Soil Water and Environmental Science (SWES)

The anomalously low affinity of yttrium (Y) for iron (Fe) (oxyhydr)oxides relative to lanthanides with similar ionic radius (e.g., Ho) has been demonstrated in experiments with isolated Fe minerals and in a variety of marine systems that contain high concentrations of solid phase Fe. However, it has not previously been demonstrated to occur during soil genesis, despite the common observation that many soils become enriched in Fe over time. We hypothesized that Y would become progressively depleted in soils relative to Ho with increased weathering. Since, trivalent Y has an anomalously low Misono softness relative to other trivalent ions included in the rare earth element and yttrium group (REY 3+), we also investigated whether soil REY fractionation reflects variation in Misono softness. To test this, we measured trends in total REY concentrations for Hawaiian soils derived from basaltic parent materials aged 0.3-4100 ky, and measured REYs released from the same samples during short-time (3 h) dissolution experiments conducted as part of a previous investigation linking dissolution with surface charge properties (Chorover et al., 2004). The chondrite-normalized Y/Ho ratios in the parent Hawaiian basalt (Chond [Y/ Ho] = 0.998) and continental dust (Chond [Y/Ho] = 0.994) inputs are remarkably similar, and thus we can interpret deviations from Chond [Y/Ho] $ 1.0 to result from soil biogeochemical processes and not source mixing. Between 0.3 and 20 ky, the Chond [Y/Ho] ratio of the subsurface soils decreased from 0.96 ± 0.07(2r) to 0.71 ± 0.05, and then remained unchanged across the rest of the weathering sequence. In contrast, the Chond [Y/Ho] ratio of the surface soils decreased from 0.99 ± 0.07 to 0.76 ± 0.05 at 150 ky and then, most likely due to continued dust inputs, increased to 1.04 ± 0.07 in the oldest soils. Analysis of the short-time dissolution experiments revealed preferential release of Y relative to Ho (and also La relative Pr) at intermediate pH where aqueous REY concentrations are governed by proton competition for adsorption sites. Proton-competition-control over REY release is bounded at high pH by the onset of colloidal dispersion-represented by the point of minimum dissolution (p.m.d.) of Al-and at low pH by the soil's point of zero net charge (p.z.n.c.) and/or when proton-promoted dissolution of REY-containing solids, including Fe-(oxyhydr)oxides, control REY release. Results of our dissolution experiments suggest that complexation of REYs by dissolved organic matter (DOM) does not drive Y-Ho fractionation during pedogenesis, but rather may suppress it. Synthesis of these field and laboratory experiments suggests the Y/Ho ratio decreases early in soil development (<20 ky) when weathering rates are high and competitive proton adsorption affects REY fractionation. Given that Fe-(oxyhydr)oxide sorbents exhibit greater affinity for Ho relative to Y, their prevalent neo-formation during incipient pedogenesis likely plays a central role in Y-Ho fractionation in these soils. Persistence of low Chond [Y/Ho] ratios in the subsurface soils even at 4100 ky suggests Y-Ho fractionation continues, albeit at a slower rate, as weathering proceeds.

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite-water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7-9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In-situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms innersphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8-9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)-Fe bond distances of ~2.92-2.94 and 3.41-3.44 Å, respectively. The As-Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As-Fe bonding mechanisms.

