Phenazine-1-Carboxylic Acid-Producing Bacteria Enhance the Reactivity of Iron Minerals in Dryland and Irrigated Wheat Rhizospheres.

Phenazine-1-carboxylic acid (PCA) is a broad-spectrum antibiotic produced by rhizobacteria in the dryland wheat fields of the Columbia Plateau. PCA and other phenazines reductively dissolve Fe and Mn oxyhydroxides in bacterial culture systems, but the impact of PCA upon Fe and Mn cycling in the rhizosphere is unknown. Here, concentrations of dithionite-extractable and poorly crystalline Fe were approximately 10% and 30-40% higher, respectively, in dryland and irrigated rhizospheres inoculated with the PCA-producing (PCA+) strain Pseudomonas synxantha 2-79 than in rhizospheres inoculated with a PCA-deficient mutant. However, rhizosphere concentrations of Fe(II) and Mn did not differ significantly, indicating that PCA-mediated redox transformations of Fe and Mn were transient or were masked by competing processes. Total Fe and Mn uptake into wheat biomass also did not differ significantly, but the PCA+ strain significantly altered Fe translocation into shoots. X-ray absorption near edge spectroscopy revealed an abundance of Fe-bearing oxyhydroxides and phyllosilicates in all rhizospheres. These results indicate that the PCA+ strain enhanced the reactivity and mobility of Fe derived from soil minerals without producing parallel changes in plant Fe uptake. This is the first report that directly links significant alterations of Fe-bearing minerals in the rhizosphere to a single bacterial trait.

Review of interactions between phosphorus and arsenic in soils from four case studies.

Arsenic is a non-essential element that poses risks in many environments, including soil, groundwater, and surface water. Insights into the environmental biogeochemistry of As can be gained by comparing As and P reaction processes. Arsenic and P are chemical analogues, and it is proposed that they have similar chemical behaviors in environmental systems. However some chemical properties of As and P are distinct, such as redox reactions, causing the biogeochemical behavior of the two elements to differ. In the environment, As occurs as either As(V) or As(III) oxyanions (e.g., AsO43- or AsO33-). In contrast, P occurs predominantly as oxidation state five plus; most commonly as the orthophosphate ion (PO43-). In this paper, data from four published case studies are presented with a focus on P and As distribution and speciation in soil. The goal is show how analyzing P chemistry in soils can provide greater insights into As reaction processes in soils. The case studies discussed include: (1) soil developed from shale parent material, (2) mine-waste impacted wetland soils, (3) phosphate-amended contaminated soil, and (4) plants grown in biochar-amended, mine-contaminated soil. Data show that while P and As have competitive reactions in soils, in most natural systems they have distinct biogeochemical processes that create differing mobility and bioavailability. These processes include redox reactions and rhizosphere processes that affect As bioavailability. Results from these case studies are used as examples to illustrate how studying P and As together allows for enhanced interpretation of As biogeochemical processes in soils.

Lead immobilization and phosphorus availability in phosphate-amended, mine-contaminated soils.

Over a century of mining activities in the Coeur d'Alene mining district in Idaho have contaminated soils of the downstream basin with lead, arsenic, zinc, and cadmium. Elevated soil-Pb levels are a significant hazard to the health of humans and wildlife in the region. One in situ treatment approach for remediating Pb-contaminated soils is application of phosphorus to promote the formation of lead phosphate minerals that have low solubility. However, this remediation strategy may result in excess P runoff to surface waters, which can lead to eutrophication, particularly when used in riparian areas. Research presented in this paper describes experiments in which monopotassium phosphate (KHPO) solution was applied to two Pb-contaminated soils from the Coeur d'Alene River valley to determine how P loading rates affect both Pb immobilization and P mobility and to determine if an optimal P amendment rate can be predicted. Toxicity characteristic leaching procedure extractions were used to assess changes in Pb availability for uptake by an organism or mobilization through the soil, and Bray extractions were used to assess P availability for leaching out of the soil system. For the two soils tested, increasing phosphate amendment caused decreasing Pb extractability. Phosphorus amendment rates above approximately 70 mg kg, however, did not provide any additional Pb immobilization. Phosphorus availability increased with increasing phosphate application rate. An empirical relationship is presented that predicts extractable Pb as a function of extractable P. This relationship allows for prediction of the amount of Pb that can be immobilized at specified P leaching amounts, such as regulatory levels that have been established to minimize risks for surface water degradation. Results suggest that phosphate can be used to immobilize Pb in contaminated wetland or riparian areas without posing risks of P loading to surface waters.

