Legacy copper/nickel mine tailings potentially harbor novel iron/sulfur cycling microorganisms within highly variable communities.

The oxidation of sulfide-bearing mine tailings catalyzed by acidophilic iron and sulfur-oxidizing bacteria releases toxic metals and other contaminants into soil and groundwater as acid mine drainage. Understanding the environmental variables that control the community structure and metabolic activity of microbes indigenous to tailings (especially the abiotic stressors of low pH and high dissolved metal content) is crucial to developing sustainable bioremediation strategies. We determined the microbial community composition along two continuous vertical gradients of Cu/Ni mine tailings at each of two tailings impoundments near Sudbury, Ontario. 16S rRNA amplicon data showed high variability in community diversity and composition between locations, as well as at different depths within each location. A temporal comparison for one tailings location showed low fluctuation in microbial communities across 2 years. Differences in community composition correlated most strongly with pore-water pH, Eh, alkalinity, salinity, and the concentration of several dissolved metals (including iron, but not copper or nickel). The relative abundances of individual genera differed in their degrees of correlation with geochemical factors. Several abundant lineages present at these locations have not previously been associated with mine tailings environments, including novel species predicted to be involved in iron and sulfur cycling.IMPORTANCEMine tailings represent a significant threat to North American freshwater, with legacy tailings areas generating acid mine drainage (AMD) that contaminates rivers, lakes, and aquifers. Microbial activity accelerates AMD formation through oxidative metabolic processes but may also ameliorate acidic tailings by promoting secondary mineral precipitation and immobilizing dissolved metals. Tailings exhibit high geochemical variation within and between mine sites and may harbor many novel extremophiles adapted to high concentrations of toxic metals. Characterizing the unique microbiomes associated with tailing environments is key to identifying consortia that may be used as the foundation for innovative mine-waste bioremediation strategies. We provide an in-depth analysis of microbial diversity at four copper/nickel mine tailings impoundments, describe how communities (and individual lineages) differ based on geochemical gradients, predict organisms involved in AMD transformations, and identify taxonomically novel groups present that have not previously been observed in mine tailings.

Microbiological and geochemical characterization of As-bearing tailings and underlying sediments.

Over the past 100 years, extensive oxidation of As-bearing sulfide-rich tailings from the abandoned Long Lake Gold Mine (Canada) has resulted in the formation of acid mine drainage (pH 2.0-3.9) containing high concentrations of dissolved As (∼400 mg L-1), SO42-, Fe and other metals. Dissolved As is predominantly present as As(III), with increased As(V) near the tailings surface. Pore-gas O2 is depleted to < 1 vol% in the upper 30-80 cm of the tailings profile. The primary sulfides, pyrite and arsenopyrite, are highly oxidized in the upper portions of the tailings. Elevated proportions of sulfide-oxidizing prokaryotes are present in this zone (mean 32.3% of total reads). The tailings are underlain by sediments rich in organic C. Enrichment in δ34S-SO4 in pore-water samples in the organic C-rich zone is consistent with dissimilatory sulfate reduction. Synchrotron-based spectroscopy indicates an abundance of ferric arsenate phases near the impoundment surface and the presence of secondary arsenic sulfides in the organic-C beneath the tailings. The persistence of elevated As concentrations beneath the tailings indicates precipitation of secondary As sulfides is not sufficient to completely remove dissolved As. The oxidation of sulfides and release of As is expected to continue for decades. The findings will inform future remediation efforts and provide a foundation for the long-term monitoring of the effectiveness of the remediation program.

Reactive transport modelling of tailings hydrogeochemistry under a composite cover.

