Systematic evaluation of methods for iron-impregnation of biochar and effects on arsenic in flooded soils.

There is a need for innovative strategies to decrease the mobility of metal(loids) including arsenic (As) and cadmium (Cd) in agricultural soils, including rice paddies, so as to minimize dietary exposure to these toxic elements. Iron (Fe)-modified biochars (FBCs) are used to immobilize As and Cd in soil-water systems, but there is a lack of clarity on optimal methods for preparing FBCs because there are only limited studies that directly compare BCs impregnated with Fe under different conditions. There is also a lack of information on the long-term performance of FBCs in flooded soil environments, where reductive dissolution of Fe (oxy)hydroxide phases loaded onto biochar surfaces may decrease the effectiveness of FBCs. This study uses material characterization methods including FTIR, SEM-EDX, BET, and adsorption isotherm experiments to investigate the effects of Fe-impregnation methods (pH, pyrolysis sequence, and sonication) on the morphology and mineralogy of Fe loaded onto the biochar surface, and to FBC adsorbent properties for arsenate (As(V)), arsenite (As(III)), and Cd. Acidic impregnation conditions favored the adsorption of As(III) onto amorphous Fe phases that were evenly distributed on the biochar surface, including within the biochar pore structure. The combination of sonication with acidic Fe-impregnation conditions led to the best adsorption capacities for As(V) and As(III) (4830 and 11,166 µg As g-1 biochar, respectively). Alkaline Fe-impregnation conditions led to the highest Cd adsorption capacity of 3054 µg Cd g-1 biochar, but had poor effectiveness as an As adsorbent. Amending soil with 5% (w/w) of an acid-impregnated and sonicated FBC was more effective than an alkaline-impregnated FBC or ferrihydrite in decreasing porewater As concentrations. The acid-impregnated FBC also had greater longevity, decreasing As by 54% and 56% in two flooded phases, probably due to the greater stability of Fe(III) within the biochar pore structure that may have a direct chemical bond to the biochar surface. This study demonstrates that FBCs can be designed with selectivity towards different As species or Cd and that they can maintain their effectiveness under anaerobic soil conditions. This is the first study to systematically test how impregnation conditions affect the stability of FBCs in soils under multiple drying-rewetting cycles.

In the presence of the other: How glyphosate and peptide molecules alter the dynamics of sorption on goethite.

The interactions with soil mineral surfaces are among the factors that determine the mobility and bioavailability of organic contaminants and of nutrients present in dissolved organic matter (DOM) in soil and aquatic environments. While most studies focus on high molar mass organic matter fractions (e.g., humic and fulvic acids), very few studies investigate the impact of DOM constituents in competitive sorption. Here we assess the sorption behavior of a heavily used herbicide (i.e., glyphosate) and a component of DOM (i.e., a peptide) at the water/goethite interface, inclusive of potential glyphosate-peptide interactions. We used in-situ ATR-FTIR (attenuated total reflectance Fourier-transform infrared) spectroscopy to study sorption kinetics and mechanisms of interaction as well as conformational changes to the secondary structure of the peptide. NMR (nuclear magnetic resonance) spectroscopy was used to assess the level of interaction between glyphosate and the peptide and changes to the peptide' secondary structure in solution. For the first time, we illustrate competition for sorption sites results in co-sorption of glyphosate and peptide molecules that affects the extent, kinetics, and mechanism of interaction of each with the surface. In the presence of the peptide, the formation of outer-sphere glyphosate-goethite complexes is favored albeit inner-sphere glyphosate-goethite bonds (i.e., POFe) are still formed. The presence of glyphosate induces secondary structural shifts of the sorbed peptide that maximizes the formation of H-bonds with the goethite surface. However, glyphosate and the peptide do not seem to interact with one another in solution nor at the goethite surface upon sorption. The results of this work highlight potential consequences of competition for sorption sites, for example the transport of organic contaminants and nutrient-rich (i.e., nitrogen) DOM components in relevant environmental systems. Predicting the rate and extent with which organic pollutants are removed from solution by a given solid is also one of the most critical factors for the design of effective sorption systems in engineering applications.