Biochar Soil Amendment Effects on Arsenic Availability to Mountain Brome ().

Biochar is a renewable energy byproduct that shows promise for remediating contaminated mine sites. A common contaminant at mine sites is arsenic (As). In this study, the effects of biochar amendments to a mine-contaminated soil on As concentrations in mountain brome ( Nees ex Steud.) were investigated. In the biochar-amended soil, mountain brome had greater root biomass and decreased root and shoot As concentrations. X-ray absorption near-edge structure spectroscopy results showed that arsenate [As(V)] is the predominant species in both the nonamended and biochar-amended soils. Soil extraction tests that measure phosphate and arsenate availability to plants failed to accurately predict plant tissue As concentrations, suggesting the arsenate bioavailability behavior in the soils is distinct from phosphate. Results from this study indicate that biochar will be a beneficial amendment to As-contaminated mine sites for remediation.

Long-term dairy manure amendment promotes legacy phosphorus buildup and mobility in calcareous soils.

Continuous application of dairy manure to soils can lead to excessive phosphorus (P) accumulation (legacy P), which requires understanding for managing nutrient availability and leaching. This study was conducted in Kimberly, ID, where dairy manure or conventional fertilizer was applied to calcareous soil plots under continuous crop rotations for 8 years (2013-2020), followed by 2 years with no amendment. To understand legacy P behavior in the soils, total P, organic/inorganic P, and plant-available Olsen bicarbonate P and Truog extraction measurements were made from surface and subsurface samples. Additionally, P in soluble and less soluble calcium phosphate (Ca-P) minerals was estimated using selective extractions, and P desorption was measured in a flow-through reactor. Manure amendments resulted in increased total soil P and plant-available P, particularly in the initial 5 years. In the 0- to 30-cm depth, 54%-65% of the soil P added from manure amendments was readily soluble by the Truog P test. Phosphorus released from the 2022 manure-amended soil in the desorption experiments was about five times greater than the fertilizer-amended soil, suggesting high leaching potential. After 8 years of manure amendment, subsurface Olsen-P levels exceeded the 40 mg kg-1 management threshold, suggesting P adsorption potential of the surface had become saturated, allowing for P leaching. In the manure-amended surface soils, calcium phosphate minerals increased compared to the controls. Even after 2 years without manure amendment, soluble Ca-P mineral phases persisted in the soils, which can be a long-term source of P leaching.

Biochar-integrated reactive filtration of wastewater for P removal and recovery, micropollutant catalytic oxidation, and negative CO2 e: Life cycle assessment and techno-economic analysis.

