Abstract: Desorption and dissolution often control the mobility and availability of phosphorus (P) in the natural environment. In this study, P desorption was compared from a soil receiving either long-term inorganic or biosolid fertilization as a part of a long-term field scale research project. A continuous-flow desorption method was used to measure cumulative P desorption over time, and P K-edge X-ray absorption near edge structure spectroscopy was used to determine the chemical species removed from the soil samples by desorption. The cumulative amount of P released in the inorganic fertilizer-amended soil was higher (895 vs. 573 mg kg-1), and the rate of P release was much faster (k = 0.012 vs. 0.005 m-1) than that of the biosolids-amended soil. The kinetics data were best described by the parabolic diffusion equation (r2 = 0.98-0.99), suggesting that P desorption was mass-transfer limited or that intraparticle diffusion could be the rate-limiting step. The X-ray absorption near edge structure results indicated that dissolution of calcium and iron phosphate minerals occurs in addition to desorption of P from the exchangeable sites. These observations suggest that the redistribution between aqueous, adsorbed, and precipitated phosphate (PO43-) species occurs rapidly when solution P concentrations are depleted. (C) 2012 Lippincott Williams & Wilkins, Inc.
Abstract: Ferrihydrite is a common iron hydroxide mineral commonly found in soils, sediments, and surface waters. Reactivity with this important environmental surface often controls the fate and mobility of both essential nutrients and inorganic contaminants. Despite the critical role of ferrihydrite in environmental geochemistry, its structure is still debated. In this work we apply bulk sensitive Fe L edge x-ray absorption spectroscopy to study the crystal field environment of the Fe in ferrihydrite and other Fe oxides of known structure. This direct probe of the local electronic structure provides verification of the presence of tetrahedrally coordinated Fe(III) in the structure of ferrihydrite and puts to rest the controversy on this issue.
Abstract: The toxicity of selenium in fish is influenced by its chemical speciation and the exposure route. In the natural environment, selenium exposure to fish occurs primarily in the form of selenomethionine in diet. Thus, the main objective of this study was to examine the tissue-specific selenium burden and speciation in fish exposed to elevated dietary selenomethionine. Rainbow trout (Oncorhynchus mykiss) were treated with dietary selenomethionine (40μg g(-1) dry mass) for 2weeks, and at the end of the exposure different tissue samples were collected to assess the tissue-specific distribution and speciation of selenium. We used synchrotron-based X-ray absorption near edge spectroscopy (XANES) to determine the selenium speciation profile. Selenomethionine, selenocysteine and selenocystine were found to be the predominant form of selenium in all of the tissues; however their relative proportion varied across different tissues. In general, the organs primarily involved in selenium handling in fish (e.g., liver, kidney) accumulated a higher percentage of selenocystine. We also found that dietary selenomethionine exposure resulted into a marked increase in selenium burden of all major tissues in fish including the brain. Collectively, our findings provide new insights into the tissue-specific distribution and speciation of selenium in fish exposed to selenomethionine via diet.
Abstract: Photoreduction is a major obstacle for using the X-ray absorption near-edge structure (XANES) fingerprint to perform metal speciation at the molecular level in biological and environmental samples, especially for metalloproteins. In this study, soft X-ray induced photoreduction was observed in organic Cu(II) compounds during XANES measurements in a third-generation synchrotron source. Next Cu L(3)-edge, O K-edge, and C K-edge XANES spectroscopy, together with the scanning transmission X-ray microscopy (STXM), were used to probe the specific radiation damage processes of Cu acetate with similar local structures to Cu metalloproteins. Breakup of the Cu-Cu bond was hypothesized for the initial photoreduction of Cu acetate. The following radiation damage of Cu acetate produced CuO and an organic Cu(I) compound with a Câ•C bond, and the further photoreduction of the resulting CuO to Cu metal was also demonstrated. Our results indicated the importance of consideration of photoreduction during soft XANES measurements for the solid state compounds with high valence metals. Reducing the radiation dose to ~0.1 MGy effectively prevented the photoreduction of organic Cu(II) compounds during these measurements. This proposed radiation damage mechanism in Cu acetate may be generally useful in explaining the photoreduction process in Cu metalloproteins.
