Remediation options to reduce bioaccessible and bioavailable lead and arsenic at a smelter impacted site - consideration of treatment efficacy.

In this study, smelter contaminated soil was treated with various soil amendments (ferric sulfate [Fe2(SO4)3], triple superphosphate [TSP] and biochar) to determine their efficacy in immobilizing soil lead (Pb) and arsenic (As). In soils incubated with ferric sulfate (0.6M), gastric phase Pb bioaccessibility was reduced from 1939 ± 17 mg kg-1 to 245 ± 4.7 mg kg-1, while intestinal phase bioaccessibility was reduced from 194 ± 25 mg kg-1 to 11.9 ± 3.5 mg kg-1, driven by the formation of plumbojarosite. In TSP treated soils, there were minor reductions in gastric phase Pb bioaccessibility (to 1631 ± 14 mg kg-1) at the highest TSP concentration (6000 mg kg-1) although greater reductions were observed in the intestinal phase, with bioaccessibility reduced to 9.3 ± 2.2 mg kg-1. Speciation analysis showed that this was primarily driven by the formation of chloropyromorphite in the intestinal phase following Pb and phosphate solubilization in the low pH gastric fluid. At the highest concentration (10% w/w), biochar treated soils showed negligible decreases in Pb bioaccessibility in both gastric and intestinal phases. Validation of bioaccessibility outcomes using an in vivo mouse assay led to similar results, with treatment effect ratios (TER) of 0.20 ± 0.01, 0.76 ± 0.11 and 1.03 ± 0.10 for ferric sulfate (0.6M), TSP (6000 mg kg-1) and biochar (10% w/w) treatments. Results of in vitro and in vivo assays showed that only ferric sulfate treatments were able to significantly reduce As bioaccessibility and bioavailability with TER at the highest application of 0.06 ± 0.00 and 0.14 ± 0.04 respectively. This study highlights the potential application of ferric sulfate treatment for the immobilization of Pb and As in co-contaminated soils.

Mechanisms of Phosphorus Removal by Phosphorus Sorbing Materials.

Stormwater filters are a structural best management practice designed to reduce dissolved P losses from runoff. Various industrial byproducts are suitable for use as P sorbing materials (PSMs) for the treatment of drainage water; P sorption by PSMs varies with material physical and chemical properties. Previously, P removal capacity by PSMs was estimated using chemical extractions. We determined the speciation of P when reacted with various PSMs using X-ray absorption near edge structure (XANES) spectroscopy. Twelve PSMs were reacted with P solution in the laboratory under batch or flow-through conditions. In addition, three slag materials were collected from working stormwater filtration structures. Phosphorus K-edge XANES spectra were collected on each reacted PSM and compared with spectra of 22 known P standards using linear combination fitting in Athena. We found evidence of formation of a variety of Ca-, Al-, and/or Fe-phosphate minerals and sorbed phases on the reacted PSMs, with the exact speciation influenced by the chemical properties of the original unreacted PSMs. We grouped PSMs into three general categories based on the dominant P removal mechanism: (i) Fe- and Al-mediated removal [i.e., adsorption of P to Fe- or Al-(hydro-)oxide minerals and/or precipitation of Fe- or Al-phosphate minerals]; (ii) Ca-mediated removal (i.e., precipitation of Ca-phosphate mineral); and (iii) both mechanisms. We recommend the use of Fe/Al sorbing PSMs for use in stormwater filtration structures where stormwater retention time is limited because reaction of P with Fe or Al generally occurs more quickly than Ca-P precipitation.

Sequestration of U(VI) from Acidic, Alkaline, and High Ionic-Strength Aqueous Media by Functionalized Magnetic Mesoporous Silica Nanoparticles: Capacity and Binding Mechanisms.

Uranium(VI) exhibits little adsorption onto sediment minerals in acidic, alkaline or high ionic-strength aqueous media that often occur in U mining or contaminated sites, which makes U(VI) very mobile and difficult to sequester. In this work, magnetic mesoporous silica nanoparticles (MMSNs) were functionalized with several organic ligands. The functionalized MMSNs were highly effective and had large binding capacity for U sequestration from high salt water (HSW) simulant (54 mg U/g sorbent). The functionalized MMSNs, after U exposure in HSW simulant, pH 3.5 and 9.6 artificial groundwater (AGW), were characterized by a host of spectroscopic methods. Among the key novel findings in this work was that in the HSW simulant or high pH AGW, the dominant U species bound to the functionalized MMSNs were uranyl or uranyl hydroxide, rather than uranyl carbonates as expected. The surface functional groups appear to be out-competing the carbonate ligands associated with the aqueous U species. The uranyl-like species were bound with N ligand as η2 bound motifs or phosphonate ligand as a monodentate, as well as on tetrahedral Si sites as an edge-sharing bidentate. The N and phosphonate ligand-functionalized MMSNs hold promise as effective sorbents for sequestering U from acidic, alkaline or high ionic-strength contaminated aqueous media.