Concentrations of organic acids in prebiotic soils were presumably low, given limitations in abiotic synthesis and the limited lifetimes of organic molecules before the ultraviolet shield developed on early Earth. Prokaryotes, the first landcolonizing organisms, commonly secrete aliphatic carboxylic acids, and, less extensively, secrete aromatic compounds as siderophores and antibiotics. In contrast, secretion of aromatic acids is considerable for fungi, lichens, and vascular plants. Aromatic acids are also produced by degradation of high-molecular-weight compounds from lignin and tannin, both abundant in vascular plants. The proportion of aromatic carboxylic acids in soil solutions therefore probably increased with the evolution of higher order organisms. As biomass of organisms increased over geological time, concentrations of organic acids in soil solutions and, in turn, the extent of ligandpromoted dissolution of minerals probably increased. To elucidate the contribution of ligands during weathering on early Earth, Columbia River basalt was dissolved under oxic and anoxic conditions in the presence (0.001 or 0.01 M) and absence of several organic ligands in batch experiments at pH 6. Release of all elements including Si was enhanced considerably in the presence of organic ligands. Citrate (tridentate) and gallate (tetradentate) increased element release to the greatest extent among the aliphatic and aromatic ligands, respectively. The extent of element mobilization observed for the aliphatic ligands decreased in the order: citrate > oxalate Ϸ malonate, and for the aromatic ligands: gallate > salicylate Ϸ phthalate. The effects of the ligands generally followed trends in cation-ligand stability constants, but aromatic ligands were less effective in element mobilization than aliphatic ligands. One exception was gallate, an aromatic ligand, which significantly enhanced Cu release. Ligand-promoted mobilization of Cu may therefore have increased over geological time with the increase in the proportion of aromatic ligands. In the presence of organic ligands, Fe was mobilized from basalt considerably more than Al even under oxic conditions. Complexation of Fe with organic ligands may have mobilized Fe in Precambrian paleosols where little Al mobility is observed. Extent of P and Y release was minor in ligand-free experiments and considerable with ligands regardless of P O 2. Release of Cu was considerable under oxic conditions, especially with ligands, and minor under anoxic conditions. Mobility patterns of P and Y could thus possibly serve as "organomarkers" (indicative of prevalence of organic ligands in soil solutions) and mobility patterns of Cu could possibly serve as "oxymarkers" (indicative of the presence of molecular oxygen), respectively, in ancient soils.

Dissolved organic matter (DOM), present in many forms in water, can interfere with analysis of organic contaminants by atmospheric pressure ionization-mass spectrometry. A quantitative analysis of this interference, or matrix effect, on organic contaminant target analyte measurements was carried out using un-fractionated and fractionated dissolved natural organic matter from the Suwannee River, GA (SROM), a standard reference material, that was directly infused into the tandem mass spectrometer during multiple reaction monitoring (MRM) of a suite of endocrine disrupting compounds-pharmaceuticals and personal care products (EDC/PPCPs). Most target analytes suffered signal suppression in the presence of both fractionated and un-fractionated SROM, however greater interferences were measured with fractionated relative to bulk SROM. This finding is consistent with the view of organic matter as a supramolecular association of low molecular mass components having separate charged and structural features revealed only after dissociation.

Many industrial locations have identified the need for treatment of polychlorinated biphenyl (PCB) wastes and remediation of PCB-contaminated sites. Biodegradation of PCBs is a potentially effective technology for treatment of PCBcontaminated soils and sludges; however, a practicable remediation technology has not yet been demonstrated. In laboratory experiments, soil slurry microcosms inoculated with microorganisms extracted from PCB-contaminated Hudson River sediments have been used for anaerobic dechlorination of weathered Aroclor 1248 in contaminated soil with a low organic carbon content. Anaerobic incubation was then followed by exposure to air, addition of biphenyl, and inoculation with Pseudomonas sp. LB400, an aerobic PCB degrader. The sequential anaerobic-aerobic treatment constituted an improvement compared to anaerobic or aerobic treatment alone by reducing the total amount of PCBs remaining and decreasing the tendency for end products to accumulate in humans. A 70% reduction of PCBs was observed during sequential treatment with products containing fewer chlorines and having a shorter half-life in humans than the original PCBs. The aerobic treatment alone was also quite effective as a stand-alone treatment reducing the PCBs by 67%. The results represent a case in Which anaerobic river sediment organisms have been successfully transferred to a matrix free of river or lake sediments.

