Mobility of Dissolved Organic Matter from the Suwannee River (Georgia, USA) in Sand-Packed Columns.

Transport of dissolved organic matter (DOM) from the Suwannee River and of synthetic polystyrene sulfonates (PSSs) was investigated in columns packed with naturally Fe/Al-oxide-coated sands from Oyster, Virginia. Surface-water samples were collected in May 2012 and processed by XAD-8 (humic substances; HPOA), XAD-4 (transphilic acids [TPIAs]), and reverse osmosis (broad range of components; NOM). Median transport time (Ro ) of PSSs increased with molecular weight (MW) from 1,000 to 8,000 Da but decreased for the largest PSS (18,000 Da), which is consistent with previous observations of MW effects on DOM adsorption and transport. Breakthrough curves (BTCs) of HPOAs and NOM were similar whereas TPIA transport was distinct; although all DOM samples had similar Ro values, BTC asymmetry and dispersivity were greater for TPIAs. All samples exhibited power-law tailing that is characteristic of heterogeneous sorbent/sorbate interactions, potentially including kinetic effects. The one-dimensional advection-dispersion equation was unable to capture the tailing but it was captured well using a continuous-time random walk (CTRW) model. CTRW parameters were similar for the NOM and HPOA samples but distinctly different for TPIAs, which had more pronounced tailing. While retardation of organics generally tends to increase with MW, the lower average MW of TPIAs did not result in decreased overall retardation, which suggests the importance of compositional differences. Results suggest that while TPIAs tend to be a relatively minor component of DOM, their transport behavior differs from that of the predominant HPOA fraction, and they might thus have different impacts on pollutant transport.

Natural Organic Matter Transport Modeling with a Continuous Time Random Walk Approach.

In transport experiments through columns packed with naturally Fe/Al oxide-coated quartz sand, breakthrough curves (BTCs) of natural organic matter (NOM) displayed strong and persistent power law tailing that could not be described by the classical advection-dispersion equation. Tailing was not observed in BTCs for a nonreactive tracer (sulforhodamine B); therefore, the anomalous transport is attributed to diverse adsorptive behavior of the polydisperse NOM sample rather than to physical heterogeneity of the porous medium. NOM BTC tailing became more pronounced with decreases in pH and increases in ionic strength, conditions previously shown to be associated with enhanced preferential adsorption of intermediate to high molecular weight NOM components. Drawing from previous work on anomalous solute transport, we develop an approach to model NOM transport within the framework of a continuous time random walk (CTRW) and show that under all conditions examined, the CTRW model is able to capture tailing of NOM BTCs by accounting for differences in transport rates of NOM fractions through a distribution of effective retardation factors. These results demonstrate the importance of considering effects of adsorptive fractionation on NOM mobility, and illustrate the ability of the CTRW model to describe transport of a multicomponent solute.

Accessibility of humic-associated Fe to a microbial siderophore: implications for bioavailability.

Microorganisms in aerobic, circum-neutral environments are challenged to acquire sufficient nutrient Fe due to low solubilities of Fe oxides. To overcome this challenge, many aerobic microbes produce low molecular weight (MW) organic ligands, or siderophores, with extremely high Fe-binding affinities. This research expands the existing understanding of siderophore-mediated Fe acquisition from minerals by examining the effects of the siderophore desferrioxamine B (DFOB) on Fe removal from aquatic humic substances (XAD-8-isolated) and other organic matter (OM) isolates (reverse osmosis, RO; and "transphilic", XAD-4) from several rivers including the Suwannee River (GA, USA). Analysis of samples by asymmetrical flow field-flow fractionation (AsFlFFF) with in-line ICP-MS and UV-vis detectors showed that Fe was naturally abundant and primarily associated with intermediate to high MW OM. An excess of DFOB (relative to naturally present Fe) removed ∼ 75% of Fe and shifted the OM MW distribution to lower MWs, perhaps due to removal of "bridging" Fe, although additional mechanistic study of MW shifts is needed. Removal of other OM-associated metals (e.g., Al, Cu, Zn) by DFOB was minimal for all but a few samples. Fe bound to humic substances and other more "transphilic" organic components therefore should be considered readily bioavailable to aerobic, siderophore-producing microorganisms.