Abstract: Site-specific risk assessments often incorporate the concepts of bioaccessibility (i.e., contaminant fraction released into gastrointestinal fluids) or bioavailability (i.e., contaminant fraction absorbed into systemic circulation) into the calculation of ingestion exposure. We evaluated total and bioaccessible metal concentrations for 19 soil samples under simulated stomach and duodenal conditions using an in vitro gastrointestinal model. We demonstrated that the median bioaccessibility of 23 metals ranged between <1 and 41% under simulated stomach conditions and < 1 and 63% under simulated duodenal conditions. Notably, these large differences in metal bioaccessibility were independent of equilibrium solubility and stability constants. Instead, the relationship (stomach phase R = 0.927; duodenum phase R = 0.891) between bioaccessibility and water exchange rates of metal cations (k(Hâ‚‚O)) indicated that desorption kinetics may influence if not control metal bioaccessibility.
Abstract: Sequential chemical extraction is a common analytical approach used to separate soil P into operationally defined fractions based on solubility in increasingly strong extractants. However, there are some concerns that the relationship between these operationally defined pools and the true chemical speciation of P may not always be correct. This study was conducted to compare the speciation of P in soils amended with either biosolids or an inorganic fertilizer as using a combination of sequential chemical extraction and synchrotron X-ray absorption near-edge structure (XANES) spectroscopy on the solid-phase residues after each extraction step. The combined results from sequential chemical extraction and XANES analysis indicate that although sequential extraction steps may remove the same broad class of P from soil, the solubility and precise chemical speciation of that P may be quite different. For example, P K-edge XANES analysis determined that calcium phosphates are removed by the HCl extraction step, but this takes the form of a poorly crystalline dicalcium phosphate in biosolid-amended plots and apatite-type calcium phosphate in the commercially fertilized plots.
Abstract: Selenium (Se) is an essential element, but causes toxic effects in fish at a slightly elevated level beyond the threshold. However, the degree of Se toxicity differs depending on the chemical forms of Se (e.g., organic vs. inorganic) to which fish are exposed to. The mechanisms of Se metabolism and toxicity in fish, particularly at cellular level, are poorly understood. The present study was designed to examine the metabolic fate of different seleno-compounds, both inorganic and organic, in isolated hepatocytes of rainbow trout (Oncorhynchus mykiss) in primary culture using XANES spectroscopy. In cells exposed to 100 μM of selenate and selenite for 6-24 h, elemental Se was found to be the primary metabolite. Whereas, selenocystine appeared to be the major metabolite in cells exposed to 100 μM seleno-L-methionine for 6-24 h. Interestingly, we recorded L-methionine-γ-lyase activity in S9 fraction of cell lysate-an enzyme that directly catalyzes selenomethionine into methylselenol. We also found concurrent reduction of glutathione (GSH) concentration following reaction of seleno-L-methionine with cellular S9 fraction. Moreover, we observed a rapid increase in cellular reactive oxygen species (ROS) generation with increasing seleno-L-methionine exposure dose (100-1000 μM). These findings indicated the rapid cellular metabolism of seleno-L-methionine into methylselenol at higher exposure dose (≥100 μM), and the occurrence of GSH mediated redox cycling of methylselenol--a process that is known to produce reactive oxygen species (ROS). Overall, our results suggest that inorganic and organic selenium are metabolized through different metabolic pathways in rainbow trout hepatocytes. The findings of our study have important implications for understanding the chemical species-specific differences in Se toxicity to fish.
Abstract: Percent arsenic bioaccessibility is occasionally dependent upon arsenic concentration; however, the mechanism(s) of this relationship has not yet been defined. To evaluate the mechanism of this relationship, the arsenic bioaccessibility from freshly synthesized poorly crystalline scorodite was measured in the stomach, small intestine, and colon stages of the Simulator of the Human Intestinal Microbial Ecosystem (SHIME). The shape of the arsenic dissolution isotherms were different between stages (stomach: linear; small intestine: exponential rise to maxima; colon: sigmoidal). These results indicate that arsenic bioaccessibility may be limited by either in vitro GI fluid saturation or in vitro GI model residence time, depending upon the chemical/microbiological conditions of the model. Gastrointestinal microorganisms increased arsenic bioaccessibility of scorodite up to two-fold in the SHIME colon; however, this was dependent upon the sample arsenic concentration. Up to 40% of the bioaccessible arsenic was reduced to arsenite; however this process was neither mediated by GI microorganisms nor associated with increased arsenic bioaccessibility.
