Trace elements in native cranberry (Vaccinium oxycoccus) were compared with the underlying Sphagnum moss on which it grows, from two remote ombrotrophic (rain-fed) peat bogs in northern Alberta, Canada. The purpose of the comparison was to distinguish between dust inputs to the berries versus plant uptake from the substrate, and to determine the natural abundance of trace elements in native berries. Using Al as an indicator of the abundance of soil-derived mineral particles, the abundance of dust on the surface of the berries is 20 to 29× lower than that of the substrate (moss). Other lithophile elements (V, Cr, Co, Ga, Li and Y) show similar differences between moss and berry. The concentrations of Rb and Ba in berries were similar to moss and Sr within a factor of 3 to 4×, probably reflecting passive uptake of these lithophile elements by the plants, even though they have no known physiological function. Of the micronutrients examined (Mn, Fe, Ni, Cu, Zn and Mo), Cu and Mn were more abundant in berries than moss, Ni and Zn yielded similar concentrations in both whereas Fe followed by Mo showed the greatest concentration difference. For these micronutrients, uptake by the plants through their roots via the substrate (moss and peat) outweighs contributions from atmospheric dusts. In respect to potentially toxic "heavy metals", Pb concentrations in the moss (BMW, 89 ±â€¯7.3 µg/kg; CMW, 93 ±â€¯27 µg/kg) are below the natural, "background" values reported for ancient layers of Swiss peat from the mid-Holocene (>6000 years old). The Pb concentrations in the berries, however, are 19 to 47× lower than in the underlying moss indicating that Pb in the berries, like Al, is exclusively supplied by dust. Cadmium in the berries is at or above the level found in moss due to active uptake by the plants from the substrate, most likely because of the chemical similarity of this element to Zn. Silver, Sb and Tl in the berries were

Trace elements in berries collected near upgraders and open pit mines in the Athabasca Bituminous Sands Region (ABSR): Distinguishing atmospheric dust deposition from plant uptake.

There are ongoing concerns regarding environmental emissions of trace elements (TEs) from bitumen mining and upgrading in the Athabasca Bituminous Sands Region (ABSR). Depending on their physical and chemical forms, elevated concentrations of potentially toxic TEs in berries could pose a health risk to local indigenous communities because native fruits are an important part of their traditional diet. The objective of this study was to distinguish between aerial deposition of TEs versus plant uptake, in cranberries, lingonberries, and blueberries growing in the ABSR. The concentrations of TEs were determined using ICP-MS in the metal-free, ultraclean SWAMP lab at the University of Alberta. The spatial variation in abundance of conservative, lithophile elements such as Y in berries resembles the published map of dust deposition rates obtained using Sphagnum moss. The presence of dust particles on the surface of the berries near open pit mines and upgraders was confirmed using SEM. Elements which show strong, positive correlation with Y include Al, Cr, Pb, U, and V; these are supplied mainly by dust. Elements which are largely independent of Y concentrations include Ba, Cd, Cu, Mn, Mo, Ni, Rb, Sr, and Zn; these are obtained primarily by plant uptake from soil. The concentrations of elements associated with dust were considerably reduced after washing with water, but the elements independent of dust inputs were unaffected. Elements which are supplied almost exclusively by dust (e.g. Y) are more abundant in berries from the ABS region (2 to 24 times), compared to berries from remote locations.

A geochemical perspective on the natural abundance of trace elements in beaver (Castor canadensis) from a rural region of southern Ontario, Canada.

Chalcophile (Ag, Cd, Co, Cu, Mo, Ni, Pb, Se, Tl, Zn) and lithophile (Al, Ba, Ce, Cr, Cs, Fe, La, Li, Mn, Nd, Rb, Sr, V, Y) trace elements (TEs) were determined in kidney, liver and muscle of beaver (Castor canadensis) from a rural watershed in southern Ontario, Canada. To estimate the relative bioavailability of TEs in the landscape, they were also determined in the dissolved (<0.45 µm) fraction of water from the river where the animals were harvested. Concentration ratios (tissue/water) always showed the greatest enrichments for Cd (kidney, 1.1 × 107; liver, 2.4 × 106; muscle, 7.2 × 105), most likely due to the metal binding properties of metallothioneins. Despite its potential toxicity, Tl also showed considerable enrichment: kidney, 4.2 × 104; liver 1.2 × 104; muscle 1.5 × 104. Enrichments of Cs and Rb exceeded those of Tl in all three tissues, suggesting that the chemical similarity of their ionic species (Cs+, Rb+, Tl+) to K+ may be the key to their uptake. Lithophile elements of limited solubility in natural waters (Al, Ce, La, Nd) show moderate enrichments, despite the lack of physiological role. The smallest enrichments were found for Sr and Ba, the two TEs which are most abundant in the river. Of the TEs considered essential for animal nutrition, V was the least enriched in tissue relative to water (liver 19×, kidney, 33× and muscle 28×). Despite the lack of physiological function and absence of any known sources of contamination, Al, Ag, Cd, Ce, Cs, La, Pb, Rb, and Tl, are all enriched in beaver tissue, relative to water, by at least three orders of magnitude, due to natural processes. The widespread abundance of beaver in Canada combined with the growing need to manage their numbers in populated regions offer a unique opportunity for monitoring environmental quality in the riparian zone.

Bioaccumulation of Tl in otoliths of Trout-perch (Percopsis omiscomaycus) from the Athabasca River, upstream and downstream of bitumen mining and upgrading.