Quantitative forecasts of acid mine drainage (AMD) production are important for remediation planning. Reactive transport simulations corresponding to a detailed sampling location at a covered legacy tailings impoundment in northern Ontario, Canada, were conducted to quantitatively assess the predominant hydrogeochemical reactions. The simulations span the period from the end of tailings deposition (circa 1970) to early 2020, 12 years after remediation by a five-layer composite cover. The conceptual model of uncovered tailings weathering and subsequent geochemistry of the covered tailings system was implemented in 1D using the multi-component reactive transport code MIN3P. Transient monthly infiltration, post-cover boundary condition changes, and a dynamic temperature regime were incorporated. The shrinking core model, including parallel O2(aq) and Fe3+ oxidation reactions for the waste rock in the cover and the underlying tailings, was implemented to simulate the oxidation of As-bearing pyrite, chalcopyrite, and sphalerite. Primary carbonate and aluminosilicate host minerals promoted acid-neutralization reactions. Precipitation of secondary phases and sorption/desorption of Cu, Zn, and arsenite were incorporated into the model. The overall agreement between key simulated and field-measured post-cover aqueous geochemical parameters suggests that the conceptual model captured the primary hydrogeochemical processes in the covered tailings. A lack of reliable data on initial tailings mineralogy and pre-cover hydrogeochemistry increased simulation uncertainty. Simulated reaction rates indicate that where intact, the cover decreased sulfide oxidation rates by both O2(aq) and Fe3+ and improved pore-water quality over time. Simulation results indicate that elevated concentrations of Zn and As are likely to persist in the tailings regardless of cover performance, whereas concentrations of Cu and Al are the parameters most sensitive to cover effectiveness.

Microbial processes with the potential to mobilize As from a circumneutral-pH mixture of flotation and roaster tailings.

The Northwest Tailings Containment Area at the inactive Giant Mine (Canada) contains a complex mixture of arsenic-containing substances, including flotation tailings (84.8 wt%; with 0.4 wt% residual S), roaster calcine wastes (14.4 wt% Fe oxides), and arsenic trioxide (0.8 wt%) derived from an electrostatic precipitator as well as As-containing water (21.3 ± 4.1 mg L-1 As) derived from the underground mine workings. In the vadose zone the tailings pore water has a pH of 7.6 and contains elevated metal(loid)s (2.37 ± 5.90 mg L-1 As); mineral oxidizers account for 2.5% of total 16S rRNA reads in solid samples. In the underlying saturated tailings, dissolved Fe and As concentrations increase with depth (up to 72 and 20 mg L-1, respectively), and the mean relative abundance of Fe(III)-reducers is 0.54% of total reads. The potential for As mobilization via both reductive and oxidative (bio)processes should be considered in Giant Mine remediation activities. The current remediation plan includes installation of an engineered cover that incorporates a geosynthetic barrier layer.

Improved precision in As speciation analysis with HERFD-XANES at the As K-edge: the case of As speciation in mine waste. Corrigendum.

The name of an author in the article by Saurette et al. (2022) [J. Synchrotron Rad. 29, 1198-1208] is corrected.

Extracting resources from abandoned mines.

Recovering minerals and metals from aband on ed mines could aid decarbonization.

Geochemical and mineralogical investigation of cemented crusts in the tailings cover at Long Lake Gold Mine, Sudbury, Canada.

In mine tailings, precipitation of secondary minerals may cement the tailings material and form cemented crusts or hardpans. Hardpans typically form beneath the surface of reactive tailings. However, at the former Long Lake Gold Mine near Sudbury, Ontario, cemented crusts formed in a clean sand cover above the tailings. We applied mineralogical and geochemical techniques to investigate the formation of these cemented crusts. Representative samples were collected from the sand cover and vertical cores from the underlying tailings. Elevated concentrations of arsenic (As), iron (Fe), and sulfur (S) in the sand cover indicate the upward transport of sulfide-mineral oxidation products. The shallow porewater of the tailings is acidic (pH 4 - 6) and contains elevated concentrations of As (up to 346 mg/L), Fe (up to 1844 mg/L), and SO4 (up to 12,000 mg/L). Mineralogical observations indicate that primary sulfide minerals in the near-surface tailings display moderate to strong oxidation, and secondary Fe-arsenate and jarosite minerals are formed both in the near-surface tailings and the sand cover. Upward migration of sulfide-mineral oxidation products leads to the formation of cemented crusts, which with continuing erosion, represent a long-term source of pollution to the surrounding environment.

Improved precision in As speciation analysis with HERFD-XANES at the As K-edge: the case of As speciation in mine waste.