Abstract: In vitro gastrointestinal models, used to measure the metal(loid) bioaccessibility for site specific risk assessment, are typically operated under fasted conditions. We evaluated the hypothesis that fed conditions increase arsenic bioaccessibility on three reference soils (NIST 2711, NIST 2709, and BGS 102) and the bulk and <38 mum size fractions of a mine tailing. The three nutritional states included a fed state with a carbohydrate mixture, a second fed state with homogenized crowberries (Empetrum nigrum), and a fasted state. The carbohydrate mixture increased arsenic bioaccessibility from four of five samples in the simulator of the human intestinal microbial ecosystem (SHIME) stomach but only three of five samples in the SHIME small intestine and colon. In contrast, crowberries increased arsenic bioaccessibility from four of five samples in the SHIME small intestine but had variable affects in the SHIME stomach and colon. The effect of nutritional status on arsenic bioaccessibility was potentially mediated via ligand-promoted dissolution in the SHIME stomach and small intestine. The displacement of arsenic with phosphate was potentially present in the SHIME small intestine but not the SHIME stomach. Microbial activity increased arsenic bioaccessibility relative to sterile conditions from four of five samples under fasted conditions and three of the five samples under fed conditions, which may suggest that in vitro gastrointestinal (GI) models operated under fed conditions and with microbes provide a more conservative estimate of in vitro bioaccessibility. However, for some samples, the arsenic bioaccessibility in the SHIME colon (with microbial activity) was equivalent to values observed in a separate physiologically based extraction test under small intestinal conditions (without microbial activity). These results suggest that the incorporation of microbial activity into in vitro GI models does not necessarily make estimates of arsenic bioaccessibility more protective than those generated using in vitro models that do not include microbial activity.
Abstract: Although widely investigated in relation to acid mine drainage systems at pH?>?1.0, we know little about the impact of sulfuric acid (H2SO4) on the geochemistry and mineralogy of clays at pH?<?1.0 (including negative pH values). Thus, laboratory batch experiments were conducted on three mixed clay samples with different mass ratios of phyllosilicates (smectite, illite, and kaolinite) to investigate the impact of H2SO4 from pH 1.0 to -3.0 for exposure periods of 14, 90, 180, and 365?days. Si and Al K- and L2,3-edge X-ray absorption near edge structure (XANES) spectroscopy were employed on these samples to determine the chemical and structural changes that occur during acidic dissolution of phyllosilicates that cannot be distinguished using X-ray diffraction analyses. A series of silicate, phyllosilicate, and Al-bearing standard compounds were also studied to provide an explanation for the observed changes in the clay samples. The Si XANES results indicated the preferential dissolution of the phyllosilicates (pH?[less-than-or-equals, slant]?1.0, t?[greater-or-equal, slanted]?14?d), the persistence of quartz even at pH?[greater-or-equal, slanted]?-3.0 and t?[greater-or-equal, slanted]?365?d, and the formation of an amorphous silica-like phase that was confined to the surface layer of the altered clay samples at pH?[less-than-or-equals, slant]?0.0 and t?[greater-or-equal, slanted]?90?d). Al XANES results demonstrated dissolution of Al-octahedral layers (pH?[less-than-or-equals, slant]?1.0, t?[greater-or-equal, slanted]?14?d), the persistence of four-fold relative to six-fold coordinated Al, and the precipitation of an Al-SO4-rich phase (pH?[less-than-or-equals, slant]?-1.0, t?[greater-or-equal, slanted]?90?d). An existing conceptual model of phyllosilicate dissolution under extremely acidic conditions was modified to include the results of this study.
