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Abstract: A peat core from an ombrotrophic bog documents the isotopic evolution of atmospheric Pb in central Ontario since AD 1804±53 (210Pb dating). Despite the introduction of unleaded gasoline in the mid-1970’s, the ratio 206Pb/207Pb in atmospheric deposition has not increased as expected, but rather continues to decline. In fact, snowpack sampling (2005 and 2009) and rainwater samples (2008) show that the isotopic composition of atmospheric Pb today is often far less radiogenic than the gasoline lead that had been used in Canada in the past. The peat, snow, and rainwater data presented here are consistent with the Pb isotope data for aerosols collected in Dorset in 1984 and 1986 which were traced by to emissions from the Noranda smelter in northern Quèbec, Canada’s largest single source of atmospheric Pb. Understanding atmospheric Pb deposition in central Ontario, therefore, requires not only consideration of natural sources and past contributions from leaded gasoline, but also emissions from metal smelting and refining. Lead in the streams which enter Kawagama Lake today (206Pb/207Pb=1.16−1.19) represents a mixture between the natural values (1.191−1.201 estimated using pre-industrial lake sediments) and the values found in the humus layer of the surrounding forest soils (206Pb/207Pb=1.15−1.19). In the lake itself, however, Pb is much less radiogenic (206Pb/207Pb as low as 1.09) than in the streams, with the dissolved fraction less radiogenic than particulate material. The evolution of Pb isotope ratios within the watershed apparently reflects preferential removal by sedimentation of comparatively dense, radiogenic, terrestrial particles (derived from the mineral fraction of soils) from the humus particles with lower ratios of 206Pb/207Pb (because of atmospheric Pb contamination). Despite the contemporary enrichments of Pb in rain and snow, concentrations of dissolved Pb in the lake are extremely low (sometimes below 10ng/l), with Pb concentrations and Pb/Sc ratios approaching “natural” values because of efficient binding to particles, and their subsequent removal in the watershed. [Copyright &y& Elsevier]

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare no competing financial interest to be submitted to Environmental Research., (Copyright © 2020. Published by Elsevier Inc.)

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.

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 × 10 7 ; liver, 2.4 × 10 6 ; muscle, 7.2 × 10 5 ), most likely due to the metal binding properties of metallothioneins. Despite its potential toxicity, Tl also showed considerable enrichment: kidney, 4.2 × 10 4 ; liver 1.2 × 10 4 ; muscle 1.5 × 10 4 . 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., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Snow samples collected from hand-dug pits at two sites in Simcoe County, Ontario, Canada were analysed for major and trace elements using the clean lab methods established for polar ice. Potentially toxic, chalcophile elements are highly enriched in snow, relative to their natural abundance in crustal rocks, with enrichment factor (EF) values (calculated using Sc) in the range 107 to 1081 for Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, Te, and Zn. Relative to M/Sc ratios in snow, water samples collected at two artesian flows in this area are significantly depleted in Ag, Al, Be, Bi, Cd, Cr, Cu, Ni, Pb, Sb, Tl, V, and Zn at both sites, and in Co, Th and Tl at one of the sites. The removal from the waters of these elements is presumably due to such processes as physical retention (filtration) of metal-bearing atmospheric aerosols by organic and mineral soil components as well as adsorption and surface complexation of ionic species onto organic, metal oxyhydroxide and clay mineral surfaces. In the case of Pb, the removal processes are so effective that apparently "natural" ratios of Pb to Sc are found in the groundwaters. Tritium measurements show that the groundwater at one of the sites is modern (ie not more than 30 years old) meaning that the inputs of Pb and other trace elements to the groundwaters may originally have been much higher than they are today; the M/Sc ratios measured in the groundwaters today, therefore, represent a conservative estimate of the extent of metal removal along the flow path.Lithogenic elements significantly enriched in the groundwaters at both sites include Ba, Ca, Li, Mg, Mn, Na, Rb, S, Si, Sr, and Ti. The abundance of these elements can largely be explained in terms of weathering of the dominant silicate (plagioclase, potassium feldspar, amphibole and biotite) and carbonate minerals (calcite, dolomite and ankerite) in the soils and sediments of the watershed. Arsenic, Mo, Te, and especially U are also highly enriched in the groundwaters, due to chemical weathering: these could easily be explained if there are small amounts of sulfides (As, Mo, Te) and apatite (U) in the soils of the source area. Elements neither significantly enriched nor depleted at both sites include Fe, Ga, Ge, and P.

Using ICP-SMS and the clean lab methods and procedures developed for determining trace element concentrations in polar snow and ice, a lower limit of detection (LOD) of 30 pg l(-1) for Sb and 5 pg l(-1) for Sc was achieved, allowing the natural abundances of Sb and Sc to be measured in pristine groundwaters. Water samples were collected from natural flows and wells between Elmvale and Wyevale in Springwater Township, Ontario, Canada. The water in this region is derived from chemical reactions between meteoric fluids and the Quaternary sediments which cover the bedrock (dolomitic limestone) to depths of more than 100 m. The chemical composition of these waters (pH 8) is primarily a reflection of reactions between the percolating fluids with calcite and dolomite. The maximum concentration of Sb was 5.0 ng l(-1), and the average of all samples collected was 2.2 +/- 1.2 ng l(-1) (n = 34). The average concentration of Sc was 8.6 +/- 4.7 ng l(-1) (n = 28). The paucity of published Sb concentration data available for comparison is probably because most of the analytical methods commonly used to date, including GFAAS, HG-AAS, HG-AFS, INAA, and ICP-QMS, have lower limits of detection which are inadequate for reliably determining the natural abundance of Sb in many uncontaminated groundwaters. Also, the measurement of extremely low concentrations of Sb requires extra care to avoid possible contamination. Given the extensive use of Sb in plastics, we show that some of the containers used to collect and store samples, and for handling and preparing samples for chemical analyses, may be important sources of contamination in the laboratory. The Sb and Sc concentrations reported here should serve as reference values for this region, against which contamination by various human impacts in future could be compared.