Positron-emitting radiotracers spatially resolve unexpected biogeochemical relationships linked with methane oxidation in Arctic soils.

Arctic soils are marked by cryoturbic features, which impact soil-atmosphere methane (CH4 ) dynamics vital to global climate regulation. Cryoturbic diapirism alters C/N chemistry within frost boils by introducing soluble organic carbon and nutrients, potentially influencing microbial CH4 oxidation. CH4 oxidation in soils, however, requires a spatio-temporal convergence of ecological factors to occur. Spatial delineation of microbial activity with respect to these key microbial and biogeochemical factors at relevant scales is experimentally challenging in inherently complex and heterogeneous natural soil matrices. This work aims to overcome this barrier by spatially linking microbial CH4 oxidation with C/N chemistry and metagenomic characteristics. This is achieved by using positron-emitting radiotracers to visualize millimeter-scale active CH4 uptake areas in Arctic soils with and without diapirism. X-ray absorption spectroscopic speciation of active and inactive areas shows CH4 uptake spatially associates with greater proportions of inorganic N in diapiric frost boils. Metagenomic analyses reveal Ralstonia pickettii associates with CH4 uptake across soils along with pertinent CH4 and inorganic N metabolism associated genes. This study highlights the critical relationship between CH4 and N cycles in Arctic soils, with potential implications for better understanding future climate. Furthermore, our experimental framework presents a novel, widely applicable strategy for unraveling ecological relationships underlying greenhouse gas dynamics under global change.

A sustainable colloidal material with sorption and nutrient-supply capabilities for in situ groundwater bioremediation.

Microbial degradation of subsurface organic contaminants is often hindered by the low availability of both contaminants and nutrients, especially phosphorus (P). The use of activated carbon and traditional P fertilizers to overcome these challenges has proved ineffective; therefore, we sought to find an innovative and effective solution. By heating bone meal-derived organic residues in water in a closed reactor, we synthesized nonporous colloids composed of aromatic and aliphatic structures linked to P groups. X-ray absorption near edge spectroscopy analysis revealed that the materials contain mostly bioavailable forms of P (i.e., adsorbed P and magnesium-bearing brushite). The capacity of the materials to adsorb organic contaminants was investigated using benzene and batch isotherm experiments. The adsorption isotherms were fitted to the linearized Freundlich model; isotherm capacity (logKF ) values for the materials ranged between 1.6 and 2.8 µg g-1 . These results indicate that the colloidal materials have a high affinity for organic contaminants. This, coupled with their possession of bioavailable P, should make them effective amendments for in situ groundwater bioremediation. Also, the materials' chemical properties suggest that they are not recalcitrant, implying that they will not become potential contaminants when released into the environment.

The Structure of Natural Biogenic Iron (Oxyhydr)oxides Formed in Circumneutral pH Environments.

Biogenic iron (Fe) (oxyhydr)oxides (BIOS) partially control the cycling of organic matter, nutrients, and pollutants in soils and water via sorption and redox reactions. Although recent studies have shown that the structure of BIOS resembles that of two-line ferrihydrite (2LFh), we lack detailed knowledge of the BIOS local coordination environment and structure required to understand the drivers of BIOS reactivity in redox active environments. Therefore, we used a combination of microscopy, scattering, and spectroscopic methods to elucidate the structure of BIOS sampled from a groundwater seep in North Carolina and compare them to 2LFh. We also simulated the effects of wet-dry cycles by varying sample preparation (e.g., freezing, flash freezing with freeze drying, freezing with freeze drying and oven drying). In general, the results show that both the long- and short-range ordering in BIOS are structurally distinct and notably more disordered than 2LFh. Our structure analysis, which utilized Fe K-edge X-ray absorption spectroscopy, Mössbauer spectroscopy, X-ray diffraction, and pair distribution function analyses, showed that the BIOS samples were more poorly ordered than 2LFh and intimately mixed with organic matter. Furthermore, pair distribution function analyses resulted in coherent scattering domains for the BIOS samples ranging from 12-18 Å, smaller than those of 2LFh (21-27 Å), consistent with reduced ordering. Additionally, Fe L-edge XAS indicated that the local coordination environment of 2LFh samples consisted of minor amounts of tetrahedral Fe(III), whereas BIOS were dominated by octahedral Fe(III), consistent with depletion of the sites due to small domain size and incorporation of impurities (e.g., organic C, Al, Si, P). Within sample sets, the frozen freeze dried and oven dried sample preparation increased the crystallinity of the 2LFh samples when compared to the frozen treatment, whereas the BIOS samples remained more poorly crystalline under all sample preparations. This research shows that BIOS formed in circumneutral pH waters are poorly ordered and more environmentally stable than 2LFh.