More movement with manure: increased mobility of erythromycin through agricultural soil in the presence of manure.

Antibiotic residues in the environment threaten soil and aquatic organisms and human and livestock health through the building of antimicrobial resistance. Manure spreading associated with animal agriculture is one source of environmental antibiotic residues. To better understand the risk of contamination, we studied the adsorption of erythromycin, a model macrolide antibiotic used across human and animal medicine. We conducted a series of equilibrium batch experiments to determine the kinetics and extent of adsorption and a continuous-flow column adsorption experiment to observe non-equilibrium adsorption patterns. We determined that the adsorption equilibration time to soil was approximately 72 h in our batch experiments. Erythromycin adsorbed to soil relatively strongly (K = 8.01 × 10-2 L/mg; qmax = 1.53 × 10-3 mg/mg), adsorbed to the soil in the presence of manure with less affinity (K = 1.99 × 10-4 L/mg) at a soil: manure ratio of 10:1 by mass, and did not adsorb to manure across the solid ratios tested. We observed multi-phased adsorption of erythromycin to the soil during the non-equilibrium column experiment, which was largely absent from the treatments with both soil and manure present. These results suggest that erythromycin is more mobile in the environment when introduced with manure, which is likely the largest source of agriculturally sourced environmental antibiotics.

Dynamic utilization of low-molecular-weight organic substrates across a microbial growth rate gradient.

AIM: Low-molecular-weight organic substances (LMWOSs) are at the nexus between micro-organisms, plant roots, detritus, and the soil mineral matrix. The nominal oxidation state of carbon (NOSC) has been suggested as a potential parameter for modelling microbial uptake rates of LMWOSs and the efficiency of carbon incorporation into new biomass. METHODS AND RESULTS: In this study, we assessed the role of compound class and oxidation state on uptake kinetics and substrate-specific carbon use efficiency (SUE) during the growth of three model soil micro-organisms, a fungal isolate (Penicillium spinulosum) and two bacterial isolates (Paraburkholderia solitsugae, and Ralstonia pickettii). Isolates were chosen that spanned a growth rate gradient (0.046-0.316 h-1 ) in media containing 34 common LMWOSs at realistically low initial concentrations (25 µM each). Clustered, co-utilization of LMWOSs occurred for all three organisms. Potential trends (p < 0.05) for early utilization of more oxidized substrates were present for the two bacterial isolates (P. solitsugae and R. pickettii), but high variability (R2 < 0.15) and a small effect of NOSC indicate these relationships are not useful for prediction. The SUEs of selected substrates ranged from 0.16 to 0.99 and there was no observed relationship between NOSC and SUE. CONCLUSION: Our results do not provide compelling population-level support for NOSC as a predictive tool for either uptake kinetics or the efficiency of use of LMWOS in soil solution. SIGNIFICANCE AND IMPACT OF THE STUDY: Metabolic strategies of organisms are likely more important than chemical identity in determining LMWOS cycling in soils. Previous community-level observations may be biased towards fast-responding bacterial community members.

Ecophysiological Study of Paraburkholderia sp. Strain 1N under Soil Solution Conditions: Dynamic Substrate Preferences and Characterization of Carbon Use Efficiency.