Effect of polydispersity on natural organic matter transport.

The mobility of humic-substance dominated natural organic matter (NOM) concentrated from a freshwater wetland by reverse osmosis was examined in sand columns at pH 5-8, in 0.001 M and 0.01 M NaClO4. Greater mobility was observed at higher pH and lower ionic strength, although breakthrough curves (BTCs) for bulk NOM exhibited extensive tailing under all conditions examined. Based on observations from previous batch experiments indicating preferential adsorption of intermediate to high molecular weight (MW) NOM, we postulate that 'adsorptive fractionation' of the NOM pool leads to the observed tailing behavior, and develop a novel approach to assess the effects of polydispersity on transport of NOM and associated contaminants. BTCs for different NOM fractions were constructed by separating column effluent MW distributions determined by high-pressure size exclusion chromatography into five discrete intervals or 'bins' and calculating the mass of NOM within each bin at four sampling times. Observed retardation factors (Ro), reflecting median arrival time relative to that of a nonreactive tracer, ranged from 1.4 to 7.9 for the various bins and generally increased with MW. NOM retarded transport of the contaminant metal Cd (2.5 ppm, in 0.01 M NaClO4) slightly at pH 5 and more substantially at pH 8. Although Cd had little or no effect on bulk NOM transport, retention of the more aromatic, IMW-HMW NOM appeared to be slightly enhanced by Cd. Study results demonstrate that heterogeneity in retardation as a function of MW is likely a major factor contributing to bulk NOM BTC tailing and may have important implications for contaminant transport.

Ferritin and ferrihydrite nanoparticles as iron sources for Pseudomonas aeruginosa.

Metabolism of iron derived from insoluble and/or scarce sources is essential for pathogenic and environmental microbes. The ability of Pseudomonas aeruginosa to acquire iron from exogenous ferritin was assessed; ferritin is an iron-concentrating and antioxidant protein complex composed of a catalytic protein and caged ferrihydrite nanomineral synthesized from Fe(II) and O(2) or H(2)O(2). Ferritin and free ferrihydrite supported growth of P. aeruginosa with indistinguishable kinetics and final culture densities. The P. aeruginosa PAO1 mutant (ΔpvdDΔpchEF), which is incapable of siderophore production, grew as well as the wild type when ferritin was the iron source. Such data suggest that P. aeruginosa can acquire iron by siderophore-independent mechanisms, including secretion of small-molecule reductant(s). Protease inhibitors abolished the growth of the siderophore-free strain on ferritins, with only a small effect on growth of the wild type; predictably, protease inhibitors had no effect on growth with free ferrihydrite as the iron source. Proteolytic activity was higher with the siderophore-free strain, suggesting that the role of proteases in the degradation of ferritin is particularly important for iron acquisition in the absence of siderophores. The combined results demonstrate the importance of both free ferrihydrite, a natural environmental form of iron and a model for an insoluble form of partly denatured ferritin called hemosiderin, and caged ferritin iron minerals as bacterial iron sources. Ferritin is also revealed as a growth promoter of opportunistic, pathogenic bacteria such a P. aeruginosa in diseased tissues such as the cystic fibrotic lung, where ferritin concentrations are abnormally high.

Size-dependent Pb sorption to nanohematite in the presence and absence of a microbial siderophore.

This study focused on the effects of particle size (40, 8.6, and 3.6 nm) and the presence of the microbial ligand desferrioxamine B (DFOB) on Pb(II) sorption to hematite, based on sorption edge experiments (i.e., sorption as a function of pH). Effects of hematite nanoparticle size on sorption edges, when plotted either as sorption density or as % Pb uptake, depended on whether the experiments were normalized to account for differences in specific surface area within the reaction vessels or postnormalized after the fact. Accounting for specific surface area within reaction vessels is needed to maintain comparable ratios of sorbate to sorbent surface sites. When normalized for BET specific surface area (A(s,BET)) within the reaction vessels, the Pb(II) sorption edge shifted ∼0.5 pH units to the left for <10 nm hematite particles, but maximum sorption density (at pH ≥ 6) was unaffected by particle size. DFOB had little or no effect on Pb(II) sorption to <10 nm particles, but DFOB decreased Pb(II) sorption to the 40 nm particles at pH ≥ 6 by ∼20%. Hematite (nano)particle size thus exerts subtle effects on Pb(II) sorption, but the effects may be more pronounced in the presence of a metal complexing agent.