High-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) is a spectroscopic method that allows for increased spectral feature resolution, and greater selectivity to decrease complex matrix effects compared with conventional XANES. XANES is an ideal tool for speciation of elements in solid-phase environmental samples. Accurate speciation of As in mine waste materials is important for understanding the mobility and toxicity of As in near-surface environments. In this study, linear combination fitting (LCF) was performed on synthetic spectra generated from mixtures of eight measured reference compounds for both HERFD-XANES and transmission-detected XANES to evaluate the improvement in quantitative speciation with HERFD-XANES spectra. The reference compounds arsenolite (As2O3), orpiment (As2S3), getchellite (AsSbS3), arsenopyrite (FeAsS), kankite (FeAsO4·3.5H2O), scorodite (FeAsO4·2H2O), sodium arsenate (Na3AsO4), and realgar (As4S4) were selected for their importance in mine waste systems. Statistical methods of principal component analysis and target transformation were employed to determine whether HERFD improves identification of the components in a dataset of mixtures of reference compounds. LCF was performed on HERFD- and total fluorescence yield (TFY)-XANES spectra collected from mine waste samples. Arsenopyrite, arsenolite, orpiment, and sodium arsenate were more accurately identified in the synthetic HERFD-XANES spectra compared with the transmission-XANES spectra. In mine waste samples containing arsenopyrite and either scorodite or kankite, LCF with HERFD-XANES measurements resulted in fits with smaller R-factors than concurrently collected TFY measurements. The improved accuracy of HERFD-XANES analysis may provide enhanced delineation of As phases controlling biogeochemical reactions in mine wastes, contaminated soils, and remediation systems.

Mechanisms of Ni removal from contaminated groundwater by calcite using X-ray absorption spectroscopy and Ni isotope measurements.

A flow-through cell (FTC) experiment was conducted to identify mechanisms of Ni removal by calcite through study of changes in Ni speciation and Ni isotope signature during the treatment of simulated Ni-contaminated groundwater. Synthetic Ni-contaminated groundwater was pumped through a FTC packed with crushed natural calcite. Effluent samples were collected to determine concentrations of anions, cations, and for Ni isotope-ratio measurement. X-ray absorption spectroscopy (XAS) was performed on chosen spots of the solid phase along the FTC length. Isotope data indicated multiple mechanisms affected Ni removal in the FTC system. Ni adsorption to and coprecipitation with calcite dominated the early part of the experiment yielding a fractionation factor of ε = -0.5 ‰. Subsequently, Ni precipitation as a Ni-hydroxide phase became the major process controlling Ni removal, resulting in a fractionation factor ε = -0.4 ‰. XAS analysis confirmed the presence of both Ni(OH)2 and (Ni, Ca)CO3 types of Ni local structural environments. Results from this study highlight the potential of Ni isotopes as auxiliary tools to determine the processes involved in Ni attenuation from the environment. The characterization of mechanisms involved in Ni removal from solution is necessary to evaluate potential impacts to the environment and to develop effective remediation strategies.

Nickel Isotope Fractionation As an Indicator of Ni Sulfide Precipitation Associated with Microbially Mediated Sulfate Reduction.

Microbially mediated sulfate reduction is a promising cost-effective and sustainable process utilized in permeable reactive barriers (PRB) and constructed wetlands to treat mine wastewater. Laboratory batch experiments were performed to evaluate nickel (Ni) isotope fractionation associated with precipitation of Ni-sulfides in the presence of the sulfate-reducing bacterium (SRB) Desulfovibrio desulfuricansT (DSM-642). Precipitates were collected anaerobically and characterized by synchrotron powder X-ray diffraction (PXRD), scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDS), and transmission electron microscopy (TEM). Solid-phase analyses showed that the precipitates associated with bacteria attached to the serum bottle walls were characterized by enhanced size and crystallinity. Lighter Ni isotopes were preferentially concentrated in the solid phase, whereas the solution was enriched in heavier Ni isotopes compared to the input solution. This fractionation pattern was consistent with closed-system equilibrium isotope fractionation, yielding a fractionation factor of Δ60Nisolid-aq = -1.99‰. The Ni isotope fractionation measured in this study indicates multiple Ni reaction mechanisms occurring in the complex SRB-Ni system. The results from this study offer insights into Ni isotope fractionation during interaction with SRB and provide a foundation for the characterization and development of Ni stable isotopes as tracers in environmental applications.