We used time-resolved metabolic footprinting, an important technical approach used to monitor changes in extracellular compound concentrations during microbial growth, to study the order of substrate utilization (i.e., substrate preferences) and kinetics of a fast-growing soil isolate, Paraburkholderia sp. strain 1N. The growth of Paraburkholderia sp. 1N was monitored under aerobic conditions in a soil-extracted solubilized organic matter medium, representing a realistic diversity of available substrates and gradient of initial concentrations. We combined multiple analytical approaches to track over 150 compounds in the medium and complemented this with bulk carbon and nitrogen measurements, allowing estimates of carbon use efficiency throughout the growth curve. Targeted methods allowed the quantification of common low-molecular-weight substrates: glucose, 20 amino acids, and 9 organic acids. All targeted compounds were depleted from the medium, and depletion followed a sigmoidal curve where sufficient data were available. Substrates were utilized in at least three distinct temporal clusters as Paraburkholderia sp. 1N produced biomass at a cumulative carbon use efficiency of 0.43. The two substrates with highest initial concentrations, glucose and valine, exhibited longer usage windows, at higher biomass-normalized rates, and later in the growth curve. Contrary to hypotheses based on previous studies, we found no clear relationship between substrate nominal oxidation state of carbon (NOSC) or maximal growth rate and the order of substrate depletion. Under soil solution conditions, the growth of Paraburkholderia sp. 1N induced multiauxic substrate depletion patterns that could not be explained by the traditional paradigm of catabolite repression.IMPORTANCE Exometabolomic footprinting methods have the capability to provide time-resolved observations of the uptake and release of hundreds of compounds during microbial growth. Of particular interest is microbial phenotyping under environmentally relevant soil conditions, consisting of relatively low concentrations and modeling pulse input events. Here, we show that growth of a bacterial soil isolate, Paraburkholderia sp. 1N, on a dilute soil extract resulted in a multiauxic metabolic response, characterized by discrete temporal clusters of substrate depletion and metabolite production. Our data did not support the hypothesis that compounds with lower energy content are used preferentially, as each cluster contained compounds with a range of nominal oxidation states of carbon. These new findings with Paraburkholderia sp. 1N, which belongs to a metabolically diverse genus, provide insights on ecological strategies employed by aerobic heterotrophs competing for low-molecular-weight substrates in soil solution.

Paraburkholderia solitsugae sp. nov. and Paraburkholderia elongata sp. nov., phenolic acid-degrading bacteria isolated from forest soil and emended description of Paraburkholderia madseniana.

Two bacterial strains, 1NT and 5NT, were isolated from hemlock forest soil using a soluble organic matter enrichment. Cells of 1NT (0.65×1.85 µm) and 5NT (0.6×1.85 µm) are Gram-stain-negative, aerobic, motile, non-sporulating and exist as single rods, diplobacilli or in chains of varying length. During growth in dilute media (≤0.1× tryptic soy broth; TSB), cells are primarily motile with flagella. At higher concentrations (≥0.3× TSB), cells of both strains increasingly form non-motile chains, and cells of 5NT elongate (0.57×~7 µm) and form especially long filaments. Optimum growth of 1NT and 5NT occurred at 25-30 °C, pH 6.5-7.0 and <0.5% salinity. Results of comparative chemotaxonomic, genomic and phylogenetic analyses revealed that 1NT and 5NT were distinct from one another and their closest related type strains: Paraburkholderia madseniana RP11T, Paraburkholderia aspalathi LMG 27731T and Paraburkholderia caffeinilytica CF1T. The genomes of 1NT and 5NT had an average nucleotide identity (91.6 and 91.3%) and in silico DNA-DNA hybridization values (45.8%±2.6 and 45.5%±2.5) and differed in functional gene content from their closest related type strains. The composition of fatty acids and patterns of substrate use, including the catabolism of phenolic acids, also differentiated strains 1NT and 5NT from each other and their closest relatives. The only ubiquinone present in strains 1NT and 5NT was Q-8. The major cellular fatty acids were C16 : 0, 3OH-C16 : 0, C17 : 0 cyclo, C19 : 0 cyclo ω8c and summed features 2 (3OH-C14 : 0 / C16 : 1 iso I), 3 (C16 : 1 ω6c/ω7c) and 8 (C18 : 1 ω7c/ω6c). A third bacterium, strain RL16-012-BIC-B, was isolated from soil associated with shallow roots and was determined to be a strain of P. madseniana (ANI, 98.8%; 16S rRNA gene similarity, 100%). Characterizations of strain RL16-012-BIC-B (DSM 110723=LMG 31706) led to proposed emendments to the species description of P. madseniana. Our polyphasic approach demonstrated that strains 1NT and 5NT represent novel species from the genus Paraburkholderia for which the names Paraburkholderia solitsugae sp. nov. (type strain 1NT=DSM 110721T=LMG 31704T) and Paraburkholderia elongata sp. nov. (type strain 5NT=DSM 110722T=LMG 31705T) are proposed.