Size-dependent bioavailability of hematite (α-Fe2O3) nanoparticles to a common aerobic bacterium.

The size-dependent bioavailability of hematite (α-Fe(2)O(3)) nanoparticles to obligate aerobic Pseudomonas mendocina bacteria was examined using the natural siderophore-producing wild type strain and a siderophore(-) mutant strain. Results showed that Fe from hematite less than a few tens of nm in size appears to be considerably more bioavailable than Fe associated with larger particles. This increased bioavailability is related to the total available particle surface area, and depends in part on greater accessibility of the Fe to the chelating siderophore(s). Greater bioavailability is also related to mechanism(s) that depend on cell/nanomineral proximity, but not on siderophores. Siderophore(-) bacteria readily acquire Fe from particles <10 nm but must be in direct physical proximity to the nanomineral; the bacteria neither produce a diffusible Fe-mobilizing agent nor accumulate a reservoir of dissolved Fe in supernatant solutions. Particles <10 nm appear to be capable of penetrating the outer cell wall, offering at least one possible pathway for Fe acquisition. Other cell-surface-associated molecules and/or processes could also be important, including a cell-wall associated reducing capability. The increased bioavailability of <10 nm particles has implications for both biogeochemical Fe cycling and applications involving engineered nanoparticles, and raises new questions regarding biogenic influences on adsorbed contaminants.

Roles of siderophores, oxalate, and ascorbate in mobilization of iron from hematite by the aerobic bacterium Pseudomonas mendocina.

In aerobic, circumneutral environments, the essential element Fe occurs primarily in scarcely soluble mineral forms. We examined the independent and combined effects of a siderophore, a reductant (ascorbate), and a low-molecular-weight carboxylic acid (oxalate) on acquisition of Fe from the mineral hematite (alpha-Fe(2)O(3)) by the obligate aerobe Pseudomonas mendocina ymp. A site-directed DeltapmhA mutant that was not capable of producing functional siderophores (i.e., siderophore(-) phenotype) did not grow on hematite as the only Fe source. The concentration of an added exogenous siderophore (1 microM desferrioxamine B [DFO-B]) needed to restore wild-type (WT)-like growth kinetics to the siderophore(-) strain was approximately 50-fold less than the concentration of the siderophore secreted by the WT organism grown under the same conditions. The roles of a reductant (ascorbate) and a simple carboxylic acid (oxalate) in the Fe acquisition process were examined in the presence and absence of the siderophore. Addition of ascorbate (50 microM) alone restored the growth of the siderophore(-) culture to the WT levels. A higher concentration of oxalate (100 microM) had little effect on the growth of a siderophore(-) culture; however, addition of 0.1 muM DFO-B and 100 muM oxalate restored the growth of the mutant to WT levels when the oxalate was prereacted with the hematite, demonstrating that a metabolizing culture benefits from a synergistic effect of DFO-B and oxalate.

Siderophore sorption to clays.

Siderophores are low molecular weight organic ligands exuded by some aerobic organisms and plants to acquire Fe under Fe-limited conditions. The hydroxamate siderophores may sorb to aluminosilicate clays through a variety of mechanisms depending upon the nature of the clay and of the siderophore along with solution conditions such as pH, ionic strength, and presence of metal cations. They may also affect metal binding to clays. Here, we review previous studies of siderophore sorption to aluminosilicate clays; briefly discuss how the techniques of X-ray diffractometry, Fourier-transform infrared spectroscopy, and X-ray absorption spectroscopy may be applied to such studies; review effects of siderophores on metal sorption to clays; and highlight some areas for future research.

Effects of the microbial siderophore DFO-B on Pb and Cd speciation in aqueous solution.

