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.

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.

Thermally Released Arsenic in Porewater from Sediments in the Cold Lake Area of Alberta, Canada.

Elevated arsenic (As) in aquifers in close proximity to in situ oil sands extraction in the Cold Lake area, Alberta, Canada is attributed to high temperature steam (~200 °C) injected into oil sands deposits to liquefy bitumen. Heat propagated from hot injection wells alters physicochemical properties of the surrounding sediments and associated porewater. Seven sediments from four different cores drilled up to ~300 m depth collected from different locations in the area were used to study the thermal effect (~200 °C) on As distribution in the sediments and its release into porewater. Sediments were moistened with synthetic aquifer or deionized water according to the moisture regimes present in aquitard, aquifer and fractured zones. Heat application greatly released As in the porewater (500-5200 and 1200-6600 µg L(-1)) from aquifer and fractured sediments, respectively. Mass balance of As chemical fractionation showed that ~89-100% of As in porewater was released from exchangeable and specifically adsorbed As in the sediments. Heat application also altered As distribution in the sediments releasing As from exchange surfaces and amorphous Fe oxides to soluble As fraction. The results provide great insight into As release mechanisms warranting development of strategies to mitigate groundwater As contamination during industrial operation.

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.

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.

Estimating bioaccessibility of trace elements in particles suspended in the Athabasca River using sequential extraction.

Employing protocols developed for polar snow and ice, water samples were collected upstream, midstream and downstream of open pit bitumen mines and upgraders along the Lower Athabasca River (AR). The purpose was to: i) estimate the bioaccessibility of trace elements associated with particulate matter in the AR using sequential extraction, and ii) determine whether their forms have been measurably impacted by industrial activities. Of the trace metals known to be enriched in bitumen (V, Ni, Mo and Re), a substantial proportion of V (78-93%) and Ni (35-81%) was found in the residual fraction representing stable minerals. In contrast, Mo and Re were partitioned mainly into more reactive forms (water soluble, acid extractable, reducible and oxidisable). Comparing the non-residual fractions in upstream versus downstream sites, only water soluble Re was significantly (P = 0.005) greater downstream of industry. In respect to the potentially toxic chalcophile elements (Cu, Pb and Tl), no measurable change was observed in Cu and Pb distribution in upstream versus downstream sites. Only residual Tl was found at upstream and midstream sites, whereas a significant proportion of Tl was also present in the reducible fraction in downstream sites. Overall, a greater proportion of trace metals in the residual fraction at midstream sites appears to be due to inputs of atmospheric dust, clearly evident in microscopic images: energy dispersive spectroscopy and x-ray diffraction analyses showed that these particles were predominantly silicates, which are assumed to have limited bioaccessibility.

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.

Arsenic speciation in the lower Athabasca River watershed: A geochemical investigation of the dissolved and particulate phases.

Human and ecosystem health concerns for arsenic (As) in the lower Athabasca River downstream of Athabasca Bituminous Sands (ABS) mining (Alberta, Canada) prompted an investigation to determine its forms in surface and groundwater upstream and downstream of industry. Dissolved As species, together with total and particulate As, were used to evaluate the potential bioavailability of As in water as well as to decipher inputs from natural geological processes and ABS mining and upgrading activities. Water samples were collected from the river in October at 13 locations in 2014 and 19 locations in 2015, spanning up to 125 km. Additional samples were collected from groundwater, tributaries and springs. "Dissolved" (<0.45 µm) As was consistently low in the Athabasca River (average 0.37 ± 0.01 and 0.34 ± 0.01 µg L-1 in 2014 and 2015, respectively) as well as tributaries and springs (<1 µg L-1), with As(V) as the predominant form. The average total As concentration was higher in 2014 (12.7 ± 2.8 µg L-1) than 2015 (3.3 ± 0.65 µg L-1) with nearly all As associated with suspended solids (>0.45 µm). In 2014, when total As concentrations were greater, a significant correlation (p < 0.05) was observed with thorium in particles > 0.45 µm, suggesting that mineral material is an important source of As. Naturally saline groundwater contained low dissolved As (<2 µg L-1) and did not appear to be a significant source to the river. Arsenic in shallow groundwater near a tailings pond exceeded 50 µg L-1 predominantly as As(III) warranting further investigation.

Arsenic fractionation and mineralogical characterization of sediments in the Cold Lake area of Alberta, Canada.

Elevated arsenic (As >0.01 mg L(-1)) in some domestic well water in the Cold Lake area of Alberta, Canada is of great concern for public health. To determine possible sources of groundwater As, sediments (n=135) collected from five different locations (up to ~300 m depth) in the area were characterized. Total As concentrations in the sediments varied from ~1 to 35 mg kg(-1). Sediments derived from shale contained high As (~13 mg kg(-1); n=14), particularly the shale of Lea Park formation where maximum average As was ~32 mg kg(-1) (n=2). Unoxidized sediments of Grand Centre (24.9 ± 4.2 mg kg(-1) As) and Bonnyville (19.9 ± 1.8 mg kg(-1) As) formations also contained high As. Sequential extraction procedure (SEP) revealed the dominance of exchangeable and specifically adsorbed As (6 to 46% of total As) in the sediments of varying As concentrations (0.8 to 35.4 mg kg(-1) As). The high As sediments (>7 mg kg(-1) As) also contained significant amount of sulfide bound As (11 to 34% of total As), while low As (<7 mg kg(-1) As) sediments had crystalline oxide minerals bound As (25 to 75% of total As) as major phases. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses confirmed the presence of pyrite, and µ-XRD analysis signaled the presence of arsenopyrite in sediments containing ~20 mg kg(-1) As. X-ray absorption near edge structure (XANES) spectroscopy analysis suggested dominance of arsenite (AsIII; ~60 to 90% of total As) in all the sediments. These findings may help to devise strategies to investigate mechanisms of As release into the groundwater.

A modified sequential extraction method for arsenic fractionation in sediments.

A modified sequential extraction method was developed to characterize arsenic (As) associated with different solid constituents in surficial deposits (sediments), which are unconsolidated glacial deposits overlying bedrock. Current sequential extraction methods produce a significant amount of unresolved As in the residual fraction, but our proposed scheme can fractionate >90% of the As present in sediments. Sediment samples containing different As concentrations (3-35 µg g(-1)) were used to assess the developed method. The pooled amount of As recovered from all the fractions using the developed method was similar (83-122%) to the total As extracted by acid digestion. The concentrations of As in different fractions using the developed scheme were comparable (89-106%) to the As fractions obtained by other existing methods. The developed method was also evaluated for the sequential extraction of other metals such as copper (Cu), cobalt (Co), chromium (Cr) and strontium (Sr) in the sediment samples. The pooled concentrations of these four individual metals from all the fractions were similar (96-104%) to their total concentrations extracted by acid digestion. During method development, we used extractants that did not contain chloride to eliminate formation of polyatomic ions of argon chloride ((40)Ar(35)Cl) that interfered with (75)As when analyzed using inductively coupled plasma mass spectrometer (ICP-MS). The results suggest that the developed method can reliably be employed for complete As and other metals' fractionation in sediments using ICP-MS.