Life cycle assessment (LCA) and techno-economic analysis (TEA) models are developed for a tertiary wastewater treatment system that employs a biochar-integrated reactive filtration (RF) approach. This innovative system incorporates the utilization of biochar (BC) either in conjunction with or independently of iron-ozone catalytic oxidation (CatOx)-resulting in two configurations: Fe-CatOx-BC-RF and BC-RF. The technology demonstrates 90%-99% total phosphorus removals, adsorption of phosphorus to biochar for recovery, and >90% destructive removal of observed micropollutants. In this work, we conduct an ISO-compliant LCA of a 49.2 m3 /day (9 gpm) field pilot-scale Fe-CatOx-BC-RF system and a 1130 m3 /day (0.3 MGD) water resource recovery facility (WRRF)-installed RF system, modeled with BC addition at the same rate of 0.45 g/L to quantify their environmental impacts. LCA results indicated that the Fe-CatOx-BC-RF pilot system is a BC dose-dependent carbon-negative technology at -1.21 kg CO2 e/m3 , where biochar addition constitutes a -1.53 kg/m3 CO2 e beneficial impact to the process. For the WRRF-installed RF system, modeled with the same rate of BC addition, the overall process changed from 0.02 kg CO2 e/m3 to a carbon negative -1.41 kg CO2 e/m3 , demonstrating potential as a biochar dose-dependent negative emissions technology. Using the C100 100-year carbon accounting approach rather than Cnet reduces these CO2 e metrics for the process by about 25%. A stochastic TEA for the cost of water treatment using this combinatorial P removal/recovery, micropollutant destructive removal, and disinfection advanced technology shows that at scale, the mean cost for treating 1130 m3 /day (0.3 MGD) WRRF secondary influent water with Fe-CatOx-BC-RF using the C100 metric is US$0.18 ± US$0.01/m3 to achieve overall process carbon neutrality. Using the same BC dose in an estimation of a 3780 m3 /day (1 MGD) Fe-CatOx-BC-RF facility, the carbon neutral cost of treatment is reduced further to US$0.08 ± $0.01 with added BC accounting for US$0.03/m3 . Overall, the results demonstrate the potential of carbon negativity to become a water treatment performance standard as important and attainable as pollutant and pathogen removal. PRACTITIONER POINTS: Life cycle assessment (LCA) of a pilot scale tertiary biochar water treatment process with or without catalytic ozonation at a WRRF shows a carbon negative global warming potential of -1.21-kg CO2e/m3 while removing 90%-99% TP and >90% of detected micropollutants. Biochar-integrated reactive filtration use can aid in long-term carbon sequestration by reducing the carbon footprint of advanced water treatment in a dose-dependent manner, allowing an overall carbon-neutral or carbon-negative process. A companion paper to this work (Yu et al., 2023) presents the details related to the process operation and mechanism and evaluates the pollutant removal performance of this Fe-CatOx-BC-RF process in engineering laboratory pilot research and field WRRF pilot-scale water resource recovery trials. Techno-economic analysis (TEA) of this biochar catalytic oxidation reactive filtration process using Monte Carlo stochastic modeling shows a forecasted carbon-neutral process cost with low P and micropollutant removal as US$0.11/m3 ± 0.01 for a 3780-m3/day (1 MGD) scale installation with BC cost at US$0.03/m3 of that total. The results demonstrate the potential of carbon negativity to become a water treatmentperformance standard as important and attainable as pollutant and pathogen removal.

Biochar integrated reactive filtration of wastewater for P removal and recovery, micropollutant catalytic oxidation, and negative CO2 e: Process operation and mechanism.

Biochar (BC) use in water treatment is a promising approach that can simultaneously help address societal needs of clean water, food security, and climate change mitigation. However, novel BC water treatment technology approaches require operational testing in field pilot-scale scenarios to advance their technology readiness assessment. Therefore, the objective of this study is to evaluate the system performance of BC integrated into hydrous ferric oxide reactive filtration (Fe-BC-RF) with and without catalytic ozonation (CatOx) process in laboratory and field pilot-scale scenarios. For this investigation, Fe-BC-RF and Fe-CatOx-BC-RF pilot-scale trials were conducted on synthetic lake water variants and at three municipal water resource recovery facilities (WRRFs) at process flows of 0.05 and 0.6 L/s, respectively. Three native and two iron-modified BCs were used in these studies. The commercially available reactive filtration process (Fe-RF without BC) had 96%-98% total phosphorus (TP) removal from 0.075- and 0.22-mg/L TP, as orthophosphate process influent in these trials. With BC integration, phosphorus removal yielded 94%-98% with the same process-influent conditions. In WRRF field pilot-scale studies, the Fe-CatOx-BC-RF process removed 84%-99% of influent total phosphorus concentrations that varied from 0.12 to 8.1 mg/L. Nutrient analysis on BC showed that the recovered BC used in the pilot-scale studies had an increase in TP from its native concentration, with the Fe-amended BC showing better P recovery at 110% than its unmodified state, which was 16%. Lastly, the field WRRF Fe-CatOx-BC-RF process studies showed successful destructive removals at >90% for more than 20 detected micropollutants, thus addressing a critical human health and environmental water quality concern. The research demonstrated that integration of BC into Fe-CatOx-RF for micropollutant removal, disinfection, and nutrient recovery is an encouraging tertiary water treatment technology that can address sustainable phosphorus recycling needs and the potential for carbon-negative operation. PRACTITIONER POINTS: A pilot-scale hydrous ferric oxide reactive sand filtration process integrating biochar injection typically yields >90% total phosphorus removal to ultralow levels. Biochar, modified with iron, recovers phosphorus from wastewater, creating a P/N nutrient upcycled soil amendment. Addition of ozone to the process stream enables biochar-iron-ozone catalytic oxidation demonstrating typically excellent (>90%) micropollutant destructive removals for the compounds tested. A companion paper to this work explores life cycle assessment (LCA) and techno-economic analysis (TEA) to explore biochar water treatment integrated reactive filtration impacts, costs, and readiness. Biochar use can aid in long-term carbon sequestration by reducing the carbon footprint of advanced water treatment in a dose-dependent manner, including enabling an overall carbon-negative process.