Lead Solubility and Mineral Structures of Coprecipitated Lead/Calcium Oxalates.

Low-molecular-weight organic acids such as oxalate, which are ubiquitous in the environment, can control the solubility and bioavailability of toxic metals such as Pb in soils and water by influencing complexation and precipitation reactions. Here, we investigated Pb solubility in relation to Pb-oxalate precipitation at pH 5.0 in the absence and presence of calcium (Ca), a common cation in environmental matrices. At Pb mole fractions less than 0.10, sequestration of Pb into Ca oxalate to form a solid solution substantially lowered Pb solubility relative to that of pure Pb oxalate to an extent inversely proportional to the Pb mole fraction. Small Pb/Ca solid-solution distribution coefficients at these low mole ratios was largely attributed to the stronger complexation of Pb compared to Ca with oxalate to form soluble metal-oxalate complexes, which in turn limited Pb incorporation into the Ca-oxalate crystal lattice. Characterization of the Pb/Ca-oxalate coprecipitates by X-ray diffraction, optical microscopy, and Fourier transform infrared spectroscopy revealed that the whewellite (Ca-oxalate monohydrate) structure was destabilized by substitution of small amounts of Pb into the lattice, and thus, the formation of the Ca-oxalate dihydrate (weddellite) was favored over the monohydrate. At Pb mole fractions above 0.20, discrete crystallites of Pb oxalate were identified. These new findings imply that Pb/Ca-oxalate coprecipitates in the presence of Ca could reduce the solubility of Pb in Pb-contaminated acid soils.

Nitrate transformation and immobilization in particulate organic matter incubations: Influence of redox, iron and (a)biotic conditions.

Nitrate can be reduced to other N inorganic species via denitrification and incorporated into organic matter by immobilization; however, the effect of biotic/abiotic and redox condition on immobilization and denitrification processes from a single system are not well documented. We hypothesize nitrate (NO3-) transformation pathways leading to the formation of dissolved- and solid-phase organic N are predominantly controlled by abiotic reactions, but the formation of soluble inorganic N species is controlled by redox condition. In this study, organic matter in the form of leaf compost (LC) was spiked with 15NO3- and incubated under oxic/anoxic and biotic/abiotic conditions at pH 6.5. We seek to understand how variations in environmental conditions impact NO3- transformation pathways through laboratory incubations. We find production of NH4+ is predominantly controlled by redox whereas NO3- conversion to dissolved organic nitrogen (DON) and immobilization in solid-phase N are predominantly controlled by abiotic processes. Twenty % of added 15N-NO3- was incorporated into DON under oxic conditions, with abiotic processes accounting for 85% of the overall incorporation. Nitrogen immobilization processes resulted in N concentrations of 4.1-6.6 µg N (g leaf compost)-1, with abiotic processes accounting for 100% and 66% of the overall (biotic+abiotic) N immobilization under anoxic and oxic conditions, respectively. 15N-NMR spectroscopy suggests 15NO3- was immobilized into amide/aminoquinones and nitro/oxime under anoxic conditions. A fraction of the NH4+ was produced abiotically under anoxic conditions (~10% of the total NH4+ production) although biotic organic N mineralization contributed to most of NH4+ production. Our results also indicate Fe(II) did not act as an electron source in biotic-oxic incubations; however, Fe(II) provided electrons for NO3- reduction in biotic-anoxic incubations although it was not the sole electron source. It is clear that, under the experimental conditions of this investigation, abiotic and redox processes play important roles in NO3- transformations. As climatic conditions change (e.g., frequency/intensity of rainfall), abiotic reactions that shift transformation pathways and N species concentrations from those controlled by biota might become more prevalent.

Oxalate-enhanced solubility of lead (Pb) in the presence of phosphate: pH control on mineral precipitation.