Desert mine tailings may accumulate toxic metals in the near surface centimeters because of low water through-flux rates. Along with other constraints, metal toxicity precludes natural plant colonization even over decadal time scales. Since unconsolidated particles can be subjected to transport by wind and water erosion, potentially resulting in direct human and ecosystem exposure, there is a need to know how the lability and form of metals change in the tailings weathering environment. A combination of chemical extractions, X-ray diffraction, micro-X-ray fluorescence spectroscopy, and micro-Raman spectroscopy were employed to study Pb and Zn contamination in surficial arid mine tailings from the Arizona Klondyke State Superfund Site. Initial site characterization indicated a wide range in pH (2.5 to 8.0) in the surficial tailings pile. Ligandpromoted (DTPA) extractions, used to assess plant-available metal pools, showed decreasing available Zn and Mn with progressive tailings acidification. Aluminum shows the inverse trend, and Pb and Fe show more complex pH dependence. Since the tailings derive from a common source and parent mineralogy, it is presumed that variations in pH and "bioavailable" metal concentrations result from associated variation in particle-scale geochemistry. Four sub-samples, ranging in pH from 2.6 to 5.4, were subjected to further characterization to elucidate micro-scale controls on metal mobility. With acidification, total Pb (ranging from 5-13 g kg −1) was increasingly associated with Fe and S in plumbojarosite aggregates. For Zn, both total (0.4-6 g kg −1) and labile fractions decreased with decreasing pH. Zinc was found to be primarily associated with the secondary Mn phases manjiroite and chalcophanite. The results suggest that progressive tailings acidification diminishes the overall lability of the total Pb and Zn pools.

Understanding the interactions of climate, physical erosion, chemical weathering and pedogenic processes is essential when considering the evolution of critical zone systems. Interactions among these components are particularly important to predicting how semiarid landscapes will respond to forecasted changes in precipitation and temperature under future climate change. The primary goal of this study was to understand how climate and landscape structure interact to control chemical denudation and mineral transformation across a range of semiarid ecosystems in southern Arizona. The research was conducted along the steep environmental gradient encompassed by the Santa Catalina Mountains Critical Zone Observatory (SCM-CZO). The gradient is dominated by granitic parent materials and spans significant range in both mean annual temperature (>10°C) and precipitation (>50 cm a À1), with concomitant shift in vegetation communities from desert scrub to mixed conifer forest. Regolith profiles were sampled from divergent and convergent landscape positions in five different ecosystems to quantify how climatelandscape position interactions control regolith development. Regolith development was quantified as depth to paralithic contact and degree of chemical weathering and mineral transformation using a combination of quantitative and semi-quantitative X-ray diffraction (XRD) analyses of bulk soils and specific particle size classes. Depth to paralithic contact was found to increase systematically with elevation for divergent positions at approximately 28 cm per 1000 m elevation, but varied inconsistently for convergent positions. The relative differences in depth between convergent and divergent landscape positions was greatest at the low and high elevation sites and is hypothesized to be a product of changes in physical erosion rates across the gradient. Quartz/Plagioclase (Q/P) ratios were used as a general proxy for bulk regolith chemical denudation. Q/P was generally higher in divergent landscape positions compared to the adjacent convergent hollows. Convergent landscape positions appear to be collecting solute-rich soil-waters from divergent positions thereby inhibiting chemical denudation. Clay mineral assemblage of the low elevation sites was dominated by smectite and partially dehydrated halloysite whereas vermiculite and kaolinite were predominant in the high elevation sites. The increased depth to paralithic contact, chemical denudation and mineral transformation are likely functions of greater water availability and increased primary productivity. Landscape position within a given ecosystem exerts strong control on chemical denudation as a result of the redistribution of water and solutes across the landscape surface. The combined data from this research demonstrates a strong interactive control of climate, landscape position and erosion on the development of soil and regolith.

Human alteration of the nitrogen cycle has stimulated research on nitrogen cycling in many aquatic and terrestrial ecosystems, where analyses of nitrate (NO 3-) by standard laboratory methods are common. A recent study by Colman et al. (Biogeochemistry 84:161-169, 2007) identified a potential analytical interference of soluble iron (Fe) with NO 3-reduction are likely to be highly dependent on microsite properties, both in situ and in the laboratory. The so-called ''ferrous wheel hypothesis'' (Davidson et al., Glob Chang Biol 9:228-236, 2003) remains an unproven, viable explanation for published observations.