Iron-ozone catalytic oxidation reactive filtration of municipal wastewater at field pilot and full-scale with high-efficiency pollutant removal and potential negative CO2 e with biochar.

Iron-ozone catalytic oxidation (CatOx) shows promise in addressing challenging wastewater pollutants. This study investigates a CatOx reactive filtration (Fe-CatOx-RF) approach with two 0.4 L/s field pilot studies and an 18-month, 18 L/s full-scale municipal wastewater deployment. We apply ozone to leverage common sand filtration and iron metal salts used in water treatment into a next-generation technology. The process combines micropollutant and pathogen destructive removal with high-efficiency phosphorus removal and recycling as a soil amendment, clean water recovery, and the potential for carbon-negative operation with integrated biochar water treatment. A key process innovation is converting a continuously renewed iron oxide coated, moving bed sand filter into a "sacrificial iron" d-orbital catalyst bed after adding O3 to the process stream. Results for the Fe-CatOx-RF pilot studies show >95% removal efficiencies for almost all >5 × LoQ detected micropollutants, with removal rates slightly increasing with biochar addition. Phosphorus removal for the pilot site with the most P-impacted discharge was >98% with serial reactive filters. The long-term, full-scale Fe-CatOx-RF optimization trials showed single reactive filter 90% TP removal and high-efficiency micropollutant removals for most of the compounds detected, but slightly less than the pilot site studies. TP removal decreased to a mean of 86% during the 18 L/s, 12-month continuous operation stability trial, and micropollutant removals remained similar to the optimization trial for many detected compounds but less efficient overall. A >4.4 log reduction of fecal coliforms and E. coli in a field pilot sub-study suggests the ability of this CatOx approach to address infectious disease concerns. Life cycle assessment modeling suggests that integrating biochar water treatment into the Fe-CatOx-RF process for P recovery as a soil amendment makes the overall process carbon-negative at -1.21 kg CO2 e/m3 . Results indicate positive Fe-CatOx-RF process performance and technology readiness in full-scale extended testing. Further work exploring operational variables is essential to establish site-specific water quality limitations and responsive engineering approaches for process optimization. PRACTITIONERS POINTS: Adding ozone to WRRF secondary influent flows into tertiary ferric/ferrous salt dosed sand filtration amplifies a mature reactive filtration technology into a catalytic oxidation process for micropollutant removal and disinfection. Expensive catalysts are not used. Iron oxide compounds used to remove phosphorus and other pollutants act as sacrificial catalysts with ozone, and these rejected iron compounds can be returned upstream to aid in secondary process TP removal. Biochar addition to the CatOx process improves CO2 e sustainability and phosphorus removal/recovery for long-term soil and water health. Short duration field pilot scale and 18-month full-scale operation at three WRRFs with good results demonstrate technology readiness.

CO2 e footprint and eco-impact of ultralow phosphorus removal by hydrous ferric oxide reactive filtration: A municipal wastewater LCA case study.

Dual upflow reactive filtration by a slowly moving sand bed with continuously renewed, hydrous ferric oxide-coated sand is used for removing polluting substances and for meeting the ultralow 0.05 mg/l total phosphorus discharge permit limits at a 1.2 million liters per day (0.32 million gallons per day) water resource recovery facility in Plummer, Idaho, in the United States. A life cycle assessment (LCA) of this reactive filtration installation was carried out to assess the environmental hotspots in the system and analyze alternative system configurations with a focus on CO2 equivalent (CO2 e) global warming potential, freshwater and marine eutrophication, and mineral resource scarcity. "What if" scenarios with alternative inputs for the energy, metal salts, and air compressor optimization show trade-offs between the impact categories. Key results that show a comparative reduction of global warming potential include the use of Fe versus Al metal salts, the use of renewable energy, and the energy efficiency benefit of optimizing process inputs, such as compressor air pressure, to match operational demand. The LCA shows a 2 × 10-2  kg CO2 e footprint per cubic meter of water, with 47% from housing concrete, and an overall freshwater eutrophication impact reduced by 99% versus no treatment. The use of renewable hydropower energy at this site isolates construction concrete as a target for lowering the CO2 e footprint. PRACTITIONER POINTS: The main LCA eco-impact hotspots in this dual reactive filtration tertiary treatment are construction concrete and the ferric sulfate used. Iron salts show smaller impact in global warming, freshwater eutrophication, and mineral resource scarcity than "what if scenario" aluminum salts. The energy mix for this site is predominantly hydropower; other energy mix "what if" scenarios show larger impacts. Operational energy efficiency and thermodynamic analysis show that fine tuning the air compressor helps reduce carbon footprint and energy use. LCA shows a favorable 2 x 10-2 kg CO2e/m3 water impact with 99% reduction of freshwater eutrophication potential versus no treatment.