Here we study the precipitation of lead (Pb)-phosphate minerals over the pH range of 4.0 to 8.0 with and without oxalate, a ubiquitous and abundant low-molecular-weight organic acid derived from plants and microorganisms in environmental matrices. In the aqueous Pb-phosphate systems, phosphate precipitated Pb efficiently, reducing the dissolved Pb concentration below 1 µM at all the tested pH values, with the minimum solubility of about 0.1 µM measured at the intermediate pH of 6.0. The measured dissolved Pb and free Pb2+ ion activity were not in agreement with predictions from generally-accepted solubility products of the Pb phosphate minerals, particularly hydroxypyromorphite [Pb5(PO4)3OH]. Discrepancies between our measured Pb phosphate solubility products and older reported values are attributed to non-ideal behavior of these minerals (incongruent dissolution) as well as uncertainties in stability constants for soluble Pb-phosphate ion pairs. The presence of equimolar levels of oxalate and phosphate resulted in up to 250-fold increase in Pb solubility at acidic pH and about a 4-fold increase at pH 7.0, due to the strong suppression of Pb phosphate precipitation by oxalate and formation of soluble Pb-oxalate complexes. At pH 4.0 and 5.0, Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) identified a Pb-oxalate mineral phase as the only precipitate despite the presence of phosphate; in the absence of oxalate, Pb hydrogen phosphate, PbHPO4, stably formed under these acidic conditions. At pH 6.0 and greater, FTIR and XRD data revealed that Pb-phosphate [Pb3(PO4)2], and hydroxypyromorphite [Pb5(PO4)3OH] to a lesser extent, were the predominant precipitates both in the absence and presence of oxalate. Therefore, oxalate did not strongly interfere with Pb-phosphate mineral formation at aqueous pH greater than 6.0 but oxalate controlled Pb solubility at acidic pH values.

Zinc alleviates copper toxicity to symbiotic nitrogen fixation in agricultural soil affected by copper mining in central Chile.

According to the Terrestrial Biotic Ligand Model, other cations might compete with Cu+2 for biotic ligand sites and provide a protective effect. In particular, evidence suggests Zn may alleviative Cu toxicity. No study, to the best of our knowledge, has focused explicitly on the alleviating effect Zn might have on Cu toxicity to soil microorganisms in field-contaminated soils. The aim of this study was to investigate the alleviating effect Zn might have on Cu toxicity to symbiotic nitrogen fixation in agricultural soils affected by copper mining in central Chile. The bioassay estimated the symbiotic nitrogen fixation capacity of a population of rhizobia in a specified soil, using the soil as inocula for Phaseolus vulgaris L. grown in a soil-less system (pots with perlite) irrigated with a sterile nitrogen-free nutrient solution. Among all soil physicochemical characteristics, the Cu/Zn ratio best explained changes in symbiotic nitrogen fixation. The effective concentration 50% (EC50) of Cu/Zn ratio for symbiotic nitrogen was equal to 1.2, with 95% confidence interval of 1.0-1.3. Symbiotic nitrogen fixation decreased with increased Cu/Zn ratio, thus suggesting that Zn alleviates Cu toxicity to nitrogen fixing microorganisms.

Simultaneous Quantification of Electron Transfer by Carbon Matrices and Functional Groups in Pyrogenic Carbon.

Pyrogenic carbon contains redox-active functional groups and polyaromatic carbon matrices that are both capable of transferring electrons. Several techniques have been explored to characterize the individual electron transfer process of either functional groups or carbon matrices individually. However, simultaneous analysis of both processes remains challenging. Using an approach that employs a four-electrode configuration and dual-interface electron transfer detection, we distinguished the electron transfer by functional groups from the electron transfer by carbon matrices and simultaneously quantified their relative contribution to the total electron transfer to and from pyrogenic carbon. Results show that at low to intermediate pyrolysis temperatures (400-500 °C), redox cycling of functional groups is the major mechanism with a contribution of 100-78% to the total electron transfer; whereas at high temperatures (650-800 °C), direct electron transfer of carbon matrices dominates electron transfer with a contribution of 87-100%. Spectroscopic and diffraction analyses of pyrogenic carbon support the electrochemical measurements by showing a molecular-level structural transition from an enrichment in functional groups to an enrichment in nanosized graphene domains with increasing pyrolysis temperatures. The method described in this study provides a new analytical approach to separately quantify the relative importance of different electron transfer pathways in natural pyrogenic carbon and has potential applications for engineered carbon materials such as graphene oxides.