Diavik Waste Rock Project: Simulation of the geochemical evolution of a large test pile using a scaled temperature and sulfide-content dependent reactive transport model.

The Diavik Waste Rock Project (DWRP) project included four principal components focused on the development of techniques for assessing the environmental impacts of waste rock at mine sites. These components were small-volume laboratory experiments, intermediate- and large-volume field experiments, and assessment of the operational-scale waste-rock stockpiles, which facilitated characterization of waste-rock weathering at different scales. The heavily instrumented large-scale field experiments (test piles) were constructed to replicate, as closely as practicable, the temperature, water flow, and gas transport regimes of a waste-rock pile that is exposed to annual freezing and thawing cycles and to facilitate characterization of the long-term weathering of a low-sulfide waste rock. An integrated conceptual model of sulfide-bearing waste-rock weathering, developed at the small scale, was applied to assess the capacity of the conceptual model to capture the geochemical evolution of the waste rock at the large field-scale test-pile experiment. The integrated conceptual model was implemented using reactive transport code MIN3P, taking into account scale-dependent mechanisms. The test-pile mineralogy was similar to the small-scale laboratory experiments and included low-sulfide waste rock with an S content of 0.053 wt% (primarily pyrrhotite). The flow regime of the test pile was simulated using parameters measured as part of other DWRP investigations, including temporally variable infiltration estimates that represented the measured precipitation events at the site. The temporally and spatially variable temperature of the test pile was interpolated from values measured using instrumentation installed at the beginning of the experiment and was included in the simulation to refine the temperature dependence of the geochemical reactions. To allow continuous, multi-year simulation, freezing was also simulated to represent the conditions experienced at the test-pile experiment. Normalized root mean square error analysis of the large-scale field experiment simulation results indicated most parameters compare well to measured daily mass flux (i.e., the fraction of the range of annual values encompassed in the residual was less than 0.5 for SO4, Fe, Ni, Si, Ca, K, Mg, Na, and pH and 1.0 or less for all parameters except Cu). The method of using an integrated conceptual model developed from the results of humidity cell experiments to implement a mechanistic approach for assessing the primary geochemical processes of waste-rock weathering on a large scale was shown to provide reasonable results; however, the results are specific to the study site and the approach requires application to various sites under different geological and climatological conditions to facilitate further refinement.

Removal of arsenic and metals from groundwater impacted by mine waste using zero-valent iron and organic carbon: Laboratory column experiments.

Acid mine drainage and the associated contaminants, including As and metals, are ongoing environmental issues. Passive remediation technologies have the potential to remove As from mine waste effluents. A series of laboratory column experiments was conducted to evaluate the effectiveness of varying mixtures of organic carbon (OC), zero-valent iron (ZVI), and limestone for the treatment of As, metals, SO42-, and acidity in groundwater from an abandoned gold mine. The onset of bacterially-mediated SO42- reduction was indicated by a decrease in Eh, a decline in aqueous SO42- concentrations coupled with enrichment of δ34S, and the presence of sulfate-reducing bacteria and H2S. Removal of As was observed within the first 3 cm of reactive material, to values below 10 µg L-1, representing > 99.9% removal. An increase in pH from 3.5 to circumneutral values and removal of metals including Al, Cu, and Zn was also observed. Synchrotron results suggest As was removed through precipitation of As-crystalline phases such as realgar and orpiment, or through adsorption as As(V) on ferrihydrite. The results indicate the potential for a mixture of OC and ZVI to remove As from acidic, mine-impacted water.

Occurrence and distribution of emerging contaminants in mine-impacted lake water and potential use as co-tracers of anthropogenic activity in the subarctic region, Northwest Territories, Canada.