Soil Buffering Capacity Can Be Used To Optimize Biostimulation of Psychrotrophic Hydrocarbon Remediation.

Effective bioremediation of hydrocarbons requires innovative approaches to minimize phosphate precipitation in soils of different buffering capacities. Understanding the mechanisms underlying sustained stimulation of bacterial activity remains a key challenge for optimizing bioremediation-particularly in northern regions. Positron emission tomography (PET) can trace microbial activity within the naturally occurring soil structure of intact soils. Here, we use PET to test two hypotheses: (1) optimizing phosphate bioavailability in soil will outperform a generic biostimulatory solution in promoting hydrocarbon remediation and (2) oligotrophic biostimulation will be more effective than eutrophic approaches. In so doing, we highlight the key bacterial taxa that underlie aerobic and anaerobic hydrocarbon degradation in subarctic soils. In particular, we showed that (i) optimized phosphate bioavailability outperformed generic biostimulatory solutions in promoting hydrocarbon degradation, (ii) oligotrophic biostimulation is more effective than eutrophic approaches, and (iii) optimized biostimulatory solutions stimulated specific soil regions and bacterial consortia. The knowledge gleaned from this study will be crucial in developing field-scale biodegradation treatments for sustained stimulation of bacterial activity in northern regions.

The role of monodentate tetrahedral borate complexes in boric acid binding to a soil organic matter analogue.

Boron is an essential plant micronutrient responsible for several important functions. Boron availability in soils may be influenced by binding with soil organic matter (SOM), particularly with aromatic diol and polyphenol groups on SOM. The mechanism by which aromatic diols bind boron, however, remains unclear. The objective of this work is to further investigate interaction between boric acid and varying concentrations of an aromatic, polyphenolic SOM analogue (tannic acid at 5, 10 and 20 g L-1) from pH = 5-9. UV/Visible spectroscopy showed boric acid enhanced tannic acid deprotonation at pH = 7.0 and 9.0, resulting in singly deprotonated tannic acid subunits. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) showed boric acid/tannic acid binding for all concentrations at pH = 7 and 9, whereas binding at pH = 5.0 was observed only at 20 g L-1 tannic acid. Uncomplexed boron species were not evident at pH = 9.0, but were detectable at pH = 7.0 at lower tannic acid concentrations and prevalent at pH = 5.0, qualitatively indicating binding affinity increases from pH = 5.0 to 9.0. ATR-FTIR results indicated tetrahedral coordination of boron upon complexation to tannic acid with a monodentate mechanism. These results collectively highlight a transition of solution planar boric acid to a tetrahedral, monodentate coordination with a single phenol group in tannic acid polyphenols. This contrasts with previous spectroscopic studies, which indicated bidentate tetrahedral or monodentate trigonal planar orientations prevail at aromatic diol sites. This work presents a previously unobserved boric acid coordination mechanism to an SOM analogue and, therefore, may better inform prediction and modeling of boron behavior in soils.

From the Outside in: An Overview of Positron Imaging of Plant and Soil Processes.