Abstract: Human exposure to contaminated soils drives clean up criteria at many urban brownfields. Current risk assessment guidelines assume that humans ingest some fraction of soil smaller than 4 mm but have no estimates of what fraction of soil is ingested by humans. Here, we evaluated soil adherence to human hands for 13 agricultural soils from Saskatchewan, Canada and 17 different soils from a brownfield located in Iqaluit, Nunavut, Canada. In addition, we estimated average particle size adhering to human hands for residents of a northern urban setting. Further, we estimated how metal concentrations differed between the adhered and bulk (< 4 mm) fraction of soil. The average particle size for adhered agricultural soils was 34 microm, adhered brownfield soils was 105 microm, and particles adhered to human residentswas 36 microm. Metals were significantly enriched in these adhered fractions with an average enrichment [(adhered-bulk)/bulk] in metal concentration of 184% (113% median) for 24 different elements. Enrichment was greater for key toxicological elements of concern such as chromium (140%), copper (140%), nickel (130%), lead (110%), and zinc (130%) and was highest for silver (810%), mercury (630%), selenium (500%), and arsenic (420%). Enrichment were positively correlated with carbonate complexation constants (but not bulk solubility products) and suggests that the dominant mechanism controlling metal enrichment in these samples is a precipitation of carbonate surfaces that subsequently adsorb metals. Our results suggest that metals of toxicological concern are selectively enriched in the fraction of soil that humans incidentally ingest. Investigators should likely process soil samples through a 45 microm sieve before estimating the risk associated with contaminated soils to humans. The chemical mechanisms resulting in metal enrichment likely differ between sites but at our site were linked to surface complexation with carbonates.
Abstract: The fate and mobility of boric acid in the environment is largely controlled by adsorption reactions with soil organic matter and soil minerals to form surface complexes (Soil Sci Soc. Am. J. 1991, 55, 1582; Geochim. Cosmochim. Acta 2002, 67, 2551; Soil Sci. Soc. Am. J. 1995, 59, 405; Environ. Sci. Technol. 1995, 29, 302). In this study, boric acid adsorption on pure am-Al(OH)3 and 5% (w/w) humic acid (HA) coated am-Al(OH)3 were investigated both as a function of pH (4.5-11) and initial boric acid concentration (0-4.5 mmol L(-1)). Batch adsorption isotherm experiments were also conducted with samples exposed to atmospheric CO2 and anaerobic (N2) conditions to examine the effects of dissolved CO2 on boric acid adsorption. Boron (B) K-edge X-ray absorption near-edge structure (XANES) spectroscopy was used to investigate the coordination of boric acid adsorbed at mineral/water interfaces. The XANES spectra of boric acid adsorption samples showed that both trigonally and tetrahedrally coordinated B complexes were present on the mineral surface. Both macroscopic and spectroscopic experiments revealed that the combination of HA coating on am-Al(OH)3 and dissolved CO2 decreased boric acid adsorption compared to adsorption on pure am-Al(OH)3.
Abstract: A combination of macroscopic experiments and in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy was used to study Cd(II)-sulfate interactions on the goethite-water interface. The presence of SO4 dramatically promoted Cd adsorption at lower pH (pH 5.5-6.5) and had a smaller effect at higher pH. ATR-FTIR studies indicated sulfate adsorption on goethite occurred via both outer- and inner-sphere complexation. The relative importance of both complexes was a function of pH and sulfate concentration. ATR-FTIR spectra provided direct evidence of the formation of Cd-SO4 ternary surface complexes on goethite. In addition to ternary complexes, Cd specifically sorbed on goethite promoted SO4 adsorption via changing the surface charge, and caused additional SO4 adsorption as both inner- and outer-sphere complexes. The relative importance of ternary complexes versus electrostatic effects depended upon pH values and Cd concentration. Ternary complex formation was promoted by low pH and high Cd levels, whereas electrostatic effects were more pronounced at high pH and low Cd levels. A portion of SO4 initially sorbed in inner-sphere complexes in the absence of Cd was transformed into Cd-SO4 ternary complexes with increased Cd concentration.