The emerging contaminant (EC) perchlorate (ClO4-), a blasting agent widely used in mining and refining operations, has been used as a practical indicator of mining activities. Widespread occurrence of ECs, such as pharmaceutical compounds, artificial sweeteners, and perfluoroalkyl substances, and their use as co-tracers of wastewater associated with anthropogenic activities in the urban and Arctic environments have been previously investigated. However, limited studies have reported the occurrence of these ECs and the feasibility of their use as co-tracers of anthropogenic activities in pristine waterbodies (e.g., continuous permafrost region) that receive effluent from mine sites. In this study, water samples were collected from the surface of 10 lakes within the Coppermine and Lockhart Watersheds in the continuous permafrost region in the Northwest Territories, Canada during the open water seasons of 2016, 2017, and 2018. Concentrations of 16 ECs were determined to delineate the spatial and temporal distribution of these compounds in waterbodies receiving effluent from mine sites. Slightly elevated concentrations of ClO4- (100-700 ng L-1), caffeine (0.2-5.9 ng L-1), acesulfame-K (0.5-1.5 ng L-1), perfluorooctanoic acid (PFOA; 5-34 ng L-1), perfluorooctane sulfonic acid (PFOS; 11-40 ng L-1), chloride (1.5-2.3 mg L-1), and sulfate (1.0-3.6 mg L-1) were observed across the two investigated watersheds, especially downstream of the mining sites. The concurrence of elevated concentrations of these target ECs combined with other dissolved constituents (chloride and sulfate) may indicate the influence of mining activity on the receiving waterbodies and the potential use of these compounds as co-indicators of anthropogenic activity. Results from this study provide novel information on the distribution of 16 ECs in pristine waterbodies that receive effluents from mining sites in the Canadian subarctic in advance of more expansive human development and increased warming and melting of mine sites, including mine wastes.

Microbiology of a multi-layer biosolid/desulfurized tailings cover on a mill tailings impoundment.

The Strathcona Waste Water Treatment System (SWWTS; Sudbury, ON, Canada) has received mill tailings from Ni/Cu ore processing from 1970 to present. Demonstration-scale, multi-layer cover systems were installed on selected tailings deposition cells at the SWWTS. The cover systems are comprised of an upper layer of organic carbon-rich material, composed of a layer biosolids fertilizer along with composted municipal food and yard waste, then a layer of desulfurized, fine-grained tailings. Organic carbon components used in these covers promote microbial communities that consume O2, thus decreasing sulfide oxidation rates in the underlying tailings. The aim of this study was to investigate the microbiology of the cover systems and the underlying tailings, using a combination of culture-dependent (most probable number) and culture-independent (16S rRNA gene amplicon sequencing) techniques, and assess the impact of the organic component of the cover system four to six years after implementation. Most tailings samples were characterized by circumneutral bulk pH and low concentrations of dissolved metals. The presence of the organic cover resulted in elevated counts of sulfate-reducers (by two orders of magnitude, compared to control samples) immediately below the organic cover, as well as an increased abundance of heterotrophic species (∼108 cells g-1) at greater depth (∼4 m) in the tailings profile. Mineral-oxidizing microorganisms were also present in the tailings, with neutrophilic sulfur-oxidizers dominating the samples (mean ∼106 cells g-1). Relative abundances of sulfur- and/or iron-oxidizers determined by sequencing ranged from 0.5 to 18.3% of total reads (mean ∼5.6% in amended tailings) and indicated the presence of local microenvironments with ongoing sulfide oxidation. This work provides a detailed characterization of the microbiology of a tailings impoundment with an organic cover, highlighting the opportunities associated with monitoring microbial processes in such remediation systems.

Effect of composting and amendment with biochar and woodchips on the fate and leachability of pharmaceuticals in biosolids destined for land application.

Land application of biosolids can improve soil fertility and enhance crop production. However, the occurrence and persistence of pharmaceutical compounds in the biosolids may result in leaching of these contaminants to surface water and groundwater, causing environmental contamination. This study evaluated the effectiveness of two organic amendments [biochar (BC) and woodchips (WC)] for reducing the concentration and leachability (mobility) of four pharmaceuticals in biosolids derived from wastewater treatment plants in southern Ontario, Canada. The effect of 360-d composting on fate and leachabilities of target pharmaceuticals in biosolid mixtures was also investigated. Composting decreased total and leachable concentrations of pharmaceuticals in unamended and BC- and WC-amended biosolids to various degrees, from 10% up to 99% depending on the compound. Blending BC or WC into the biosolids greatly increased the removal rates of the target pharmaceuticals, while simultaneously decreasing their half-lives (t0.5), compared to unamended biosolids. The t0.5 of contaminants in this study followed the order: carbamazepine (304-3053 d) > gemfibrozil (42.3-92.4 d) > naproxen (15.3-104 d) > ibuprofen (12.5-19.0 d). Amendment with BC and(or) WC significantly reduced the leachability of carbamazepine, ibuprofen, and gemfibrozil to variable extents, but significantly enhanced the leachability of naproxen, compared to unamended biosolids (P < 0.05). Biochar and WC exhibited different (positive or negative) effects on the leachability of individual pharmaceuticals. Significantly lower concentrations of total and(or) leachable (mobile) pharmaceuticals were observed in amended biosolids than unamended biosolids (P < 0.05). Biochar and WC are effective amendments that can reduce the environmental impact of biosolid land applications with respect to pharmaceutical contamination.