Positron-emitting nuclides have long been used as imaging agents in medical science to spatially trace processes non-invasively, allowing for real-time molecular imaging using low tracer concentrations. This ability to non-destructively visualize processes in real time also makes positron imaging uniquely suitable for probing various processes in plants and porous environmental media, such as soils and sediments. Here, we provide an overview of historical and current applications of positron imaging in environmental research. We highlight plant physiological research, where positron imaging has been used extensively to image dynamics of macronutrients, signalling molecules, trace elements, and contaminant metals under various conditions and perturbations. We describe how positron imaging is used in porous soils and sediments to visualize transport, flow, and microbial metabolic processes. We also address the interface between positron imaging and other imaging approaches, and present accompanying chemical analysis of labelled compounds for reviewed topics, highlighting the bridge between positron imaging and complementary techniques across scales. Finally, we discuss possible future applications of positron imaging and its potential as a nexus of interdisciplinary biogeochemical research.

Preferential adsorption of selenium oxyanions onto {1 1 0} and {0 1 2} nano-hematite facets.

As the commercial use of nano metal oxides, including iron oxides, becomes more prevalent, there is a need to understand functionality as it relates to the inherent properties of the nanomaterial. Many applications of nanomaterials rely on adsorption, ranging from catalysis to aqueous remediation. In this paper, adsorption of selenium (Se), an aqueous contaminant, is used as a model sorbate to elucidate the relationships of structure, property, and (adsorptive) function of nano-hematite (nα-Fe2O3). As such, six nα-Fe2O3 particles were synthesized controlling for size, shape and surface area without capping agents. Sorbent characteristics of the six particles were then assessed for their impact on selenite (HSeO3-) and selenate (SeO42-) adsorption capacity and mechanism. Mechanism was assessed using in-situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and extended X-ray absorption fine edge spectroscopy (EXAFS). Regression analyses were then performed to determine which characteristics best describe adsorption capacity and binding mechanisms of Se on nα-Fe2O3. The results demonstrate that crystal surface structure, specifically presence of the {0 1 2} facet promotes adsorption of Se and the presence of {0 1 2} facets promotes SeO42- sorption to a greater extent than HSeO3-. The data further indicates that {1 1 0} facets bind HSeO3- with binuclear complexes while {0 1 2} facets bind HSeO3- via mononuclear inner-sphere complexes. Specific nα-Fe2O3 facets also likely direct the ratio of inner to outer-sphere complexes in SeO42- adsorption.

Effects of chemical speciation on the bioaccessibility of zinc in spiked and smelter-affected soils.

Previous studies have suggested that understanding soil metal speciation, rather than relying solely on total metal content, can improve the accuracy and utility of contaminated site risk assessments. Because soil properties and reaction time can alter metal speciation, speciation should influence metal bioaccessibility. For example, under gastrointestinal conditions, it is expected that metal species will differ in bioaccessibility depending on their stability in acidic pH environments. We studied the links between metal speciation and bioaccessibility. A combination of synchrotron-based X-ray diffraction and X-ray absorption near edge structure (XANES) was used to identify the zinc (Zn) speciation in spiked and smelter-affected soils. After conducting in vitro digestion tests on the soil samples, XANES and linear combination fitting were carried out on the residual pellets to identify the species of Zn that remained after digesting the soils in the simulated gastric and duodenal fluids. The metal species that were not present in the residual pellets were inferred to have been dissolved and, thus, more bioaccessible. Sphalerite (ZnS), ZnO, and outer-sphere Zn contributed more to Zn bioaccessibility than franklinite (ZnFe2 O4 ) and Zn incorporated into a hydroxy interlayer mineral (Zn-HIM). The bioaccessibility of Zn-aluminum layered double hydroxides (Zn-Al-LDH) was found to be inversely proportional to its residence time in soil. It was also observed that the relatively high pH of the duodenum favors metal reprecipitation and readsorption, leading to a reduction in bioaccessible metal concentration. These results imply that metal speciation mainly controls metal bioaccessibility. Environ Toxicol Chem 2019;38:448-459. © 2018 SETAC.