Soil solution interactions may limit Pb remediation using P amendments in an urban soil.

Lead (Pb) contaminated soils are a potential exposure hazard to the public. Amending soils with phosphorus (P) may reduce Pb soil hazards. Soil from Cleveland, OH containing 726 ± 14 mg Pb kg-1 was amended in a laboratory study with bone meal and triple super phosphate (TSP) at 5:1 P:Pb molar ratios. Soil was acidified, neturalized and re-acidified to encourage Pb phosphate formation. PRSTM-probes were used to evaluate changes in soil solution chemistry. Soil acidification did not decrease in vitro bioaccessible (IVBA) Pb using either a pH 1.5, 0.4 M glycine solution or a pH 2.5 solution with organic acids. PRSTM-probe data found soluble Pb increased 10-fold in acidic conditions compared to circumnetural pH conditions. In acidic conditions (p = 3-4), TSP treated soils increased detected P 10-fold over untreated soils. Bone meal application did not increase PRSTM-probe detected P, indicating there may have been insufficient P to react with Pb. X-ray absorption spectroscopy suggested a 10% increase in pyromorphite formation for the TSP treated soil only. Treatments increased soil electrical conductivity above 16 mS cm-1, potentially causing a new salinity hazard. This study used a novel approach by combining the human ingestion endpoint, PRSTM-probes, and X-ray absorption spectroscopy to evaluate treatment efficacy. PRSTM-probe data indicated potentially excess Ca relative to P across incubation steps that could have competed with Pb for soluble P. More research is needed to characterize soil solutions in Pb contaminated urban soils to identify where P treatments might be effective and when competing cations, such as Ca, Fe, and Zn may limit low rate P applications for treating Pb soils.

Uranium fate in wetland mesocosms: Effects of plants at two iron loadings with different pH values.

Small-scale continuous flow wetland mesocosms (∼0.8 L) were used to evaluate how plant roots under different iron loadings affect uranium (U) mobility. When significant concentrations of ferrous iron (Fe) were present at circumneutral pH values, U concentrations in root exposed sediments were an order of magnitude greater than concentrations in root excluded sediments. Micro X-ray absorption near-edge structure (µ-XANES) spectroscopy indicated that U was associated with the plant roots primarily as U(VI) or U(V), with limited evidence of U(IV). Micro X-ray fluorescence (µ-XRF) of plant roots suggested that for high iron loading at circumneutral pH, U was co-located with Fe, perhaps co-precipitated with root Fe plaques, while for low iron loading at a pH of ∼4 the correlation between U and Fe was not significant, consistent with previous observations of U associated with organic matter. Quantitative PCR analyses indicated that the root exposed sediments also contained elevated numbers of Geobacter spp., which are likely associated with enhanced iron cycling, but may also reduce mobile U(VI) to less mobile U(IV) species.

Iron mineralogy and uranium-binding environment in the rhizosphere of a wetland soil.

Wetlands mitigate the migration of groundwater contaminants through a series of biogeochemical gradients that enhance multiple contaminant-binding processes. The hypothesis of this study was that wetland plant roots contribute organic carbon and release O2 within the rhizosphere (plant-impact soil zone) that promote the formation of Fe(III)-(oxyhydr)oxides. In turn, these Fe(III)-(oxyhydr)oxides stabilize organic matter that together contribute to contaminant immobilization. Mineralogy and U binding environments of the rhizosphere were evaluated in samples collected from contaminated and non-contaminated areas of a wetland on the Savannah River Site in South Carolina. Based on Mössbauer spectroscopy, rhizosphere soil was greatly enriched with nanogoethite, ferrihydrite-like nanoparticulates, and hematite, with negligible Fe(II) present. X-ray computed tomography and various microscopy techniques showed that root plaques were tens-of-microns thick and consisted of highly oriented Fe-nanoparticles, suggesting that the roots were involved in creating the biogeochemical conditions conducive to the nanoparticle formation. XAS showed that a majority of the U in the bulk wetland soil was in the +6 oxidation state and was not well correlated spatially to Fe concentrations. SEM/EDS confirm that U was enriched on root plaques, where it was always found in association with P. Together these findings support our hypothesis and suggest that plants can alter mineralogical conditions that may be conducive to contaminant immobilization in wetlands.