Supramolecular Association Impacts Biomolecule Adsorption onto Goethite.

Formation of biomolecule-rich supramolecular complexes in dissolved organic matter (DOM) and subsequent adsorption onto minerals is important for the development of mineral-stabilized organic matter, yet the impact of supramolecular association on interfacial behavior is seldom studied. A series of supramolecular complexes of model biomolecules (deoxyribonucleic acid (DNA) and bovine serum albumin (BSA)) are synthesized, characterized, and adsorbed onto goethite. Complexes represent 0.1 mg/mL DNA mixed with BSA concentrations from 0.05 to 0.5 mg/mL in 5 mM KCl at pH = 5.0. Circular dichroism demonstrates strong binding between DNA and BSA, with DNA saturation when (BSA) ≈ 0.4 mg/mL. Dynamic light scattering and electrophoretic mobility measurements suggest DNA-BSA binding reduces DNA-DNA electrostatic repulsion. Spectroscopic studies of DNA/BSA complex adsorption show complexation hinders coordination of DNA phosphodiester groups with goethite. Increasing BSA (≤0.4 mg/mL) in DNA/BSA complexes enhances DNA adsorption, due to reduced repulsion between adsorbed DNA helices. When (BSA) > 0.4 mg/mL, however, DNA adsorption is decreased. We hypothesize this results from blocking of surface sites by fast adsorption of BSA loosely associated with DNA/BSA complexes. We posit an additional mechanism describing multilayered architecture formation of organo-mineral associations in soil, suggesting solution interactions may represent an overlooked factor when considering mineral retention of DOM.

Kinetic and Conformational Insights of Protein Adsorption onto Montmorillonite Revealed Using in Situ ATR-FTIR/2D-COS.

Protein adsorption onto clay minerals is a process with wide-ranging impacts on the environmental cycling of nutrients and contaminants. This process is influenced by kinetic and conformational factors that are often challenging to probe in situ. This study represents an in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic investigation of the adsorption of a model protein (bovine serum albumin (BSA)) onto a clay mineral (montmorillonite) at four concentrations (1.50, 3.75, 7.50, and 15.0 µM) under environmentally relevant conditions. At all concentrations probed, FTIR spectra show that BSA readily adsorbs onto montmorillonite. Adsorption kinetics follow an Elovich model, suggesting that primary limitations on adsorption rates are surface-related heterogeneous energetic restrictions associated with protein rearrangement and lateral protein-protein interaction. BSA adsorption onto montmorillonite fits the Langmuir model, yielding K = 5.97 × 10(5) M(-1). Deconvolution and curve fitting of the amide I band at the end of the adsorption process (∼120 min) shows a large extent of BSA unfolding upon adsorption at 1.50 µM, with extended chains and turns increasing at the expense of α-helices. At higher concentrations/surface coverages, BSA unfolding is less pronounced and a more compact structure is assumed. Two-dimensional correlation spectroscopic (2D-COS) analysis reveals three different pathways corresponding to adsorbed conformations. At 1.50 µM, adsorption increases extended chains, followed by a loss in α-helices and a subsequent increase in turns. At 3.75 µM, extended chains decrease and then aggregated strands increase and side chains decrease, followed by a decrease in turns. With 7.50 and 15.0 µM BSA, the loss of side-chain vibrations is followed by an increase in aggregated strands and a subsequent decrease in turns and extended chains. Overall, the BSA concentration and resultant surface coverage have a profound impact on the dynamics of BSA adsorption onto montmorillonite. These results enhance our understanding of the molecular-level protein dynamics and stabilization of organic matter at mineral surfaces.

Fe biogeochemistry in reclaimed acid mine drainage precipitates--implications for phytoremediation.