This study investigates the complexation environments of aqueous Pb and Cd in the presence of the trihydroxamate microbial siderophore, desferrioxamine-B (DFO-B) as a function of pH. Complexation of aqueous Pb and Cd with DFO-B was predicted using equilibrium speciation calculation. Synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy at Pb L(III) edge and Cd K edge was used to characterize Pb and Cd-DFO-B complexes at pH values predicted to best represent each of the metal-siderophore complexes. Pb was not found to be complexed measurably by DFO-B at pH 3.0, but was complexed by all three hydroxamate groups to form a totally "caged" hexadentate structure at pH 7.5-9.0. At the intermediate pH value (pH 4.8), a mixture of Pb-DFOB complexes involving binding of the metal through one and two hydroxamate groups was observed. Cd, on the other hand, remained as hydrated Cd2+ at pH 5.0, occurred as a mixture of Cd-DFOB and inorganic species at pH 8.0, and was bound by three hydroxamate groups from DFO-B at pH 9.0. Overall, the solution species observed with EXAFS were consistent with those predicted thermodynamically. However, Pb speciation at higher pH values differed from that predicted and suggests that published constants underestimate the binding constant for complexation of Pb with all three hydroxamate groups of the DFO-B ligand. This molecular-level understanding of metal-siderophore solution coordination provides physical evidence for complexes of Pb and Cd with DFO-B, and is an important first step toward understanding processes at the microbial- and/or mineral-water interface in the presence of siderophores.

Nanominerals, mineral nanoparticles, and Earth systems.

Minerals are more complex than previously thought because of the discovery that their chemical properties vary as a function of particle size when smaller, in at least one dimension, than a few nanometers, to perhaps as much as several tens of nanometers. These variations are most likely due, at least in part, to differences in surface and near-surface atomic structure, as well as crystal shape and surface topography as a function of size in this smallest of size regimes. It has now been established that these variations may make a difference in important geochemical and biogeochemical reactions and kinetics. This recognition is broadening and enriching our view of how minerals influence the hydrosphere, pedosphere, biosphere, and atmosphere.

Dissolved organic matter concentration and quality influences upon structure and function of freshwater microbial communities.

Past studies have suggested that the concentration and quality of dissolved organic matter (DOM) may influence microbial community structure. In this study, we cross-inoculated the bacterial communities from two streams and a dystrophic lake that varied in DOM concentration and chemistry, to yield nine fully crossed treatments. We measured dissolved organic carbon (DOC) concentration and heterotrophic microbial community productivity throughout a 72-h incubation period, characterized DOM quality by molecular weight, and determined microbial community structure at the initial and final time points. Our results indicate that all bacterial inoculate sources had similar effects upon DOC concentration and DOM quality, regardless of the DOM source. These effects included an overall decrease in DOM M (W) and an initial period of DOC concentration variability between 0-24h. In contrast, microbial communities and their metabolic rates converged to profiles that reflected the DOM source upon which they were growing, regardless of the initial bacterial inoculation. The one exception was that the bacterial community from the low-concentration and low-molecular-weight DOM source exhibited a greater denaturing gradient gel electrophoresis (DGGE) band richness when grown in its own DOM source than when grown in the highest concentration and molecular weight DOM source. This treatment also exhibited a higher rate of productivity. In general, our data suggest that microbial communities are selected by the DOM sources to which they are exposed. A microbial community will utilize the low-molecular-weight (or labile) DOM sources as well as parts of the high-molecular-weight (refractory) DOM, until a community develops that can efficiently metabolize the more abundant high-molecular-weight source. This experiment examines some of the complex interactions between microbial community selection and the combined factors of DOM quality and concentration. Our data suggest that the roles of aerobic aquatic heterotrophic bacteria in carbon cycling, as well as the importance of high-molecular-weight DOM as a carbon source, may be more complex than is conventionally recognized.

Comparison of the effects of sonolysis and gamma-radiolysis on dissolved organic matter.