Bioaccessibility tests accurately estimate bioavailability of lead to quail.

Hazards of soil-borne lead (Pb) to wild birds may be more accurately quantified if the bioavailability of that Pb is known. To better understand the bioavailability of Pb to birds, the authors measured blood Pb concentrations in Japanese quail (Coturnix japonica) fed diets containing Pb-contaminated soils. Relative bioavailabilities were expressed by comparison with blood Pb concentrations in quail fed a Pb acetate reference diet. Diets containing soil from 5 Pb-contaminated Superfund sites had relative bioavailabilities from 33% to 63%, with a mean of approximately 50%. Treatment of 2 of the soils with phosphorus (P) significantly reduced the bioavailability of Pb. Bioaccessibility of Pb in the test soils was then measured in 6 in vitro tests and regressed on bioavailability: the relative bioavailability leaching procedure at pH 1.5, the same test conducted at pH 2.5, the Ohio State University in vitro gastrointestinal method, the urban soil bioaccessible lead test, the modified physiologically based extraction test, and the waterfowl physiologically based extraction test. All regressions had positive slopes. Based on criteria of slope and coefficient of determination, the relative bioavailability leaching procedure at pH 2.5 and Ohio State University in vitro gastrointestinal tests performed very well. Speciation by X-ray absorption spectroscopy demonstrated that, on average, most of the Pb in the sampled soils was sorbed to minerals (30%), bound to organic matter (24%), or present as Pb sulfate (18%). Additional Pb was associated with P (chloropyromorphite, hydroxypyromorphite, and tertiary Pb phosphate) and with Pb carbonates, leadhillite (a lead sulfate carbonate hydroxide), and Pb sulfide. The formation of chloropyromorphite reduced the bioavailability of Pb, and the amendment of Pb-contaminated soils with P may be a thermodynamically favored means to sequester Pb. Environ Toxicol Chem 2016;35:2311-2319. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and, as such, is in the public domain in the United States of America.

Uranium Redistribution Due to Water Table Fluctuations in Sandy Wetland Mesocosms.

To understand better the fate and stability of immobilized uranium (U) in wetland sediments, and how intermittent dry periods affect U stability, we dosed saturated sandy wetland mesocosms planted with Scirpus acutus with low levels of uranyl acetate for 4 months before imposing a short drying and rewetting period. Concentrations of U in mesocosm effluent increased after drying and rewetting, but the cumulative amount of U released following the dry period constituted less than 1% of the total U immobilized in the soil during the 4 months prior. This low level of remobilization suggests, and XANES analyses confirm, that microbial reduction was not the primary means of U immobilization, as the U immobilized in mesocosms was primarily U(VI) rather than U(IV). Drying followed by rewetting caused a redistribution of U downward in the soil profile and to root surfaces. Although the U on roots before drying was primarily associated with minerals, the U that relocated to the roots during drying and rewetting was bound diffusely. Results show that short periods of drought conditions in a sandy wetland, which expose reduced sediments to air, may impact U distribution without causing large releases of soil-bound U to surface waters.

Spectroscopic evidence of uranium immobilization in acidic wetlands by natural organic matter and plant roots.

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at ∼2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland processes, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication for the long-term stewardship of U-contaminated wetlands.

Uranium immobilization in an iron-rich rhizosphere of a native wetland plant from the Savannah River Site under reducing conditions.