Four-fold variation in leaf-litter Ca concentration among 14 tree species growing in a common garden in central Poland was linked to variation in soil pH, exchangeable Ca, soil base saturation, forest floor turnover rates, and earthworm abundance. Given the potential importance of tissue Ca to biogeochemical

Reactions at ionizable functional groups in extracellular polymeric substances (EPS) from Bacillus subtilis are found to affect aqueous phase conformation and adsorption to mineral surfaces. Characterization by HPSEC, XPS, and FTIR indicates a wide range in apparent molecular mass (0.57-128 kDa), with functional group composition depending on cell growth phase (exponential vs stationary) and location in suspension (free vs cell-bound). ATR-FTIR spectroscopy shows complexation and dissociation of protons on acidic functional groups that result in R-helical protein conformation at pH < 2.6 and random coil (unordered) conformation at higher pH (>6). EPS exhibit higher affinity for adsorption to R-FeOOH than amorphous SiO 2 because of surface charge effects. Increased amide II band intensity and an amide I band shift to higher frequency indicate changes in protein structure upon adsorption. Goethite-EPS spectra show emergent vibrations consistent with P-O-Fe bonding, which suggests a role of phosphodiester groups in the adsorption reaction.

The primary objective of this research was to investigate the effects of aliphatic and aromatic low molecular weight organic acids (LMWOAs) on rare earth element and yttrium (REY) release from the phosphate minerals apatite and monazite. Since prior studies have shown that redox status can affect REY partitioning during incongruent dissolution, a secondary objective was to assess the influence of dissolved O 2 concentration. Increasing LMWOA concentrations from 0 to 10 mM resulted in enhanced REY release. In general, REY release increased in the order: no ligand ≈ salicylate b phthalate ≈ oxalate b citrate. REY-ligand stability constants were only useful for predicting REY release for oxalate reacted with apatite and phthalate reacted with monazite. The role of dissolved oxygen in dissolution of the phosphate minerals was mixed and inconsistent. Mineral type was observed to significantly affect REY pattern development. REY release patterns for apatite range from nearly flat to those exhibiting the lanthanide contraction effect (radiusdependent fractionation); whereas, monazite REY release patterns are best described as exhibiting an Mtype lanthanide tetrad effect (radius-independent fractionation). Weathering of apatite in the presence of aliphatic LMWOAs resulted in development of the lanthanide contraction effect fractionation pattern, and the aliphatic LMWOAs further developed MREE and radius-independent fractionation during monazite dissolution. Geochemical and mineral-specific REY signatures may, therefore, have utility for distinguishing the impacts of biota on soil weathering processes on early Earth. The development of such signatures may be mitigated, in part, by accessory mineral composition, the types and concentration of LMWOAs present, and precipitation of secondary minerals.

We have previously suggested that mobility patterns of P and Y in paleosols could serve as "organomarkers" to denote the presence of organic ligands secreted by terrestrial organisms on early Earth. In addition, our data indicate that Cu depletion may provide a viable oxymarker for determining the presence of atmospheric oxygen during soil weathering processes. In this research, we continue pursuing the potential for utilizing these elements as markers by investigating dissolution of Durango apatite (Ca 5 (PO 4) 2.82 (F,Cl,OH) 1.54) and Messina chalcopyrite (CuFeS 2) reacted under batch conditions in the presence and absence of two aliphatic and aromatic organic acids under oxic and anoxic conditions. In general, results show that organic acids enhance element release from apatite (Ca, P and Y) and chalcopyrite (Cu, Fe, and Y), and increasing organic acid concentrations from 1 to 10 mM results in greater dissolution. The aliphatic organic acid citrate enhances mineral dissolution to the greatest extent and dissolution in the presence of aromatic salicylate or absence of ligand is lowest. Release of Ca, P, and Y from apatite was not impacted by dissolved O 2 (g) while release of Cu from chalcopyrite was impacted. Aqueous Cu concentrations at the end of batch experiments with chalcopyrite are four orders of magnitude greater under oxic conditions, whereas Fe concentrations are substantially higher under anoxic conditions. These data support the hypothesis that release of P and Y from apatite is enhanced by organic acids and that Cu release is impacted significantly by dissolved O 2 (g) and, to a lesser extent, organic acids. Thus, it seems plausible that geochemical and mineralogical signatures of P, Y, and Cu may have utility for distinguishing the presence of terrestrial organisms and atmospheric conditions during soil weathering processes on early Earth.