Chemical speciation and bioavailability of selenium in the rhizosphere of Symphyotrichum eatonii from reclaimed mine soils.

Knowledge of rhizosphere influences on Se speciation and bioavailability is required to predict Se bioavailability to plants. In the present study, plant-availability of Se to aster (Symphyotrichum eatonii (A. Gray) G.L. Nesom) was compared in rhizosphere soils and nonrhizosphere (bulk) soils collected from a reclaimed mine site in southeastern Idaho, U.S. X-ray spectroscopy was used to characterize the oxidation state and elemental distribution of Se in aster roots, rhizosphere soils, and bulk soils. Percent extractable Se in aster rhizosphere soil was greater than extractable Se in corresponding bulk soils in all samples (n = 4, p = 0.042, 0.051, and 0.052 for three extractions). Selenium oxidation state mapping of 28 regions within the samples and X-ray absorption near edge structure (XANES) spectra from 26 points within the samples indicated that the rhizosphere and bulk soil Se species was predominantly reduced Se(-II,0), while in the aster roots, high concentrations of Se(VI) were present. Results show that within the rhizosphere, enhanced Se bioavailability is occurring via oxidation of reduced soil Se to more soluble Se(VI) species.

Fifty years of articles in JEQ on trace elements in the environment and future outlook.

Fifty years ago, the Journal of Environmental Quality (JEQ) was launched to provide an outlet for publication of research on the impacts of agriculture on the environment, and vice versa. A core concept of JEQ is advancement of environmental science, with emphasis on understanding factors that affect the fate, risks, and quality of soil, water, and atmospheric systems, and how these system processes affect plants, microbes, and animals. Trace elements are a focus area of JEQ because when present at higher than natural concentrations, they may pose risks to environmental quality and ecosystem health, depending on their bioavailability. Trace element biogeochemical cycling is affected by anthropogenic influences on land, air, and water, including land management practices such as agriculture and mining. The Journal of Environmental Quality has published a prolific catalog of scientific research publications on trace elements and their risks to humans, soil health, water quality, and the environment. In this review, research on trace elements and their impacts on environmental quality is presented, with a special focus on work published in JEQ.

Association between extracted copper and dissolved organic matter in dairy-manure amended soils.

Dairy manure often has elevated concentrations of copper (Cu) that when applied to soil may create toxicity risks to seedlings and soil microbes. Manure application also increases dissolved organic matter (DOM) in soil solution. We hypothesize that high rates of dairy manure amendment over several years will cause increased DOM in the soil that complexes Cu, increasing its mobility. To test this hypothesis, this study investigated water soluble Cu concentrations and dissolved organic carbon (DOC) in soil samples from 3 years of manure-amended soils. Samples were collected at two depths over the first 3 years of a long-term manure-amendment field trial. DOC, Cu, Fe, and P concentrations were measured in water extracts from the samples. Ultraviolet/visible (UV/Vis) spectra were used to assess the DOC characteristics. After 3 years of manure application, extractable Cu concentration was approximately four times greater in the surface and two times greater in subsurface samples of manure-amended soils as compared to non-amended control soils and traditional mineral fertilizer-amended soils. The extractable Cu concentration was greatest in plots that had the highest manure amendment rates (35 t ha-1 and 52 t ha-1, dry weight). The UV/Vis parameters SUVA254 and E2/E3 correlated with Cu concentration in the extracts (p < 0.05), suggesting that DOC characteristics are important in Cu-binding. The molecular characteristics of the DOC in the subsurface after 3 years of manure amendment were distinct from the DOC in the control plot, suggesting that manure amendment creates mobile DOC that may facilitate Cu mobilization through soil. The 10-fold increase in extractable Cu concentration after only 3 years of manure application indicates that repeated applications of the dairy manure sources used in this study at rates of 35 t/ha or greater may create risks for Cu toxicity and leaching of Cu into ground and surface waters.

