Oxide- and Silicate-Water Interfaces and Their Roles in Technology and the Environment.

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

Surface Site Density of Synthetic Goethites and Its Relationship to Atomic Surface Roughness and Crystal Size.

The capacity for crystals to adsorb elements and molecules is a function of the structures of their crystal faces and the relative proportions of those faces. More importantly, this study shows that the surface structure of crystal faces is affected by their surface roughness and is the dominant factor controlling the absorption site density. In a continuation of the study of synthetic goethites with varying single crystal size distributions, two more synthetic goethites with intermediate sizes were analyzed by Brunauer-Emmett-Teller (BET) and atomic-resolution scanning transmission electron microscopy (STEM) to determine the effects of crystal size on their shape, atomic-scale surface roughness, and ultimately on their total surface site density. Results show that surface roughness scales directly with the size [or inversely with the specific surface area (SSA)] of synthetic goethites in the SSA range of 40-75 m2/g. This surface roughness, in turn, increases the total site density over ideal atomically smooth crystals. The total site density of synthetic goethite increases from a combination of decreasing crystal length/width ratio and increasing surface roughness.

Autopoiesis, Thermodynamics, and the Natural Drift of Living Beings: Another Way to the New Evolutionary Synthesis.

The New Evolutionary Synthesis (NES) groups a series of theories that, departing from the gene-centric approach of Modern Synthesis evolutionary theory (MS), place the organism as the central agent of evolution. Two versions of NES, each one with advantages and disadvantages, can be distinguished in this regard; the restrictive NES and the comprehensive NES. Comparatively, the comprehensive NES is a more robust theoretical construction than the restrictive one because it comes grounded on a general, thermodynamically informed theory of living beings (something that the restrictive NES lacks). However, due to its strong teleological commitments, the comprehensive NES has serious problems fitting with modern science's methodological framework; a problem that the restrictive version, with no explicit commitment to teleology, does not face. In this paper, we propose the autopoietic approach to evolution as a way of integrating these two versions of NES, combining the theoretical robustness of the comprehensive view with the methodological appropriateness of the restrictive one. The autopoietic approach, we show, offers a non-teleological, organism-centered theory of evolution, namely the natural drift theory (NDT), and a grounding on a thermodynamic theory of living beings, namely the embodied autopoietic theory (EAT). We conclude that, from the programmatic point of view, an autopoietic (NDT plus EAT) approach to evolution offers a promising way to develop the NES project.

Transformation of Hexagonal Birnessite upon Reaction with Thallium(I): Effects of Birnessite Crystallinity, pH, and Thallium Concentration.

We examined the uptake of Tl(I) by two hexagonal birnessites and related phase transformations in laboratory experiments over 12 sequential additions of 0.01 M Tl(I)/Mn at pH 4.0, 6.0, and 8.0. The Tl-reacted Mn oxides were characterized for their structure, Tl binding, and morphology using X-ray diffraction, X-ray photoelectron and X-ray absorption spectroscopies, and transmission electron microscopy. Very limited Tl oxidation was observed in contrast to previous works, where equal Tl(I)/Mn was added in a single step. Instead, both birnessites transformed into a 2 × 2 tunneled phase with dehydrated Tl(I) in its tunnels at pH 4, but only partially at pH 6, and at pH 8.0 they remained layered. The first four to nine sequential Tl(I)/Mn additions resulted in lower residual dissolved Tl+ concentrations than when the same amounts of Tl(I)/Mn were added in single steps. This study thus shows that the repeated reaction of hexagonal birnessites with smaller Tl(I)/Mn at ambient temperature triggers a complete phase conversion with Tl(I) as the sole reacting cation. The novel pathway found may be more relevant for contaminated environments and may help explain the formation of minerals like thalliomelane [Tl+(Mn7.54+Cu0.52+)O16]; it also points to the possibility that other reducing species trigger similar Mn oxide transformation reactions.

The Energy Homeostasis Principle: A Naturalistic Approach to Explain the Emergence of Behavior.

It is still elusive to explain the emergence of behavior and understanding based on its neural mechanisms. One renowned proposal is the Free Energy Principle (FEP), which uses an information-theoretic framework derived from thermodynamic considerations to describe how behavior and understanding emerge. FEP starts from a whole-organism approach, based on mental states and phenomena, mapping them into the neuronal substrate. An alternative approach, the Energy Homeostasis Principle (EHP), initiates a similar explanatory effort but starts from single-neuron phenomena and builds up to whole-organism behavior and understanding. In this work, we further develop the EHP as a distinct but complementary vision to FEP and try to explain how behavior and understanding would emerge from the local requirements of the neurons. Based on EHP and a strict naturalist approach that sees living beings as physical and deterministic systems, we explain scenarios where learning would emerge without the need for volition or goals. Given these starting points, we state several considerations of how we see the nervous system, particularly the role of the function, purpose, and conception of goal-oriented behavior. We problematize these conceptions, giving an alternative teleology-free framework in which behavior and, ultimately, understanding would still emerge. We reinterpret neural processing by explaining basic learning scenarios up to simple anticipatory behavior. Finally, we end the article with an evolutionary perspective of how this non-goal-oriented behavior appeared. We acknowledge that our proposal, in its current form, is still far from explaining the emergence of understanding. Nonetheless, we set the ground for an alternative neuron-based framework to ultimately explain understanding.