At a 50-year-old coal mine drainage barrens in central Pennsylvania, USA, we evaluated the biogeochemistry of acidic, Fe(III)oxy(hydr)oxide precipitates in reclaimed plots and compared them to untreated precipitates in control areas. Reclaimed plots supported successional vegetation that became established after a one-time compost and lime treatment in 2006, while control plots supported biological crusts. Precipitates were sampled from moist yet unsaturated surface layers in an area with lateral subsurface flow of mine drainage above a fragipan. Fe(II) concentrations were three- to five-fold higher in reclaimed than control precipitates. Organically bound Fe and amorphous iron oxides, as fractions of total Fe, were also higher in reclaimed than control precipitates. Estimates of Fe-reducing and Fe-oxidizing bacteria were four- to tenfold higher in root-adherent than both types of control precipitates. By scaling up measurements from experimental plots, total Fe losses during the 5-yr following reclamation were estimated at 45 t Fe ha(-1) yr(-1).

Importance of dynamic soil properties in metal retention: an example from long-term Cu partitioning and redistribution studies using model systems.

The effect of initial conditions and reaction pathways in the long term solid-solution partitioning and solid-phase distribution of Cu among ferrihydrite, leaf compost (LC), and montmorillonite (K-SWy2) were established using compartmentalized batch reactors by varying the sequence of mixing of the sorbents. Copper was allowed to react with a single solid phase for 30 days (1st equilibration) before introducing the other two solid phases and equilibration for 8 additional months (2nd equilibration). The systems were labeled Fe-Ox, Organic, or Smectitic reflecting the single initial solid phase present during the first equilibration. Total dissolved Cu and total Cu in individual solid phases were determined as a function of time during the first and second equilibrations. Results showed that different initial conditions elicited different dynamic responses where the generation of dissolved organic carbon (DOC) and diffusion of colloidal ferrihydrite seemed to influence the long-term partitioning and distribution of Cu. Trends in total dissolved Cu for the systems at the end of the first equilibration were Fe-Ox > Organic > Smectitic, while at the end of the second equilibration the organic system was the least effective in the removal of Cu from solution (Organic > Fe-Ox ≈ Smectitic). Furthermore, our results indicated Cu redistribution toward organic matter and montmorillonite, with small amounts of Cu retained by ferrihydrite. These results are attributed to reaction pathways where the formation of soluble Cu-organic complexes and colloidal Cu-ferrihydrite, and their subsequent reaction with the solids present in the systems, were operative. The experiments reported herein show dynamic properties dictate Cu reaction pathways in multiphase-multicomponent systems and might help to explain unexpected higher mobility of metals after soil remediation.

Highly charged swelling mica reduces Cu bioavailability in Cu-contaminated soils.

This is the first test of a highly charged swelling mica's (Na-2-mica) ability to reduce the plant-absorbed Cu in Cu-contaminated soils from Chile. Perennial ryegrass (Lolium perenne L.) was grown in two acid soils (Sector 2: pH 4.2, total Cu = 172 mg Cu kg(-1) and Sector 3: pH 4.2, total Cu = 112 mg Cu kg(-1)) amended with 0.5% and 1% (w/w) mica, and 1% (w/w) montmorillonite. At 10 weeks of growth, both mica treatments decreased the shoot Cu of ryegrass grown in Sector 2 producing shoot Cu concentrations above 21-22 mg Cu kg(-1) (the phytotoxicity threshold for that species), yet the mica treatments did not reduce shoot Cu concentrations when grown in Sector 3, which were at a typical level. The mica treatments improved shoot growth in Sector 3 by reducing free and extractable Cu to low enough levels where other nutrients could compete for plant absorption and translocation. In addition, the mica treatments improved root growth in both soils, and the 1% mica treatment reduced root Cu in both soils. This swelling mica warrants further testing of its ability to assist re-vegetation and reduce Cu bioavailability in Cu-contaminated surface soils.

Copper--alumina--organic matter mixed systems: alumina transformation and copper speciation as revealed by EPR spectroscopy.