A FTIRM study of the interactive effects of metals (zinc, copper and cadmium) in binary mixtures on the biochemical constituents of the gills in rainbow trout (Oncorhynchus mykiss).

We employed Fourier Transform Infrared Microspectroscopy to examine, in situ, the effects of waterborne Cu, Cd and Zn, alone and in binary mixtures, during acute exposure on the integrity of major lipid and protein constituents of the gill of a model teleost species, rainbow trout (Oncorhynchus mykiss). Our findings demonstrated that acute exposure to metals, both individually and in binary mixture, resulted in the degradations of various components of proteins and lipids in the gill tissue. Generally, when comparing the effects of individual metals, Cu was found to induce the maximum adverse effects followed by Cd and Zn, respectively. Among the binary metal-mixture combinations, Cu and Cd produced additive effects on the degradation of major proteins and lipid moieties, whereas the co-exposure of Zn with Cd or Cu elicited ameliorative effects, indicating antagonistic (less than additive) interactions between Zn and Cd or Cu in the rainbow trout gill. Overall, the present study demonstrates that FTIRM can be a useful tool to gain novel mechanistic insights into the biochemical changes induced by metals in the fish gill, which could influence the overall toxicity of metals to fish.

Distribution and speciation of zinc in the gills of rainbow trout (Oncorhynchus mykiss) during acute waterborne zinc exposure: Interactions with cadmium or copper.

We utilized micro X-ray fluorescence imaging (µ-XFI) and micro X-ray absorption near-edge spectroscopy (µ-XANES), which are both synchrotron-based techniques to investigate Zn distribution profile, its co-localization patterns with Ca, S, and Fe and speciation in the gills of rainbow trout (RBT). Fish (~100 g) were exposed to acutely toxic levels of waterborne Zn alone and in combination with waterborne Cd or Cu for 24 h (each at 1 × 96 h LC50). Gill sections were prepared and analyzed at the VESPERS beamline of the Canadian Light Source. The primary lamellae of the fish gill were found to be the primary area of Zn accumulation. These regions also correspond to the zones of mitochondria rich cells localization in fish gills, supporting the putative roles of these cells in metal uptake. Zn was also found to predominantly co-localize with Ca and S, but not with Fe, indicating the roles of Ca and S in intracellular Zn handling. Zn distribution in the gill was markedly reduced during co-exposure to Cd, but not to Cu, suggesting a competitive interaction between Zn and Cd for uptake. The speciation of Zn in the gill was dominated by Zn-phosphate, Zn-histidine and Zn-cysteine species; however, the interactions of Zn with Cd or Cu resulted in the loss of Zn-cysteine. Overall, our findings provide important novel insights into the interactions of Zn, Cd and Cu in the fish gill, which may ultimately help to explain the mechanisms underlying the acute toxicity of these metals in binary mixture to fish.

Phosphorus speciation in a prairie soil amended with MBM and DDG ash: Sequential chemical extraction and synchrotron-based XANES spectroscopy investigations.

Sequential chemical extraction and synchrotron-based XANES spectroscopy techniques were used to identify P species in two ashes before and after addition to a prairie soil. The used ashes were: meat and bone meal ash (MBMA) and dried distillers grains ash (DDGA) plus mineral P fertilizer (MP) for comparison. Soil treated with MP contained higher content of resin-Pi and NaHCO3-Pi followed by DDGA and MBMA. The MBMA amended soil had the highest (47%) proportion of the soil P contained in recalcitrant HCl extractable fraction, reflecting more Ca-bound P present and being formed in soil after application. Analysis of both ashes with XANES spectroscopy before application to soil revealed that MBMA had strong spectral features consistent with hydroxyapatite (Ca5(PO4)3(OH)). DDGA exhibited spectral features consistent with a mixture of several Mg and K phosphate salts rather than a single mineral species. The distinctive features in the XANES spectra of both ashes largely disappeared after amendment to the soil, suggesting transformation to different P forms in the soil after application. It is also possible that the added amount of P to the studied soil via DDGS or MBMA was small enough so that P speciation is not different from the background P level.