Protein-conformational diseases in childhood: Naturally-occurring hIAPP amyloid-oligomers and early ß-cell damage in obesity and diabetes.

BACKGROUND AND AIMS: This is the first time that obesity and diabetes mellitus (DM) as protein conformational diseases (PCD) are reported in children and they are typically diagnosed too late, when ß-cell damage is evident. Here we wanted to investigate the level of naturally-ocurring or real (not synthetic) oligomeric aggregates of the human islet amyloid polypeptide (hIAPP) that we called RIAO in sera of pediatric patients with obesity and diabetes. We aimed to reduce the gap between basic biomedical research, clinical practice-health decision making and to explore whether RIAO work as a potential biomarker of early ß-cell damage. MATERIALS AND METHODS: We performed a multicentric collaborative, cross-sectional, analytical, ambispective and blinded study; the RIAO from pretreated samples (PTS) of sera of 146 pediatric patients with obesity or DM and 16 healthy children, were isolated, measured by sound indirect ELISA with novel anti-hIAPP cytotoxic oligomers polyclonal antibody (MEX1). We carried out morphological and functional studied and cluster-clinical data driven analysis. RESULTS: We demonstrated by western blot, Transmission Electron Microscopy and cell viability experiments that RIAO circulate in the blood and can be measured by ELISA; are elevated in serum of childhood obesity and diabetes; are neurotoxics and works as biomarkers of early ß-cell failure. We explored the range of evidence-based medicine clusters that included the RIAO level, which allowed us to classify and stratify the obesity patients with high cardiometabolic risk. CONCLUSIONS: RIAO level increases as the number of complications rises; RIAOs > 3.35 µg/ml is a predictor of changes in the current indicators of ß-cell damage. We proposed a novel physio-pathological pathway and shows that PCD affect not only elderly patients but also children. Here we reduced the gap between basic biomedical research, clinical practice and health decision making.

Fractionation and mobility of thallium in areas impacted by mining-metallurgical activities: Identification of a water-soluble Tl(I) fraction.

Mining and metallurgy generate residues that may contain thallium (Tl), a highly toxic metal, for which it is currently not feasible to determine its geochemical speciation through X-ray absorption spectroscopy due to a combination of very low contents and the interference of accompanying high arsenic contents. Therefore, fractionation studies in residues and soils are required to analyze the mobility and bioavailability of this metal, which in turn provide information to infer its speciation. For this purpose, in this work a modification of the BCR procedure was applied to residues and contaminated soils from three mining zones of Mexico and two mining zones of Spain, spanning samples with acidic to alkaline pH values. The Tl extraction procedure consisted of the following fractions: (1) water-extractable, (2) easily exchangeable and associated to carbonates, associated to (3) poorly-crystalline and (4) crystalline Fe and Mn oxyhydroxides, and (5) associated to organic matter and sulfides; and finally a residual fraction as associated to refractory primary and other secondary minerals. The extracted contents were analyzed by Inductively-Coupled Plasma with Mass Spectrometry. Surprisingly, water-soluble, in Tl(I) oxidation state, was detected in most areas, regardless of the pH, a fact that has not been reported before in these environments, and alerts to potential health risks not previously identified. Most of the samples from a metallurgy area showed high levels of Tl in non-residual fractions and a strong correlation was obtained between extracted Mn and Tl in the third fraction, suggesting its association to poorly crystalline manganese oxides. In the majority of samples from purely mining environments, most of the Tl was found in the residual fraction, most probably bound to alumino-silicate minerals. The remaining Tl fractions were extracted mainly associated to the reducible mineral fractions, and in one case also in the oxidizable fraction (presumably associated to sulfides). Capsule: Soluble Tl(I) was found in all soil samples contaminated with either mining or metallurgical wastes. Additionally, in those affected by metallurgical wastes a very strong Tl-Mn correlation was found.

Iron oxide - clay composite vectors on long-distance transport of arsenic and toxic metals in mining-affected areas.