The effects of 640 kHz sonolysis and 60Co gamma-radiolysis on dissolved organic matter (DOM) were compared through UV/ vis absorption spectrometric, dissolved organic carbon concentration ([DOC]), and potentiometric titration analyses. A reverse-phase chromatographic technique was used to compare changes in the DOM hydrophobicity distribution, and a size exclusion chromatographic technique with inline UV-A absorbance, fluorescence, and [DOC] detectors was used to compare changes in the DOM molecular weight distribution. Whereas upon radiolysis major decreases in absorbance and [DOC] were induced and near-total DOC removal was achieved, upon sonolysis there were major decreases in UV/vis absorbance but only minor decreases in [DOC], and a substantial quantity of hydrophilic nonchromophoric material remained in solution. In radiolysis, hydrophilic and hydrophobic DOM solution components were exposed to equal hydroxyl radical (*OH) concentrations. However, in sonolysis, hydrophobic DOM components were exposed to more elevated *OH concentrations than the hydrophilic components and consequently had enhanced rates of degradation. Sonolysis may be of interest in the design of advanced oxidation processes in which the selective elimination of hydrophobic solution components, such as hydrophobic organic contaminants and hydrophobic DOM domains into which they partition, is desired.

Hydrogeochemical controls on the organic matter and bacterial ecology of a small freshwater wetland in the New Jersey Pine Barrens.

This study investigated the effects of variable ground-water/surface-water exchange and photoinduced processes on longitudinal patterns in dissolved organic matter (DOM) and bacterial communities in a small first-order stream in the New Jersey Pine Barrens. DOM concentration, along with DOM weight average molecular weight (Mw) and absorptivity (epsilon280, an estimator of aromaticity), and bacterial cell counts all decreased from the stream and hyporheic zone into the shallow aquifer in a ground-water recharge zone. Further downstream, influx of ground water into the stream resulted in a lower Mw DOM pool and was accompanied by decreased cell counts. The observed effect of this ground-water discharge on bacterial numbers may be direct, if discharge temporarily dilutes cell counts, or indirect, if changes in DOM concentration and properties control the bacterial community. In either case, this study suggested the importance of considering ground-water-surface-water exchange in studies of longitudinal changes in the bacterial communities of streams.

A comparison of surface water natural organic matter in raw filtered water samples, XAD, and reverse osmosis isolates.

This research compared raw filtered waters (RFWs), XAD resin isolates (XAD-8 and XAD-4), and reverse osmosis (RO) isolates of several surface water samples from McDonalds Branch, a small freshwater fen in the New Jersey Pine Barrens (USA). RO and XAD-8 are two of the most common techniques used to isolate natural organic matter (NOM) for studies of composition and reactivity; therefore, it is important to understand how the isolates differ from bulk (unisolated) samples and from one another. Although, any comparison between the isolation methods needs to consider that XAD-8 is specifically designed to isolate the humic fraction, whereas RO concentrates a broad range of organic matter and is not specific to humics. The comparison included for all samples: weight average molecular weight (Mw), number average molecular weight (Mn), polydispersity (rho), absorbance at 280 nm normalized to moles C (epsilon280) (RFW and isolates); and for isolates only: elemental analysis, % carbon distribution by 13C NMR, and aqueous FTIR spectra. As expected, RO isolation gave higher yield of NOM than XAD-8, but also higher ash content, especially Si and S. Mw decreased in the order: RO > XAD-8 > RFW > XAD-4. The Mw differences of isolates compared with RFW may be due to selective isolation (fractionation), or possibly in the case of RO to condensation or coagulation during isolation. 13C NMR results were roughly similar for the two methods, but the XAD-8 isolate was slightly higher in 'aromatic' C and the RO isolate was slightly higher in heteroaliphatic and carbonyl C. Infrared spectra indicated a higher carboxyl content for the XAD-8 isolates and a higher ester:carboxyl ratio for the RO isolates. The spectroscopic data thus are consistent with selective isolation of more hydrophobic compounds by XAD-8, and also with potential ester hydrolysis during that process, although further study is needed to determine whether ester hydrolysis does indeed occur. Researchers choosing between XAD and RO isolation methods for NOM need to consider first the purpose of the isolation; i.e., whether humic fractionation is desirable. Beyond that, they should consider the C yield and ash content, as well as the potential for alteration of NOM by ester hydrolysis (XAD) or condensation/coagulation (RO). Furthermore, the RO and XAD methods produce different fractions or isolates so that researchers should be careful when comparing the compositions and reactivities of NOM samples isolated by these two different techniques.