The hypothesis of this study was that iron plaques formed on the roots of wetland plants and their rhizospheres create environmental conditions favorable for iron reducing bacteria that promote the in situ immobilization of uranium. Greenhouse microcosm studies were conducted using native plants (Sparganium americanum) from a wetland located on the Savannah River Site, Aiken, SC. After iron plaques were established during a 73-day period by using an anoxic Fe(II)-rich nutrient solution, a U(VI) amended nutrient solution was added to the system for an additional two months. Compared to plant-free control microcosms, microcosms containing iron plaques successfully stimulated the growth of targeted iron reducing bacteria, Geobacter spp. Their population continuously increased after the introduction of the U(VI) nutrient solution. The reduction of some of the U(VI) to U(IV) by iron reducing bacteria was deduced based on the observations that the aqueous Fe(II) concentrations increased while the U(VI) concentrations decreased. The Fe(II) produced by the iron reducing bacteria was assumed to be reoxidized by the oxygen released from the roots. Advanced spectroscopic analyses revealed that a significant fraction of the U(VI) had been reduced to U(IV) and they were commonly deposited in association with phosphorus on the iron plaque.

Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site.

Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and µ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding.

Grain accumulation of selenium species in rice (Oryza sativa L.).

Efficient Se biofortification programs require a thorough understanding of the accumulation and distribution of Se species within the rice grain. Therefore, the translocation of Se species to the filling grain and their spatial unloading were investigated. Se species were supplied via cut flag leaves of intact plants and excised panicle stems subjected to a ± stem-girdling treatment during grain fill. Total Se concentrations in the flag leaves and grain were quantified by inductively coupled plasma mass spectrometry. Spatial accumulation was investigated using synchrotron X-ray fluorescence microtomography. Selenomethionine (SeMet) and selenomethylcysteine (SeMeSeCys) were transported to the grain more efficiently than selenite and selenate. SeMet and SeMeSeCys were translocated exclusively via the phloem, while inorganic Se was transported via both the phloem and xylem. For SeMet- and SeMeSeCys-fed grain, Se dispersed throughout the external grain layers and into the endosperm and, for SeMeSeCys, into the embryo. Selenite was retained at the point of grain entry. These results demonstrate that the organic Se species SeMet and SeMeSeCys are rapidly loaded into the phloem and transported to the grain far more efficiently than inorganic species. Organic Se species are distributed more readily, and extensively, throughout the grain than selenite.

Selenium adsorption to aluminum-based water treatment residuals.

Aluminum-based water treatment residuals (WTR) can adsorb water- and soil-borne P, As(V), As(III), and perchlorate, and may be able to adsorb excess environmental selenium. WTR, clay minerals, and amorphous aluminum hydroxide were shaken for 24 h in selenate or selenite solutions at pH values of 5-9, and then analyzed for selenium content. Selenate and selenite adsorption edges were unaffected across the pH range studied. Selenate adsorbed on to WTR, reference mineral phases, and amorphous aluminum hydroxide occurred as outer sphere complexes (relatively loosely bound), while selenite adsorption was identified as inner-sphere complexation (relatively tightly bound). Selenite sorption to WTR in an anoxic environment reduced Se(IV) to Se(0), and oxidation of Se(0) or Se(IV) appeared irreversible once sorbed to WTR. Al-based WTR could play a favorable role in sequestering excess Se in affected water sources.

Speciation, characterization, and mobility of As, Se, and Hg in flue gas desulphurization residues.

Flue gas from coal combustion contains significant amounts of volatile toxic trace elements such as arsenic (As), selenium (Se), and mercury (Hg). The capture of these elements in the flue gas desulphurization (FGD) scrubber unit has resulted in generation of a metal-laden residue. With increasing reuse of the FGD residues in beneficial applications, it is important to determine metal speciation and mobilityto understand the environmental impact of its reuse. In this paper, we report the solid phase speciation of As, Se, and Hg in FGD residues using X-ray absorption spectroscopy (XAS), X-ray fluorescence spectroscopy (XRF), and sequential chemical extraction (SCE) techniques. The SCE results combined with XRF data indicated a strong possibility of As association with iron oxides, whereas Se was distributed among all geochemical phases. Hg appeared to be mainly distributed in the strong-complexed phase. XRF images also suggested a strong association of Hg with Fe oxide materials within FGD residues. XAS analysis indicated that As existed in its oxidized state (As(V)), whereas Se and Hg was observed in primarily reduced states as selenite (Se(IV)) and Hg(I), respectively. The results from the SCE and variable pH leaching tests indicated that the labile fractions of As, Se, and Hg were fairly low and thus suggestive of their stability in the FGD residues. However, the presence of a fine fraction enriched in metal content in the FGD residue suggested that size fractionation is important in assessing the environmental risks associated with their reuse.

Bioaccessibility of lead sequestered to corundum and ferrihydrite in a simulated gastrointestinal system.