Mine wastes from abandoned exploitations are sources of high concentrations of hazardous metal(oid)s. Although these contaminants can be attenuated by sorbing to secondary minerals, in this work we identified a mechanism for long-distance dispersion of arsenic and metals through their association to mobile colloids. We characterize the colloids and their sorbed contaminants using spectrometric and physicochemical fractionation techniques. Mechanical action through erosion may release and transport high concentrations of colloid-associated metal(oid)s towards nearby stream waters, promoting their dispersion from the contamination source. Poorly crystalline ferrihydrite acts as the principal As-sorbing mineral, but in this study we find that this nanomineral does not mobilize As independently, rather, it is transported as surface coatings bound to mineral particles, perhaps through electrostatic biding interactions due to opposing surface charges at acidic to circumneutral pH values. This association is very stable and effective in carrying along metal(oid)s in concentrations above regulatory levels. The unlimited source of toxic elements in mine residues causes ongoing, decades-long mobilization of toxic elements into stream waters. The ferrihydrite-clay colloidal composites and their high mobility limit the attenuating role that iron oxides alone show through adsorption of metal(oid)s and their immobilization in situ. This may have important implications for the potential bioavailability of these contaminants, as well as for the use of this water for human consumption.

Crystal Face Distributions and Surface Site Densities of Two Synthetic Goethites: Implications for Adsorption Capacities as a Function of Particle Size.

Two synthetic goethites of varying crystal size distributions were analyzed by BET, conventional TEM, cryo-TEM, atomic resolution STEM and HRTEM, and electron tomography in order to determine the effects of crystal size, shape, and atomic scale surface roughness on their adsorption capacities. The two samples were determined by BET to have very different site densities based on CrVI adsorption experiments. Model specific surface areas generated from TEM observations showed that, based on size and shape, there should be little difference in their adsorption capacities. Electron tomography revealed that both samples crystallized with an asymmetric {101} tablet habit. STEM and HRTEM images showed a significant increase in atomic-scale surface roughness of the larger goethite. This difference in roughness was quantified based on measurements of relative abundances of crystal faces {101} and {201} for the two goethites, and a reactive surface site density was calculated for each goethite. Singly coordinated sites on face {210} are 2.5 more dense than on face {101}, and the larger goethite showed an average total of 36% {210} as compared to 14% for the smaller goethite. This difference explains the considerably larger adsorption capacitiy of the larger goethite vs the smaller sample and points toward the necessity of knowing the atomic scale surface structure in predicting mineral adsorption processes.

Redox Reactions between Mn(II) and Hexagonal Birnessite Change Its Layer Symmetry.

Birnessite, a phyllomanganate and the most common type of Mn oxide, affects the fate and transport of numerous contaminants and nutrients in nature. Birnessite exhibits hexagonal (HexLayBir) or orthogonal (OrthLayBir) layer symmetry. The two types of birnessite contain contrasting content of layer vacancies and Mn(III), and accordingly have different sorption and oxidation abilities. OrthLayBir can transform to HexLayBir, but it is still vaguely understood if and how the reverse transformation occurs. Here, we show that HexLayBir (e.g., δ-MnO2 and acid birnessite) transforms to OrthLayBir after reaction with aqueous Mn(II) at low Mn(II)/Mn (in HexLayBir) molar ratios (5-24%) and pH ≥ 8. The transformation is promoted by higher pH values, as well as smaller particle size, and/or greater stacking disorder of HexLayBir. The transformation is ascribed to Mn(III) formation via the comproportionation reaction between Mn(II) adsorbed on vacant sites and the surrounding layer Mn(IV), and the subsequent migration of the Mn(III) into the vacancies with an ordered distribution in the birnessite layers. This study indicates that aqueous Mn(II) and pH are critical environmental factors controlling birnessite layer structure and reactivity in the environment.

Optimizing the use of natural and synthetic magnetites with very small amounts of coarse Fe(0) particles for reduction of aqueous Cr(VI).

Remediation of highly toxic aqueous Cr(VI) includes its chemical reduction to the very insoluble Cr(III) species. In this work we investigated the Cr(VI) reduction performance of synthetic and natural magnetites of different particle size sat three pH values (4, 6, 8), with the purpose of cost-optimizing the procedure at the laboratory scale. Only the finest magnetite showed considerable Cr(VI) reduction yields, but rates were low and after 25 days no equilibrium was attained. Mechano chemical mixing of the finer magnetites with 5% micron-sized Fe(0) increased dramatically their reductive reactivity, especially at pH 4 and 6, and at pH 8 only for the finest sample, despite the fact that the same quantity of Fe(0) added by itself reducednegligible amounts of Cr(VI). Increasing Fe(0) concentrations in the mixtures to 10 and 15% allowed considerable improvements in the reactivity of the intermediate-sized magnetites (of ca. 7m(2)/g), but not that of the coarser samples for up to 20% Fe(0). This promises to be an optimal technology for remediation or treatment of Cr(VI) polluted aqueous environments and residues, that may prove beneficial for industries and pollution clean-up government agencies, because it uses readily available solid mineral samples and minimizes the use of acid reagents.