It has been suggested that open pit mining and upgrading of bitumen in northern Alberta releases Tl and other potentially toxic elements to the Athabasca River and its watershed. We examined Tl and other trace elements in otoliths of Trout-perch (Percopsis omiscomaycus), a non-migratory fish species, collected along the Athabasca River. Otoliths were analyzed using ICP-QMS, following acid digestion, in the metal-free, ultraclean SWAMP laboratory. Compared to their average abundance in the dissolved (<0.45 µm) fraction of Athabasca River, Tl showed the greatest enrichment in otoliths of any of the trace elements, with enrichments decreasing in the order Tl, Sr, Mn, Zn, Ba, Th, Ni, Rb, Fe, Al, Cr, Ni, Cu, Pb, Co, Li, Y, V, and Mo. Normalizing Tl in the otoliths to the concentrations of lithophile elements such as Li, Rb, Al or Y in the same tissue reveals average enrichments of 177, 22, 19 and 190 times, respectively, relative to the corresponding ratios in the water. None of the element concentrations (Tl, Li, Rb, Al, Y) or ratios were significantly greater downstream of industry compared to upstream. This natural bioaccumulation of Tl most likely reflects the similarity in geochemical and biological properties of Tl+ and K+. SUMMARY OF MAIN FINDINGS: Thallium is enriched in fish otoliths, relative to the chemical composition of the river, to the same degree both upstream and downstream of industry.

Spatial assessment of major and trace element concentrations from Lower Athabasca Region Trout-perch (Percopsis omiscomaycus) otoliths.

The Lower Athabasca Region (LAR) is home to the largest bitumen deposit in Alberta, and has seen industrial development related to the extraction and processing of bituminous sands since the late 1960s. Along with industrial and economic growth related to oil sands development, environmental concerns have increased in recent decades, including those about potential effects on fish. We measured major and trace element concentrations in Trout-perch otoliths from the Athabasca and Clearwater Rivers in the LAR, to illustrate spatial variations and identify possible industrial impacts. Both laser ablation ICP-MS and solution-based ICP-MS methods were employed. Of the trace elements enriched in bitumen (V, Ni, Mo and Re), only Ni and Re were above the limits of detection using at least one of the methods. The only significant differences in element concentrations between upstream and downstream locations were found for Li, Cu, and Pb which were more abundant upstream of industry. For comparison and additional perspective, otoliths from the same fish species, but taken from the Batchawana River in northern Ontario, were also examined. The fish from Alberta yielded greater concentrations of Ba, Bi, Li, Mg, Na, Re, Sc, Th and Y, but the Ontario fish had more Cr, Rb and Tl, likely because of differences in geology.

Size-resolved Pb distribution in the Athabasca River shows snowmelt in the bituminous sands region an insignificant source of dissolved Pb.

Lead (Pb) is a metal of special importance because of its long history of commercial and industrial use, global atmospheric contamination accelerated by the use of gasoline additives, and health effects, with children being especially vulnerable. Global atmospheric Pb pollution reached its zenith in the 1970's, but subsequent impacts on freshwater aquatic systems are poorly understood. Employing metal-free sampling and handling protocols, we show that snowmelt from the Athabasca bituminous sands region is an insignificant source of dissolved Pb to the Athabasca River (AR). Total Pb in the AR is low, and almost entirely in particulate form. Lead in the suspended solids in the AR exactly follows thorium (Th), a conservative lithophile element, and a linear regression of Pb against Th (Pb = 1.6 × Th + 0.0; R2 = 0.99) yields a slope identical to the Pb/Th ratio in the Upper Continental Crust. In the "dissolved" fraction, the Pb/Th ratio is equivalent to that of deep, open ocean seawater; and dominated by colloidal forms. Taken together, these results show that the efforts of recent decades to reduce anthropogenic Pb to the environment have been successful: Pb loading to the river can now be explained predominantly by natural processes, namely erosion plus chemical weathering.

Trace metals in the dissolved fraction (<0.45µm) of the lower Athabasca River: Analytical challenges and environmental implications.

Water samples were collected on the Athabasca River (AR), upstream and downstream from bitumen mines and upgrading facilities, to identify changes in water quality due to industrial activities in this region of northern Alberta, Canada. Starting upstream of Fort McMurray and proceeding downstream ca. 100km, waters were collected in duplicate at 13 locations on the main stem of the river, as well as 5 tributary streams, using ultraclean sampling protocols developed for polar snow and ice. To estimate potential bioaccessibility, trace elements of concern (Ag, Cd, Pb, Sb, Tl) were determined in the dissolved fraction (<0.45µm) along with metals known for their enrichments in bitumen (V, Ni, Mo, Re) and those found mainly in ionic (Li, Sr) or colloidal forms (Al, Co, Cr, Fe, Ga, Mn, Th, Y). Analyses were performed in the metal-free, ultraclean SWAMP lab using quadrupole and sector-field ICP-MS. Concentrations of Ag, Cd, Pb, Sb and Tl were extremely low, not significantly more abundant downstream of industry and probably reflect "background" values. In contrast, V, Ni, Mo and Re concentrations were all significantly (p<0.05) greater downstream of industry. However, chloride also increased downstream, due to natural inputs of saline groundwaters and it is unclear whether the increases in V, Ni, Mo and Re are due to natural or anthropogenic inputs to the river. Although it had been claimed that the industrial development of the Athabasca Bituminous Sands (ABS) is a significant source of Ag, Cd, Pb, Sb and Tl to the river, our study failed to find any evidence to support this. Here we provide a first, robust (accurate and precise) description of baseline values for these trace elements in the AR, and suggest that V, Ni, Mo and Re are more valuable tracers for environmental monitoring and source assessment.