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of Pb-contaminated soil. Lead was sorbed to model oxide minerals of corundum (alpha-Al(2)O(3)) and ferrihydrite (Fe(5)HO(8).4H(2)O). The Pb-sorbed minerals were placed in a simulated gastrointestinal tract (in vitro) to simulate ingestion of Pb-contaminated soil. The changes in Pb speciation were determined using extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES). Both corundum (sorption maximum of 2.13 g kg(-1)) and ferrihydrite (sorption maximum of 38.6 g kg(-1)) have been shown to sorb Pb, with ferrihydrite having a very high affinity for Pb. The gastric bioaccessible Pb for corundum was >85% for corundum when the concentration of Pb was >200 mg kg(-1). Bioaccessible Pb was not detectable at 4. However, much of the sorbed Pb will become bioaccessible under gastric conditions (pH 1.5-2.5) if this soil is ingested. Caution should be used before using these materials to remediate a soil where soil ingestion is an important exposure pathway.

Spectroscopic speciation and quantification of lead in phosphate-amended soils.

The immobilization of Pb in contaminated soils as pyromorphite [Pb(5)(PO(4))(3)Cl, OH, F] through the addition of various phosphate amendments has gained much attention in the remediation community. However, it is difficult to fully determine the speciation and amount of soil Pb converted to pyromorphite by previously employed methods, such as selective sequential extraction procedures and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, which often lead to erroneous results in these non-equilibrated and heterogeneous systems. Statistical analysis by linear combination fitting (LCF) applied to X-ray absorption fine structure (XAFS) spectroscopic data of Pb-contaminated soil samples relative to known Pb reference material provides direct, in situ evidence of dominate Pb species in the amended soils without chemical or physical disruption to the Pb species as well as a weighted quantification output. The LCF-XAFS approach illustrated that pyromorphite concentration ranged from 0% (control soil) to 45% (1% phosphoric acid amendment, residence time of 32 mo) relative to the total Pb concentration. The Pb speciation in the nonamended control soil included Pb-sulfur species (galena + angelsite = 53%), adsorbed Pb (inner-sphere + outer-sphere + organic-bound = 45%), and Pb-carbonate phases (cerussite + hydrocerussite = 2%). The addition of P promoted pyromorphite formation and the rate of formation increased with increasing P concentration (up to 45%). The supplemental addition of an iron amendment as an iron-rich byproduct with triple superphosphate (TSP) enhanced pyromorphite formation relative to independent TSP amendment of like concentrations (41 versus 29%). However, the amendment of biosolids and biosolids plus TSP observed little pyromorphite formation (1-16% of total Pb), but a significant increase of sorbed Pb was determined by LCF-XAFS.

Assessment of a sequential extraction procedure for perturbed lead-contaminated samples with and without phosphorus amendments.

Sequential extraction procedures are used to determine the solid-phase association in which elements of interest exist in soil and sediment matrixes. Foundational work by Tessier et al. (Tessier, A.; Campbell, P. G. C.; Bisson, M. Anal. Chem. 1979, 51, 844-851) has found widespread acceptance and has been employed as an operational definition for metal speciation in solid matrixes. However, a major obstacle confronting sequential extraction procedures is species alteration of extracted metals before, during, and after separation of solids from solution. If this occurs, the results obtained from sequential extraction do not provide an accurate account of metal speciation within the matrix because the metal forms are altered from their field state. Many researchers dismiss this drawback since several sorption and precipitation processes are believed to occur at time scales much longer than any particular extraction step. This assumption may not be valid. The objectives of this study were to investigate the potential formation of pyromorphite (Pb5(PO4)3Cl) during the sequential extraction steps of Pb-spiked samples with and without calcium phosphate amendments and to examine the differences in the operationally defined distribution of Pb in samples with and without the presence of P. The systems that were examined in the absence of phosphate behaved, for the most part, adequately according to the operational definitions of the extraction procedure. However, when the samples were amended with phosphate, results were drastically changed with a significant shift of extractable Pb to the residual phase. This redistribution was due to pyromorphite formation during the extraction procedure as confirmed by X-ray diffraction and X-ray absorption (XAS) spectroscopies. These results indicate that sequential extraction methods may not be suitable for Pb speciation in perturbed environmental systems (i.e., fertilized agricultural soils or amended contaminated soils) and that rigorous interpretation should be avoided, if not supported by methods to definitively prove metal speciation (e.g., XAS).