A cross scale investigation of galena oxidation and controls on mobilization of lead in mine waste rock.

Galena and Pb-bearing secondary phases are the main sources of Pb in the terrestrial environment. Oxidative dissolution of galena releases aqueous Pb and SO4 to the surficial environment and commonly causes the formation of anglesite (in acidic environments) or cerussite (in alkaline environments). However, conditions prevalent in weathering environments are diverse and different reaction mechanisms reflect this variability at various scales. Here we applied complementary techniques across a range of scales, from nanometers to 10 s of meters, to study the oxidation of galena and accumulation of secondary phases that influence the release and mobilization of Pb within a sulfide-bearing waste-rock pile. Within the neutral-pH pore-water environment, the oxidation of galena releases Pb ions resulting in the formation of secondary Pb-bearing carbonate precipitates. Cerussite is the dominant phase and shannonite is a possible minor phase. Dissolved Cu from the pore water reacts at the surface of galena, forming covellite at the interface. Nanometer scale characterization suggests that secondary covellite is intergrown with secondary Pb-bearing carbonates at the interface. A small amount of the S derived from galena is sequestered with the secondary covellite, but the majority of the S is oxidized to sulfate and released to the pore water.

Impact of multiple drying and rewetting events on biochar amendments for Hg stabilization in floodplain soil from South River, VA.

Frequent drying and rewetting due to flooding/precipitation and drainage events in floodplains induces changes in biogeochemical conditions that may influence the effectiveness of in situ Hg stabilization using biochars as soil amendments. This study evaluated two selected biochars anaerobic digestate (DIG) and sulfurized hardwood (MOAK)) as potential amendment materials in moderately reduced floodplain soil under repeated drying and rewetting events using a modified humidity cell protocol. Enhanced release of filter-passing (0.45-µm) total Hg (THg) and MeHg was observed at early times. Elevated concentrations of 0.45-µm THg were associated with DOC and Mn in sediment control and biochar-amended systems. Elevated concentrations of MeHg were associated with Mn in the MOAK-amended system. Thereafter, decreases in 0.45-µm (up to 57%) and unfiltered THg (up to 93%) were observed. As wetting and drying events continued, decreases in pH and alkalinity as well as increases in SO42- (up to 796 mg L-1) and Ca (up to 215 mg L-1) were observed in the MOAK-amended systems with the microbial community shifted towards sulfur-oxidizing bacteria, indicating microbially-driven oxidation of MOAK. Although results of S K-edge X-ray absorption near edge structure (XANES) analysis suggest polysulfur is the predominant S phase in both MOAK- and DIG-amended systems, microbially-driven oxidation of DIG was not observed. Polysulfur in MOAK from the sulfurization process is more bioavailable to sulfur oxidizing communities than in DIG under the repeated drying and wetting conditions. Results of this study suggest biogeochemical conditions as well as biochar properties should be considered when planning full-scale field applications.

Application of biochar prepared from ethanol refinery by-products for Hg stabilization in floodplain soil: Impacts of drying and rewetting.

This study evaluated three biochars derived from bioenergy by-products - manure-based anaerobic digestate (DIG), distillers' grains (DIS), and a mixture thereof (75G25S) - as amendments to stabilize Hg in contaminated floodplain soil under long-term saturated (up to 200 d) and cyclic drying and rewetting conditions. Greater total Hg (THg) removal (72 to nearly 100%) and limited MeHg production (<65 ng L-1) were observed in digestate-based biochar-amended systems under initial saturated conditions. Drying and rewetting resulted in limited THg release, increased aqueous MeHg, and decreased solid MeHg in digestate-based biochar-amended systems. Changes in Fe and S chemistry as well as microbial communities during drying and rewetting potentially affected MeHg production. Digestate-based biochars may be more effective as amendments to control Hg release and minimize MeHg production in floodplain soils under long-term saturated and drying and rewetting conditions compared to distillers' grains biochar.