The chemical forms and solubility of Cu in alumina-organic matter systems were studied separately (Cu/Al and Cu/OM) and in mixtures (Cu/Al/OM) during long-term (up to 8 years) equilibrations at pH 6 and 7.5. The transformation of alumina was monitored by XRD, while the chemical forms of Cu were probed by EPR spectroscopy. Total dissolved Cu was determined by voltammetry. Alumina transformation to gibbsite was more rapid and complete in the Cu/Al system equilibrated at pH 7.5 than at pH 6. The presence of colloidal organic matter (Cu/Al/OM) retarded the transformation of alumina. This effect was more pronounced in the system aged at pH 7.5, likely due to the higher pH that promotes formation of Al3+--organic matter coordination complexes. As expected, the systems at pH 7.5 resulted in lower dissolved Cu concentrations than corresponding systems at pH 6. After long-term equilibrations (8 and 5 years) at pH 6 and 7.5, however, the alumina-containing coprecipitates resulted in the lowest concentrations of Cu in solution (Cu/Al < Cu/Al/OM < Cu/OM). Analyses by EPR spectroscopy indicated that Cu forms inner-sphere complexes in all systems at both pH values. Changes in the chemical forms of coprecipitated Cu (Cu/Al and Cu/Al/OM systems) occurred with time and included Cu occupying discrete sites where Cu-O-Al bond formation was dominant followed by formation of clusters (Cu-O-Cu associations) and in some cases precipitates. The anisotropic EPR parameters of the Cu/OM systems suggested that stronger interactions exist between Cu and organic matter functional groups as compared to Cu interactions with alumina-containing coprecipitates; yet, Cu solubility was highest in the Cu/OM systems. The geochemical processes described in this investigation may be effective in forest soils and wastewater treatment plants where Al and Fe salts are used as flocculation agents and to remove metal contaminants from solution.

Solid- and solution-phase organics dictate copper distribution and speciation in multicomponent systems containing ferrihydrite, organic matter, and montmorillonite.

Copper retention by ferrihydrite, leaf compost, and montmorillonite was studied over 8 months in systems that emulate a natural soil where different solid phases compete for Cu through a common solution in a compartmentalized batch reactor. Copper speciation in solution (total dissolved, DPASV-labile, and free) and exchangeable and total Cu in individual solid phases were determined. Organic carbon in solution (DOC) and that retained by the mineral phases were also determined. Cu sorption reached steady-state after 4 months and accounted for 80% of the Cu initially added to the system (0.15 mg L(-1)). The remaining 20% stayed in solution as nonlabile (82.8%), labile (17%), and free (0.2%) Cu species. Copper sorption followed the order organic matter > silicate clays > iron oxides. Within each solid phase, exchangeable Cu was < or = 10% of the total Cu sorbed. DOC reached steady state (22 mg L(-1)) after 4 months and seemed to control Cu solubility and sorption behavior by the formation of soluble Cu-DOC complexes and by sorbing onto the mineral phases. DOC sorption onto ferrihydrite prevented Cu retention by this solid phase. Using a multicomponent system and 8 months equilibrations, we were able to capture some of the more important aspects of the complexity of soil environments bytaking into account diffusion processes and competition among solid- and solution-phase soil constituents in the retention of a metal cation.

Highly charged swelling mica-type clays for selective Cu exchange.

There is a need to develop highly CU2+ selective materials which can potentially remediate copper contaminated soils and water. Here we show that several highly charged synthetic swelling mica-type clays are highly selective for copper exchange. The synthetic micas have cation exchange capacities (CECs), which are close to their theoretical values. Both Na-saturated and Mg-saturated micas were investigated for Cu ion exchange selectivity. Ion exchange isotherms and Kielland plots were constructed using the equilibrated solution analyses. From these studies it was found that Na-4-mica and Na-3-mica could selectively exchange copper at lower concentrations from solution, whereas Na-2-mica sample performed better by showing Cu ion exchange selectively to almost its capacity. The EPR spectra of Cu-exchanged micas coincide with the mica's charge characteristics that predict increased binding strength of exchangeable Cu in Na-4-mica and Na-3-mica than in Na-2-mica.