Chemical speciation and fate of tripolyphosphate after application to a calcareous soil.

Adsorption and precipitation reactions often dictate the availability of phosphorus in soil environments. Tripolyphosphate (TPP) is considered a form of slow release P fertilizer in P limited soils, however, investigations of the chemical fate of TPP in soils are limited. It has been proposed that TPP rapidly hydrolyzes in the soil solution before adsorbing or precipitating with soil surfaces, but in model systems, TPP also adsorbs rapidly onto mineral surfaces. To study the adsorption behavior of TPP in calcareous soils, a short-term (48 h) TPP spike was performed under laboratory conditions. To determine the fate of TPP under field conditions, two different liquid TPP amendments were applied to a P limited subsurface field site via an in-ground injection system. Phosphorus speciation was assessed using X-ray absorption spectroscopy, total and labile extractable P, and X-ray diffraction. Adsorption of TPP to soil mineral surfaces was rapid (< 48 h) and persisted without fully hydrolyzing to ortho-P. Linear combination fitting of XAS data indicated that the distribution of adsorbed P was highest (~ 30-40%) throughout the site after the first TPP amendment application (high water volume and low TPP concentrations). In contrast, lower water volumes with more concentrated TPP resulted in lower relative fractions of adsorbed P (15-25%), but a significant increase in total P concentrations (~ 3000 mg P kg soil) and adsorbed P (60%) directly adjacent to the injection system. This demonstrates that TPP application increases the adsorbed P fraction of calcareous soils through rapid adsorption reactions with soil mineral surfaces.

Citrate Addition Increased Phosphorus Bioavailability and Enhanced Gasoline Bioremediation.

Phosphorus (P) bioavailability often limits gasoline biodegradation in calcareous cold-region soils. One possible method to increase P bioavailability in such soils is the addition of citrate. Citrate addition at the field scale may increase hydrocarbon degradation by: (i) enhancing inorganic and organic P dissolution and desorption, (ii) increasing hydrocarbon bioavailability, and/or (iii) stimulating microbial activity. Alternatively, citrate addition may inhibit activity due to competitive effects on carbon metabolism. Using a field-scale in situ biostimulation study, we evaluated if citrate could stimulate gasoline degradation and what the dominant mechanism of this stimulation will be. Two large bore injectors were constructed at a site contaminated with gasoline, and a biostimulation solution of 11 mM MgSO, 1 mM HPO, and 0.08 mM HNO at pH 6.5 in municipal potable water was injected at ∼5000 L d for about 4 mo. Following this, 10 mM citric acid was incorporated into the existing biostimulation solution and the site continued to be stimulated for 8 mo. After citrate addition, the bioavailable P fraction in groundwater and soil increased. Iron(II) groundwater concentrations increased and corresponded to decreases in benzene, toluene, ethylbenzene, xylenes (BTEX) in groundwater, as well as a decrease in F1 in the soil saturated zone. Overall, citrate addition increased P bioavailability and may stimulate anaerobic microbial activity, resulting in accelerated anaerobic gasoline bioremediation in cold-region calcareous soils.

Inhibition of phosphorus sorption on calcite by dairy manure-sourced DOC.

In confined animal feeding operations, such as dairies, manure is amended to soils at high rates leading to increases in P and organic matter in the soils. Phosphorus reacts with soil-Ca to form Ca-P minerals, which controls P availability for leaching and transport through the watershed. In this research, the effects of manure sourced dissolved organic matter (DOM) on P sorption on calcite were measured at different reaction times and concentrations. Reactions were monitored in 1% and 10% manure-to-water extract solutions spiked with P. When manure-DOM was present, a significant reduction in P sorption occurred (2-90% absolute decrease) compared to samples without manure-DOM. The greatest decrease occurred in the samples reacted in the 10% manure solution. XANES spectroscopic analysis showed that at 1% manure solution, a Ca-P phase similar to hydroxyapatite formed. In the calcite samples reacted in the 10% manure solution, K-edge XANES spectroscopy revealed that P occurred as a Ca-Mg-P phase instead of the less soluble hydroxyapatite-like phase. Results from this study suggest that in manure-amended calcareous soils, increased DOM from manure will decrease P sorption capacity and increase the overall P concentration in solution, which will increase the mobility of P and subsequently pose greater risks for impairment of surface water quality.