We measured iron isotopic composition of surface (10-20 cm) and subsurface (50-70 cm) basaltic soil horizons from the Island of Maui along a climate gradient (MCG) ranging from 2.2 to 4.2 m mean annual precipitation (MAP). All soil forming factors except climate were conserved. The MCG has a documented decrease in Fe with increasing rainfall that is highly correlated with decreasing mean annual Eh values. We found that increasing MAP from 2.8 to 4.2 m resulted in a surface plus subsurface average increase of 0.56‰ ± 0.09‰ δ 56 Fe with the subsurface consistently 0.33 ± 0.06‰ δ 56 Fe greater than the surface horizons. Based on loss of Fe relative to Nb, Rayleigh fractionation was observed with 10 3 lnα lost-retained values of − 0.37 ± 0.03 and − 0.34 ± 0.04 for the surface and subsurface, respectively. Equivalent 10 3 lnα lost-retained values for the surface and subsurface soils suggests Fe loss is driven by similar mechanisms throughout the soil profile. Our calculated fractionation factor is about 1/3 the magnitude of laboratory determined fractionation factors for Fe reduction, suggesting other processes (organic complexation, Fe re-precipitation) modulate the net Fe loss along the MCG. These results offer field-scale confirmation of laboratory experiments on model systems that show anoxic weathering reactions produce materials enriched in heavy Fe isotopes.

Complexation by humic acid (HA) of basic (quinoline) and neutral (naphthalene) polycyclic aromatic compounds (PACs) was compared using fluorescence spectroscopy and equilibrium dialysis (ED). These compounds sorb to HA via cation exchange and hydrophobic interactions, respectively. Ionization of quinoline strongly affects its sorption to HA; maximum sorption is observed at pH close to log K b (4.92), and competition with H þ and electrolyte cation (Li þ) is evident. Spectroscopic experiments indicate that quinolinium (QH þ) cation fluorescence is quenched via a static mechanism (i.e., a dark complex is formed) when the protonated form is adsorbed via ion exchange to HA. The extent of sorption, calculated from fluorescence data using the Stern-Volmer equation, was compared to independent ED measurements. Although both methods indicated the same trends with solution chemistry, fluorescence quenching data suggested more extensive complexation than that measured using ED. In contrast to ionizable PACs, studied here and previously, interaction of naphthalene with HA is unaffected by changes in solution conditions (pH, ionic strength).

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The formation and structure of hematite aggregates were examined by dynamic and static light scattering techniques. A large range in coagulation kinetics was studied by varying either indifferent electrolyte (KC1) concentration or surface complexing anion (H2PO4) concentration, PT, at pH 6.0 ~ 0.1. Diffusion limited aggregation (DLA) was induced by counterion screening at [KC1] > 80 mM or by surface charge neutralization at Pr = 31 IxM (and ionic strength = 1.0 raM). In DLA, the fractal dimension, de, of aggregates formed by either surface charge neutralization or counterion screening was 1.7 2 0.1. A reduction in the rate of coagulation in KC1 for [KC1] < critical coagulation concentration (CCC) produced an increase in df to 2.1 _+ 0.1. For aggregation induced by phosphate adsorption at constant ionic strength, there was no apparent trend in df with coagulation rate. The value of df was consistently less than 1.8 when reaction limited aggregation (RLA) resulted from surface charge neutralization rather than counterion screening. TEM observations of aggregates formed in the presence or absence of phosphate confirm that, when RLA is induced by phosphate adsorption, resulting aggregates are much looser in structure than those formed by counterion screening. The results suggest that the high-affinity binding of phosphate to hematite may result in a nonrandom distribution of surface charge that facilitates the coalescence of positive and negative charge crystal faces.