Abstract: Recent studies have applied surface complexation models (SCMs) to describe metal adsorption by mesophilic bacteria. However, only one SCM has been developed for metal biosorption by a thermophile and the study was limited to adsorption of Cd. In this study, we quantify adsorption of a variety of metals onto the thermophile Anoxybacillus flavithermus with surface complexation modeling. We conduct both single and multi-metal sorption studies using Cd, Cu, Mn, Ni, Pb, and/or Zn, in order to compare the relative affinities of the metals for the cell surface and investigate if these individual affinities change in the presence of other metals. We also use linear free energy relationships (LFERs) to compare the stability constants for the metal-bacteria surface complexes with a variety of aqueous metal-ligand stability constants, and we compare the metal binding capacity of Cd, Cu, Mn, Pb, Ni, and Zn of A. flavithermus to that of the commonly studied mesophile Bacillus subtilis. We find that the metals exhibit different preferences for the bacterial surface in the order Mn?[approximate]?Ni?<?Zn?<?Cd?<?Pb?[approximate]?Cu. Metal binding is described best by formation of a M-carboxyl complex and either a MOH-carboxyl, M-phosphoryl, or MOH-phosphoryl complex (where M is the metal cation). Stability constants determined from the single metal and multi-metal systems are comparable. It is therefore possible to obtain reasonable stability constants in multi-metal systems. This has the potential to greatly simplify the acquisition of metal-bacteria thermodynamic data. However, stability constants obtained from the single metal systems remain more accurate because the experimental conditions are more ideal. Under our experimental conditions, competition effects are observed for the low affinity metals in the presence of higher affinity metals. The LFER plot using the formation of M-carboxyl and MOH-carboxyl with M-acetate complexes yields linear correlation coefficients (r) of 0.82 and 0.73, respectively. We also observe that A. flavithermus generally adsorbs less metal than B. subtilis at similar metal-to-biomass concentration ratio over the pH range studied.
Abstract: It is well known that dissolved organic matter (DOM) increases in lakes associated with forestry activity but characterization of the DOM structure is incomplete. Twenty-three lakes with a wide range of forestry activities located in central Quebec, Canada were sampled and analyzed for dissolved organic carbon (DOC) concentration, DOC fluorescence, and ultra violet-visible (UV-VIS) absorption spectra. The results show that DOC increases (as does the associated DOC fluorescence) with increased logging (slope=0.122, r2=0.581, p<0.001; and slope=0.283, r2=0.308, p<0.01, respectively) in the 23 lakes sampled however, the aromaticity of the DOM does not change with changes in logging (as found by UV-VIS ratios, absorbance slope in the UV region, and DOC normalized fluorescence (slope=1.42x10(-2), r2=0.331, p<0.01). The DOM from four of these lakes was concentrated using reverse osmosis (RO) followed by freeze-drying. The structures of the concentrated dissolved organic matter (DOM) samples were analyzed using X-ray analysis of near edge structures (XANES), X-ray diffraction (XRD), and 13C solid-state nuclear magnetic resonance (13C NMR) analysis. XANES analysis of functional groups in the four concentrated samples shows that there are significant differences in reduced sulphur between the samples, however there was no clear relationship with forestry activity in the associated catchment. XRD data showed the presence of amorphous sulphide minerals associated with the DOM concentrate that may be important sites for mercury binding. The 13C NMR spectra of these samples show that the percentage of carbon present in carboxylic functional groups increases with increasing logging. Such structures are important for binding photo-reducible mercury and their presence may limit mercury photo-reduction and volatilization. We propose a mechanism by which increased logging leads to increased carboxylic groups in DOM and thereby increased weak binding of photo-reducible mercury. These results, in part, explain the decrease in dissolved gaseous mercury (DGM) production rates with increased logging found in our previous work.