Aqua regia digestion cannot completely extract Hg from biochar: A synchrotron-based study.

Mercury (Hg) is commonly extracted from solid phase samples using aqua regia for total Hg (tHg) analysis. However, uncertainties exist regarding the complete extraction of Hg by aqua regia, especially from carbonaceous materials. To investigate whether aqua regia can completely extract Hg from biochars, batch-style experiments were carried out to evaluate extraction efficiency of aqua regia with respect to Hg-loaded biochar and to characterize the residual Hg speciation and spatial distribution. Different types of biochars (raw, FeCl3-modified, and FeSO4-modified, prepared at different temperatures) were reacted with Hg-spiked solution before the digestion experiments. Adsorption analyses indicate the biochars were successfully loaded with Hg and that the Hg content was higher in biochars pyrolyzed at higher temperature (900 versus 300 or 600 °C). The results of digestion experiments indicate Hg could not be completely extracted from the biochars tested, with a greater percentage of residual Hg in biochars pyrolyzed at 600 (60 ± 15%) and 900 (75 ± 22%) than 300 °C (7 ± 2%). Furthermore, the fraction of residual Hg in FeSO4-modified biochars after aqua regia digestion was significantly lower than in FeCl3-modified and unmodified biochars. Confocal micro-X-ray fluorescence imaging (CMXRFI) showed residual Hg in biochars is concentrated on surfaces prior to digestion, but more homogeneously distributed after digestion, which indicates Hg on biochar surface is more easily digested. Hg extended X-ray absorption fine structure (EXAFS) spectra modelling showed residual Hg in biochars mainly exists as Hg(II)-Cl. These results indicate extra caution should be paid for tHg determinations using aqua regia digestion method in soil (especially in forest), sediment, and peat samples containing black carbon, activated carbon, or biochar.

Application of zero-valent iron coupled with biochar for removal of perfluoroalkyl carboxylic and sulfonic acids from water under ambient environmental conditions.

Advanced oxidation and reduction processes have been intensively investigated as potential methods to promote the decomposition of perfluoroalkyl substances (PFASs). However, extreme operational conditions such as highly acidic pH, high temperature, and high pressure are required to promote degradation reactions, which makes these technologies costly and less feasible for full-scale applications. The objective of this study was to evaluate the effectiveness of zero-valent iron (ZVI) alone and a mixture of ZVI and biochar (ZVI + BC) for removal of seven target PFASs from water under ambient environmental conditions. Target PFASs included three perfluoroalkyl carboxylic acids (PFCAs) [perfluorooctanoic acid (PFOA, C8-PFCA), perfluoroheptanoic acid (C7-PFCA), and perfluorohexanoic acid (C6-PFCA)] and four perfluoroalkyl sulfonic acids (PFSAs) [perfluorooctane sulfonic acid (PFOS, C8-PFSA), perfluoroheptane sulfonic acid (C7-PFSA), perfluorohexane sulfonic acid (C6-PFSA), and perfluorobutane sulfonic acid (C4-PFSA)]. Batch test results show that PFSAs (up to 94% removal) were more effectively removed than PFCAs (up to 60% removal) when utilizing either ZVI or (ZVI + BC). About 20-60% of input PFOA (~18,550 µg L-1) and 90-94% of input PFOS (~18,580 µg L-1) were removed by ZVI alone or the mixture of (ZVI + BC). The removal efficiencies of PFCAs and PFSAs by reactive media increased with increasing chain length, from 0 to 17% for short-chain PFCAs (C6-C7) and 20 to 70% for short-chain PFSAs (C4-C7). About 5-10% of input PFOA and PFOS was partially defluorinated by ZVI alone as indicated by F- release; however, the defluorination efficiency may be underestimated due to the sorption of F- by the reactive media. Overall, the reactive mixture (ZVI + BC) may be an effective and environmentally sustainable material for removing PFASs from water under ambient environmental conditions.