Mechanisms of tripolyphosphate adsorption and hydrolysis on goethite.

Linear tripolyphosphates (TPP) are used extensively in liquid fertilizers though little is known about their chemical fate after sorption on mineral surfaces. The initial rapid adsorption of TPP to metal oxide surfaces has been observed, but it is not known whether this adsorption will catalyze or inhibit TPP hydrolysis. To determine the effects of adsorption upon TPP hydrolysis, batch reactors were set up with two surface loadings of TPP adsorbed on goethite (α-FeOOH) for up to 3months at pH 4.5, 6.5 and 8.5. Samples were analyzed for; adsorbed phosphorus (P), P speciation via both P K-edge XANES and FTIR vibrational spectroscopies. Additionally, it was learned through in-situ ATR-FTIR that drying of adsorbed TPP in the presence of Ca results in the formation of a Ca-trimetaphosphate type of surface complex. The rates of adsorbed TPP hydrolysis as measured with ex-situ FTIR were most rapid at pH 4.5 with 100% of the TPP fully hydrolyzed by 3months. Slower rates were observed at pH 6.5 and 8.5 through 3months. Compared to published rates of aqueous TPP hydrolysis, adsorption to mineral surfaces catalyzes TPP hydrolysis.

Effects of Dolomitic Limestone Application on Zinc Speciation in Boreal Forest Smelter-Contaminated Soils.

Anthropogenic activities at the HudBay Minerals, Inc., Flin Flon (Manitoba, Canada) mining and processing facility have severely affected the surrounding boreal forest ecosystem. Soil contamination occurred via a combination of metal and sulfuric acid deposition and has resulted in forest dieback and ineffective natural recovery. A community-led effort to revegetate areas of the landscape through the application of a dolomitic limestone has been met with varied success. Zinc (Zn) speciation has shown to be closely linked to the presence or absence of an invasive metal-tolerant grass species, with soils being broadly classed into two revegetation response groups. Group I, characterized by the absence of metal-tolerant grasses, and group II, characterized by the presence of metal-tolerant grasses. The systematic approach used to lime areas of the landscape produced a liming chronosequence for each group. This study used a combination of X-ray absorption spectroscopy, X-ray fluorescence mapping, and X-ray diffraction techniques to determine the effect of liming on Zn speciation in these chronosequences. Liming group I soils resulted in the formation of a neo-phase Zn-Al-hydroxy interlayer coprecipitate and subsequent rapid boreal forest revegetation. The effect of liming on Zn speciation on the group II soils resulted in a gradual transition of increasingly stable adsorption species, culminating with a stable Zn-Al-layered double hydroxide precipitate. Boreal forest vegetation has failed to recolonize group II soils during the study. However, the formation of the layered double hydroxide species resulted in a significant reduction in CaCl-extractable Zn. Further research is required to determine how to promote the revegetation of these soils.

Total Phosphate Influences the Rate of Hydrocarbon Degradation but Phosphate Mineralogy Shapes Microbial Community Composition in Cold-Region Calcareous Soils.