Abstract: Sorption processes at the mineral/water interface typically control the mobility and bioaccessibility of many inorganic contaminants such as oxyanions. Selenium is an important micronutrient for human and animal health, but at elevated concentrations selenium toxicity is a concern. The objective of this study was to determine the bonding mechanisms of selenate (SeO4(2-) and selenite (SeO3(2-) on hydrous aluminum oxide (HAO) over a wide range of reaction pH using extended X-ray absorption fine structure (EXAFS) spectroscopy. Additionally, selenate adsorption on corundum (alpha-Al2O3) was studied to determine if adsorption mechanisms change as the aluminum oxide surface structure changes. The overall findings were that selenite forms a mixture of outer-sphere and inner-sphere bidentate-binuclear (corner-sharing) surface complexes on HAO, selenate forms primarily outer-sphere surface complexes on HAO, and on corundum selenate forms outer-sphere surface complexes at pH 3.5 but inner-sphere monodentate surface complexes at pH 4.5 and above. It is possible that the lack of inner-sphere complex formation at pH 3.5 is caused by changes in the corundum surface at low pH or secondary precipitate formation. The results are consistent with a structure-based reactivity for metal oxides, wherein hydrous metal oxides form outer-sphere complexes with sulfate and selenate, but inner-sphere monodentate surface complexes are formed between sulfate and selenate and alpha-Me2O3.
Abstract: Numerous studies have utilized surface complexation theory to model proton adsorption behaviour onto mesophilic bacteria. However, few experiments, to date, have investigated the effects of pH and ionic strength on proton interactions with thermophilic bacteria. In this study, we characterize proton adsorption by the thermophile Anoxybacillus flavithermus by performing acid-base titrations and electrophoretic mobility measurements in NaNO3 (0.001-0.1?M). Equilibrium thermodynamics (Donnan model) were applied to describe the specific chemical reactions that occur at the water-bacteria interface. Acid-base titrations were used to determine deprotonation constants and site concentrations for the important cell wall functional groups, while electrophoretic mobility data were used to further constrain the model. We observe that with increasing pH and ionic strength, the buffering capacity increases and the electrophoretic mobility decreases. We develop a single surface complexation model to describe proton interactions with the cells, both as a function of pH and ionic strength. Based on the model, the acid-base properties of the cell wall of A. flavithermus can best be characterized by invoking three distinct types of cell wall functional groups, with pKa values of 4.94, 6.85, and 7.85, and site concentrations of 5.33, 1.79, and 1.42?× 10-4 moles per gram of dry bacteria, respectively. A. flavithermus imparts less buffering capacity than pure mesophilic bacteria studied to date because the thermophile possesses a lower total site density (8.54?× 10-4 moles per dry gram bacteria).
Abstract: Several recent studies have applied surface complexation theory to model metal adsorption behaviour onto mesophilic bacteria. However, no investigations have used this approach to characterise metal adsorption by thermophilic bacteria. In this study, we perform batch adsorption experiments to quantify cadmium adsorption onto the thermophile Anoxybacillus flavithermus. Surface complexation models (incorporating the Donnan electrostatic model) are developed to determine stability constants corresponding to specific adsorption reactions. Adsorption reactions and stoichiometries are constrained using spectroscopic techniques (XANES, EXAFS, and ATR-FTIR). The results indicate that the Cd adsorption behaviour of A. flavithermus is similar to that of other mesophilic bacteria. At high bacteria-to-Cd ratios, Cd adsorption occurs by formation of a 1:1 complex with deprotonated cell wall carboxyl functional groups. At lower bacteria-to-Cd ratios, a second adsorption mechanism occurs at pH?>?7, which may correspond to the formation of a Cd-phosphoryl, CdOH-carboxyl, or CdOH-phosphoryl surface complex. X-ray absorption spectroscopic investigations confirm the formation of the 1:1 Cd-carboxyl surface complex, but due to the bacteria-to-Cd ratio used in these experiments, other complexation mechanism(s) could not be unequivocally resolved by the spectroscopic data.