Characterization of iron- and manganese-cemented redoximorphic aggregates in wetland soils contaminated with mine wastes.

In wetlands, translocation of Fe and Mn from reducing to oxidizing zones creates localized enrichments and depletions of oxide minerals. In zones of enrichment, oxides cement matrix particles together into aggregates. In this paper, we describe the various Fe- and Mn-cemented features present in the 1 to 2-mm size fraction of mine-waste contaminated wetland soils of the Coeur d'Alene (CDA) River Basin in northern Idaho. These aggregates are categorized based on color and morphology. Total Fe and Mn concentrations are also reported. Distribution of the aggregates in soil profiles along an elevation transect with varying water table heights was investigated. Six distinct categories of aggregates were characterized in the 1 to 2-mm size fraction. The two most predominant categories were aggregates cemented by only Fe oxides and aggregates cemented by a mixture of Fe and Mn oxides. Iron-depleted aggregates, Fe and Mn-cemented sand aggregates, and root channel linings were also identified. The remaining aggregates were categorized into a catch-all category that consisted of primarily charcoal particles. The highest Fe content was in the root channel linings, and the highest Mn content was in the Fe/Mn cemented particles. Iron-cemented aggregates were most common in surface horizons at all sites, and root channels were most common in the 30 to 45-cm core at the lowland point, reflecting the presence of deep rooting vegetation at this site. Spatial distributions of other aggregates at the site were not significant.

Sample drying effects on lead bioaccessibility in reduced soil.

Risk-assessment tests of contaminated wetland soils often use experimental protocols that artificially oxidize the soils. Oxidation may impact bioavailability of contaminants from the soils, creating erroneous results and leading to improper management and remediation. The goal of this study was to determine if oxygenation of reduced sediments and soils influences Pb bioaccessibility measurements. The study site is located on the Coeur d'Alene River floodplain, downstream from the Silver Valley Mining District in Idaho. A physiologically based extraction test designed to simulate the gastrointestinal tract of waterfowl (W-PBET) was used to measure relative Pb bioavailability (bioaccessibility) from the soils. The soils were collected from a submerged wetland. One set of samples was allowed to air-dry, another set was freeze-dried, and a third set was analyzed wet. The wet soil showed decreased Pb bioaccessibility compared with the air- and freeze-dried soils. The changes in extractability of Fe and Mn on air-drying were opposite from each other: Fe extractability decreased while Mn increased. The results from this study show that redox changes may have significant impacts on Pb bioavailability, and should be considered when assessing Pb contamination risks in reduced 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.

Risk assessment test for lead bioaccessibility to waterfowl in mine-impacted soils.

Due to variations in soil physicochemical properties, species physiology, and contaminant speciation, Pb toxicity is difficult to evaluate without conducting in vivo dose-response studies. Such tests, however, are expensive and time consuming, making them impractical to use in assessment and management of contaminated environments. One possible alternative is to develop a physiologically based extraction test (PBET) that can be used to measure relative bioaccessibility. We developed and correlated a PBET designed to measure the bioaccessibility of Pb to waterfowl (W-PBET) in mine-impacted soils located in the Coeur d'Alene River Basin, Idaho. The W-PBET was also used to evaluate the impact of P amendments on Pb bioavailability. The W-PBET results were correlated to waterfowl-tissue Pb levels from a mallard duck [Anas platyrhynchos (L.)] feeding study. The W-PBET Pb concentrations were significantly less in the P-amended soils than in the unamended soils. Results from this study show that the W-PBET can be used to assess relative changes in Pb bioaccessibility to waterfowl in these mine-impacted soils, and therefore will be a valuable test to help manage and remediate contaminated soils.

Micro-spectroscopic investigation of selenium-bearing minerals from the Western US Phosphate Resource Area.

Mining activities in the US Western Phosphate Resource Area (WPRA) have released Se into the environment. Selenium has several different oxidation states and species, each having varying degrees of solubility, reactivity, and bioavailability. In this study we are investigating the speciation of Se in mine-waste rocks. Selenium speciation was determined using bulk and micro-x-ray absorption spectroscopy (XAS), as well as micro-x-ray fluorescence mapping. Rocks used for bulk-XAS were ground into fine powders. Shale used for micro-XAS was broken along depositional planes to expose unweathered surfaces. The near edge region of the XAS spectra (XANES) for the bulk rock samples revealed multiple oxidation states, with peaks indicative of Se(-II), Se(IV), and Se(+VI) species. Micro-XANES analysis of the shale indicated that three unique Se-bearing species were present. Using the XANES data together with ab initio fitting of the extended x-ray absorption fine structure region of the micro-XAS data (micro-EXAFS) the three Se-bearing species were identified as dzharkenite, a di-selenide carbon compound, and Se-substituted pyrite. Results from this research will allow for a better understanding of the biogeochemical cycling of Se in the WPRA.