Managing phosphorus bioaccessibility is critical for the bioremediation of hydrocarbons in calcareous soils. This paper explores how soil mineralogy interacts with a novel biostimulatory solution to both control phosphorus bioavailability and influence bioremediation. Two large bore infiltrators (1 m diameter) were installed at a PHC contaminated site and continuously supplied with a solution containing nutrients and an electron acceptor. Soils from eight contaminated sites were prepared and pretreated, analyzed pretrial, spiked with diesel, placed into nylon bags into the infiltrators, and removed after 3 months. From XAS, we learned that three principal phosphate phases had formed: adsorbed phosphate, brushite, and newberyite. All measures of biodegradation in the samples (in situ degradation estimates, mineralization assays, culturable bacteria, catabolic genes) varied depending upon the soil's phosphate speciation. Notably, adsorbed phosphate increased anaerobic phenanthrene degradation and bzdN catabolic gene prevalence. The dominant mineralogical constraints on community composition were the relative amounts of adsorbed phosphate, brushite, and newberyite. Overall, this study finds that total phosphate influences microbial community phenotypes whereas relative percentages of phosphate minerals influences microbial community genotype composition.

Characterizing Zinc Speciation in Soils from a Smelter-Affected Boreal Forest Ecosystem.

HudBay Minerals, Inc., has mined and/or processed Zn and Cu ore in Flin Flon, MB, Canada, since the 1930s. The boreal forest ecosystem and soil surrounding these facilities have been severely impacted by mixed metal contamination and HSO deposition. Zinc is one of the most prevalent smelter-derived contaminants and has been identified as a key factor that may be limiting revegetation. Metal toxicity is related to both total concentrations and speciation; therefore, X-ray absorption spectroscopy and X-ray fluorescence mapping were used to characterize Zn speciation in soils throughout the most heavily contaminated areas of the landscape. Zinc speciation was linked to two distinct soil types. Group I soils consist of exposed soils in weathered positions of bedrock outcrops with Zn present primarily as franklinite, a (ZnFeO) spinel mineral. Group II soils are stabilized by an invasive metal-tolerant grass species, with Zn found as a mixture of octahedral (Fe oxides) and tetrahedral Mn oxides) adsorption complexes with a franklinite component. Soil erosion influences Zn speciation through the redistribution of Zn and soil particulates from Group I landscape positions to Group II soils. Despite Group II soils having the highest concentrations of CaCl-extractable Zn, they support metal-tolerant plant growth. The metal-tolerant plants are probably preferentially colonizing these areas due to better soil and nutrient conditions as a result of soil deposition from upslope Group I areas. Zinc concentration and speciation appears to not influence the colonization by metal-tolerant grasses, but the overall soil properties and erosion effects prevent the revegetation by native boreal forest species.

Solid-liquid separation method governs the in vitro bioaccessibility of metals in contaminated soil-like test materials.

An in vitro gastrointestinal model was used to explore the role of solid-liquid separation method on the bioaccessibility of trace elements in a smelter-impacted soil (NIST-2711) from Helena, MT and a mine overburden from an open-pit gold and silver mine in Mount Nansen, YK (YK-OVB). Separation methods studied included centrifugation (5,000 g, 12,000 g), syringe microfiltration (0.45 µm), and ultrafiltration (1,000 kDa, 50 kDa, 30 kDa, 10 kDa, 3 kDa). Results indicated that the use of syringe microfiltration generally yields the same bioaccessibility as the use of centrifugation and that the speed of centrifugation does not typically affect metal bioaccessibility. However, ultrafiltration consistently yields a significantly lower bioaccessibility than the use of centrifugation and syringe microfiltration. There are rarely any differences between bioaccessibility estimates generated using a low-resistance (1,000 kDa) and a high-resistance (3 kDa) ultrafiltration membrane; therefore, under the in vitro gastrointestinal conditions modeled herein, negligible quantities of trace elements are complexed to small molecules between 3 and 1,000 kDa. The primary exceptions to these trends were observed for Pb in NIST-2711 (5,000 g>12,000 g>0.45 µm>ultrafiltration) and for Tl in NIST-2711 and YK-OVB (5000 g∼12,000 g>0.45 µm>ultrafiltration). These results provide valuable information to researchers attempting to expand the use of in vitro bioaccessibility beyond soil Pb and As.