Abstract: Modifying poultry diets by reducing mineral P supplementation and/or adding phytase may change the chemical composition of P in manures and affect the mobility of P in manure-amended soils. We studied the speciation of P in manures produced by broiler chickens and turkeys from either normal diets, or diets with reduced amounts of non-phytate phosphorus (NPP) and/or phytase, using a combination of chemical fractionation and synchrotron X-ray absorption near edge structure (XANES) spectroscopy. All broiler litters were rich in dicalcium phosphate (65-76%), followed by aqueous phosphate (13-18%), and phytic acid (7-20%); however, no hydroxylapatite was observed. Similarly, normal turkey manure had 77% of P as dicalcium phosphate and had no hydroxylapatite, while turkey manure from diets that had reduced NPP and phytase contained equal proportions of dicalcium phosphate (33-45%) and hydroxylapatite (35-39%). This is attributed to the higher total Ca to P ratio (>2) in modified turkey manures that resulted in transformation of more soluble (dicalcium phosphate) to less soluble P compounds (hydroxylapatite). Chemical fractionation showed that H2O-extractable P was the predominant form in broiler litter (56-77%), whereas aqueous phosphate determined with XANES was <18% indicating that H2O probably dissolved mineral forms of P (e.g., dicalcium phosphate). Results show that HCl extraction primarily removed phytic acid from broiler litters and normal turkey manure, while it removed a mixture of hydroxylapatite and phytic acid from modified turkey manures. The combination of chemical fractionation and XANES provided information about the nature of P in these manures, which may help to devise best management practices for manure use.
Abstract: Boron is an important micronutrient for plants, but high B levels in soils are often responsible for toxicity effects in plants. It is therefore important to understand reactions that may affect B availability in soils. In this study, Attenuated Total Reflectance Fourier transform Infrared (ATR-FTIR) spectroscopy was employed to investigate mechanisms of boric acid (B(OH)3) and borate (B(OH)4-) adsorption on hydrous ferric oxide (HFO). On the HFO surface, boric acid adsorbs via both physical adsorption (outer-sphere) and ligand exchange (inner-sphere) reactions. Both trigonal (boric acid) and tetrahedral (borate) boron are complexed on the HFO surface, and a mechanism where trigonal boric acid in solution reacts to form either trigonal or tetrahedral surface complexes is proposed based upon the spectroscopic results. The presence of outer-sphere boric acid complexes can be explained based on the Lewis acidity of the B metal center, and this complex has important implications for boron transport and availability. Outer-sphere boric acid is more likely to leach downward in soils in response to water flow. Outer-sphere boron would also be expected to be more available for plant uptake than more strongly bound boron complexes, and may more readily return to the soil solution when solution concentrations decrease.
Abstract: While alum amendments have shown to be effective in lowering water-soluble phosphate levels in poultry litter, the mechanism by which this occurs is not fully known. To determine the solid-state speciation of phosphate in litter samples, experiments were conducted with X-ray absorption near edge structure (XANES) spectroscopy. XANES analysis reveals that, in unamended samples, phosphate is present as weakly bound inorganic as well as some organic phosphate, with some dicalcium phosphate-type calcium phosphates also present. When alum is applied in the houses, XANES results suggest that it precipitates out as amorphous Al(OH)3 and then reacts with phosphate via an adsorption mechanism. No evidence was found of aluminum phosphate precipitation in any samples.
Abstract: Selenate (SeO4(2-)) is an oxyanion of environmental importance because of its toxicity to animals and its mobility in the soil environment. It is known that iron(III) oxides and hydroxides are important sorbents for SeO4(2-) in soils and sediments, but the mechanism of selenate adsorption on iron oxides has been the subject of intense debate. Our research employed Extended X-ray absorption fine structure and attenuated total reflectance-Fourier transform infrared spectroscopies to determine SeO4(2-) bonding mechanisms on hematite, goethite, and hydrous ferric oxide (HFO). It was learned that selenate forms only inner-sphere surface complexes on hematite but forms a mixture of outer- and inner-sphere surface complexes on goethite and HFO. This continuum of adsorption mechanisms is strongly affected by both pH and ionic strength. These results suggest that adsorption experiments should be conducted on several different iron oxides and over a wide range of reaction conditions to accurately assess the reactivity of oxyanions on iron oxides.