Lipopolysaccharides (LPS) are ubiquitous in natural aqueous systems because of bacterial cell turnover and lysis. LPS sorption and conformation at the mineral/water interface are strongly influenced by both solution and surface chemistry. In this study, the interaction of LPS with various surfaces (ZnSe, GeO 2 , ␣-Fe 2 O 3 , ␣-Al 2 O 3) that vary in surface charge and hydrophobicity was investigated using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The presence of Ca 2+ (versus Na +) in LPS solutions resulted in aggregate reorientation and increased sorptive retention. ATR-FTIR spectra of Na-LPS systems are consistent with reduced surface affinity and are similar to those of solution phase LPS. Ca-LPS spectra reveal hydrophobic interactions of the lipid A region at the ZnSe internal reflection element (IRE). However, pH-dependent charge controls Ca-LPS sorption to hydrophilic surfaces (GeO 2 , ␣-Fe 2 O 3 , and ␣-Al 2 O 3), where bonding occurs principally via O-antigen functional groups. As a result of accumulation at the solid-liquid interface, spectra of Ca-LPS represent primarily surface-bound LPS. Variable-angle ATR-FTIR spectra of Ca-LPS systems show depth-dependent trends that occur at the spatial scale of LPS aggregates, consistent with the formation of vesicular structures.

The conformation of amphiphilic lipopolysaccharides (LPS) influences the behavior of free and cell-bound LPS in aqueous environments, including their adhesion to surfaces. Conformational changes in Pseudomonas aeruginosa serotype 10 LPS aggregates resulting from changes in solution pH (3, 6, and 9), ionic strength [I] 1, 10, and 100 mmol L −1 , and electrolyte composition (NaCl and CaCl 2) were investigated via attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy. ATR-FTIR data indicate that LPS forms more stable aggregates in NaCl relative to CaCl 2 solutions. Time-and cation-dependent changes in ATR-FTIR data suggest that LPS aggregates are perturbed by Ca 2+ complexation at lipid A phosphoryl groups, which leads to reorientation of the lipid A at the surface of a ZnSe ATR internal reflection element (IRE). Polarized ATR-FTIR investigations reveal orientation of LPS dipoles approximately perpendicular to the IRE plane for both Na-and Ca-LPS. The results indicate that changes in solution chemistry strongly impact the conformation, intermolecular and interfacial behavior of LPS in aqueous systems.

Prior infrared spectroscopic studies of extracellular polymeric substances (EPS) and live bacterial cells have indicated that organic phosphate groups mediate cell adhesion to iron oxides via inner-sphere P-OFe surface complexation. Since cell membrane phospholipids are a potential source of organic phosphate groups, we investigated the adhesion of phospholipidic vesicles to the surfaces of the iron (oxyhydr)oxides goethite (␣-FeOOH) and hematite (␣-Fe 2 O 3) using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. l-␣-Phosphatidylcholine (PC), phosphatidylethanolamine (PE) and phosphatidic acid (PA) were used because they are vesicle forming phospholipids representative of prokaryotic and eukaryotic cell surface membranes. Phospholipid vesicles, formed in aqueous suspension, were characterized by transmission electron microscopy (TEM), multi-angle laser light scattering (MALS) and quasi-elastic light scattering (QELS). Their adhesion to goethite and hematite surfaces was studied with ATR-FTIR at pH 5. Results indicate that PC and PE adsorption is affected by electrostatic interaction and Hbonding (PE). Conversely, adsorption of PA involves phosphate inner-sphere complexes, for both goethite and hematite, via P-OFe bond formation. Biomolecule adsorption at the interface was observed to occur on the scale of minutes to hours. Exponential and linear increases in peak intensity were observed for goethite and hematite, respectively. Our ATR-FTIR results on the PA terminal phosphate are in good agreement with those on EPS reacted with goethite and on bacterial cell adhesion to hematite. These findings suggest that the plasma membrane, and the PA terminal phosphate in particular, may play a role in mediating the interaction between bacteria and iron oxide surfaces during initial stages of biofilm formation.