Molecular-level investigation into copper complexes on vermiculite: effect of reduction of structural iron on copper complexation.

In this paper we present results that describe the speciation of Cu sorbed to the clay mineral vermiculite, with special attention to the effects of reduction on Cu sorption complexes. Sorption complexes were studied using powdered extended X-ray absorption fine structure (EXAFS) spectroscopy, polarized EXAFS spectroscopy, and X-ray diffraction (XRD). Ionic strength (I), background ion, and clay reduction (structural iron) were varied in the sorption samples. At low I EXAFS results indicate that Cu was surrounded by up to six water molecules sorbed in the interlayer of reduced vermiculite. EXAFS results from Cu-equilibrated reduced vermiculite with high I Ca background electrolyte revealed that Cu was surrounded by 4 O atoms at 1.95 Angatroms and 8 second shell O atoms at 3.14 Angstroms. Angular dependence of the second shell O atoms interpreted from the polarized-EXAFS spectra indicated that the atoms are out of plane from the basal plane of the vermiculite (inclined approximately 25 degrees from the ab plane). The local atomic environment and angular dependence of the EXAFS spectra suggest that the Cu atoms are adsorbed above the hexagonal cavities of the reduced clay mineral and form a Cu dimer in the interlayer. This adsorption mechanism was not observed in the non-reduced vermiculite under identical equilibration conditions. Our results provide molecular level evidence that Cu sorption mechanisms on vermiculite are dependent on solution conditions, such as redox potential and background electrolyte. These results can be used to develop better models of Cu sorption mechanisms on clay mineral surfaces.

Phosphorus speciation in manure-amended alkaline soils.

Two common manure storage practices are stockpiles and lagoons. The manure from stockpiles is applied to soils in solid form, while lagoon manure is applied as a liquid. Soil amendment with manure in any form introduces a significant amount of phosphorus (P) that exists in both organic and inorganic forms. However, little is known about P speciation in manure stored under different conditions, or the subsequent forms when applied to soils. We used solution (31)P nuclear magnetic resonance (NMR) spectroscopy and conventional P fractionation and speciation methods to investigate P forms in dairy manure and liquid lagoon manure, and to study how long-term amendment with these manures influenced surface and subsurface soil P speciation. Our results show that the P forms in solid and lagoon manure are similar. About 30% of the total P was organic, mostly as orthophosphate monoesters. On a dry weight basis, total P was much higher in the solid manure. In the manure-amended soils the total P concentrations of the surface soils were similar, regardless of manure type. Total P in the subsurface soil was greater in the lagoon-manure-amended soil than the solid-manure-amended subsurface soil. However, the fraction of organic P was greater in the subsurface of the solid-manure-amended soil. The NMR results indicate that the majority of organic P in the soils is phytic acid, which is enriched in the surface soils compared with the subsurface soils. These results provide insight into P speciation and dynamics in manure-amended soils that will further increase our understanding on how best to manage manure disposal on soils.

Metal content of charcoal in mining-impacted wetland sediments.

Charcoal is well known to accumulate contaminants, but its association with metals and other toxic elements in natural settings has not been well studied. Association of contaminants with charcoal in soil and sediment may affect their mobility, bioavailability, and fate in the environment. In this paper, natural wildfire charcoal samples collected from a wetland site that has been heavily contaminated by mine waste were analyzed for elemental contents and compared to the surrounding soil. Results showed that the charcoal particles were enriched over the host soils by factors of two to 40 times in all contaminant elements analyzed. Principal component analysis was carried out on the data to determine whether element enrichment patterns in the soil profile charcoal are related to those in the soils. The results suggest that manganese and zinc concentrations in charcoal are controlled by geochemical processes in the surrounding soil, whereas the concentrations of arsenic, lead, zinc, iron, phosphorus, and sulfur in charcoal are unrelated to those in the surrounding soil. This study shows evidence that charcoal in soils can have a distinct and important role in controlling contaminant speciation and fate in the environment.