Abstract: We used a combination of in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray absorption fine structure (XAFS) spectroscopy to conduct molecular scale studies on Pb(II)-sulfate interactions at the solid-water interface of goethite at pH 4.5, 5.0, and 6.0. Both the ATR-FTIR studies (probing sorbed SO4 in a flow cell setup as a function of the Pb concentration) and the EXAFS studies (probing sorbed Pb at high levels of co-adsorbing SO4) indicated the formation Pb-SO4 ternary complexes at the goethite surface. Based on the combined information from the IR and XAFS studies, possible Pb-SO4 ternary complex configurations were presented and discussed by comparison to a set of reference sulfate FTIR spectra. In addition to forming ternary complexes with SO4, adsorption of Pb also promoted SO4 sorption to the goethite surface by changing the surface charge, leading to additional formation of inner- and outer-sphere SO4 sorption complexes not coordinated by Pb. The relative impacts of these mechanisms (i.e., ternary complex formation versus electrostatic effects) appeared to be a function of pH and the level of Pb addition. Formation of ternary complexes was promoted (relative to the importance of electrostatic effects) at low pH values and high Pb concentrations, whereas electrostatic effects were more pronounced at high pH values and low Pb concentrations. In addition, it was found that part of the SO4 initially sorbed at the goethite surface as inner-sphere complexes without being coordinated by Pb was transformed into SO4-Pb ternary complexes as the Pb concentration was increased, an effect most pronounced at low pH. This study shows that co-adsorption of SO4 and Pb may lead to changes in both the extent and mechanisms of the adsorption of these contaminants to the goethite surface relative to binary Pb/goethite and SO4/goethite systems. The presence of co-adsorbing metals or anions may therefore significantly impact the behavior of contaminants in environmental settings.
Abstract: The mechanism of sulfate adsorption on goethite was investigated in situ using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Sulfate adsorption was investigated at ionic strengths between 0.005 and 0.1 M, reactant concentrations between 5 and 500 µM, and pH values between 3.5 and 9.0. It was determined that sulfate forms both outer-sphere and inner-sphere surface complexes on goethite at pH less than 6. At pH values greater than 6, sulfate adsorbs on goethite only as an outer-sphere complex. The relative amount of outer-sphere sulfate surface complexation increased with decreasing ionic strength. The spectrum of sulfate adsorbed on goethite was also compared to the infrared spectrum of synthetic schwertmannite, an iron(III) oxy-hydroxy-sulfate. It was determined that in situ spectra of both schwertmannite and adsorbed sulfate are quite similar, suggesting that a continuum of outer- and inner-sphere sulfate occurs in both cases. Copyright 1999 Academic Press.
Abstract: There is international interest today in the fate and transformation of phosphorus (P) applied to soils due to historical overapplication of P from organic wastes. This overapplication has increased soil solution P concentrations and enriched the erodible fraction of soil with P. This is of major concern as significant water quality deterioration can occur if P applied to soils in organic wastes reaches water bodies. Just as the bioavailability of P compounds depends upon their chemical form, it is becoming increasingly apparent that information about different forms of P is needed for holistic management of organic wastes. A number of chemical and biological methods have been employed to partition total P into more specific chemical forms in organic wastes. However, there has been no previous effort to review and synthesize the literature and to critically analyze the various techniques with promise for chemical speciation of P in organic wastes. In this chapter, we review various types of organic wastes and factors affecting P composition in organic wastes, from production to land disposal. Then, we discuss the various methods that have been used to characterize P forms, including water extractable P (WEP) physicochemical fractionation, sequential chemical fractionation, enzymatic hydrolysis, nuclear magnetic resonance (NMR), and x[hyphen (true graphic)]ray absorption near edge structure (XANES) spectroscopy. To summarize the conclusions, WEP is quick chemical test that should be employed to determine the readily dissolved P in organic wastes and to assess the potential risk of wastes on water quality. The potential bioavailability of P forms in the liquid wastes can be similarly assessed by a rapid and low cost physicochemical fractionation method. Enzymatic hydrolysis and solution state NMR can be of great benefit to characterize organic P species in wastes, whereas solid[hyphen (true graphic)]state NMR and XANES spectroscopy are better suited to study the inorganic P minerals in the wastes. NMR and XANES methods are both quantitative and can be used to study the influence of management practices on P speciation. Solid[hyphen (true graphic)]state NMR and XANES methods are capable of performing analysis of heterogeneous material and provides complementary information about P compounds in organic wastes. The combined use of sequential chemical fractionation and spectroscopic methods (NMR, XANES) allows for accurate identification of P compounds in the sequential extracts. Case studies are included throughout the chapter to discuss wider applicability of a particular method. We conclude this chapter by suggesting that more than one method may be necessary for complete determination of P species in organic wastes.