Arsenic mobility controlled by solid calcium arsenates: a case study in Mexico showcasing a potentially widespread environmental problem.

An As-contaminated perched aquifer under an urban area affected by mining was studied over a year to determine the contamination source species and the mechanism of As mobilization. Results show that the dissolution of calcium arsenates in residues disposed on an inactive smelter has caused high levels of As pollution in the adjoining downgradient 6-km perched aquifer, reaching up to 158 mg/L of dissolved As, and releasing a total of ca. 7.5 tons of As in a year. Furthermore, free calcium ion availability was found to control As mobility in the aquifer through the diagenetic precipitation of calcium arsenates (Ca5H2(AsO4)4·cH2O) preventing further mobilization of As. Results shown here represent a model for understanding a highly underreported mechanism of retention of arsenate species likely to dominate in calcium-rich environments, such as those in calcareous sediments and soils, where the commonly reported mechanism of adsorption to iron(III) oxyhydroxides is not the dominant process.

Searching for biosignatures using electron paramagnetic resonance (EPR) analysis of manganese oxides.

Manganese oxide (Mn oxide) minerals from bacterial sources produce electron paramagnetic resonance (EPR) spectral signatures that are mostly distinct from those of synthetic simulants and abiogenic mineral Mn oxides. Biogenic Mn oxides exhibit only narrow EPR spectral linewidths (∼500 G), whereas abiogenic Mn oxides produce spectral linewidths that are 2-6 times broader and range from 1200 to 3000 G. This distinction is consistent with X-ray structural observations that biogenic Mn oxides have abundant layer site vacancies and edge terminations and are mostly of single ionic species [i.e., Mn(IV)], all of which favor narrow EPR linewidths. In contrast, abiogenic Mn oxides have fewer lattice vacancies, larger particle sizes, and mixed ionic species [Mn(III) and Mn(IV)], which lead to the broader linewidths. These properties could be utilized in the search for extraterrestrial physicochemical biosignatures, for example, on Mars missions that include a miniature version of an EPR spectrometer.

Goethite surface reactivity: II. A microscopic site-density model that describes its surface area-normalized variability.

The model described in this investigation explains the variable macroscopic surface reactivity of different goethite preparations when adsorption data are normalized by surface area, especially the high reactivity of low specific surface area goethites. A simplified model of crystalline face distributions for each of the goethite preparations, in combination with experimental maximum chromate adsorption values previously determined, allowed a crystallographic site-density analysis that would explain the latter values. In addition, a surface complexation modeling approach was coupled to the previous model and provided individual affinity constants for proton and ion binding for singly, doubly, and triply coordinated surface sites. The proposed microscopic model is able to accurately describe the macroscopic adsorption behavior of protons, carbonate, chromate, and lead(II) ions on three goethites of specific surface areas of 50, 70, and 94 m(2)/g, using the same affinity constants. The model results indicate that the surface of high specific surface area nanoparticulate goethites may be described mostly as a combination of (1 0 1) and (0 0 1) faces, with reactive singly and triply coordinated surface oxygen sites; while the model for low specific surface area goethites requires, in addition to one of the above faces, a variable but high degree of (0 1 0)/(2 1 0) faces containing high surface densities of reactive singly and doubly coordinated oxygen groups. The model is potentially very useful and may be applied to any goethite provided its maximum ion adsorption capacity and proton charging behavior are known.

Midterm survivorship of a press-fit, plasma-sprayed, tri-spike acetabular component.

Press-fit acetabular cups without screw holes can limit migration of particulate wear debris and reduce risk of acetabular osteolysis and device loosening. The Tri-Spike cup (Biomet, Inc, Warsaw, Ind) includes a titanium alloy plasma spray porous surface and does not require screw fixation. We retrospectively examined the incidence of cup loosening and acetabular osteolysis after implantation of 45 cups (44 patients) with mean follow-up of 7.3 years (range, 4-9 years). Only one patient (one cup) had evidence of less than 1 mm of retroacetabular radiolucency at 3 years (nonprogressive), which was found to remain firmly fixed during revision of the aseptically loosened femoral component. No cups were removed or revised at latest follow-up. Projected Kaplan-Meier survivorship at 9 years was 100% for cup loosening/revision and 97.8% for radiolucency.

Goethite surface reactivity: a macroscopic investigation unifying proton, chromate, carbonate, and lead(II) adsorption.

The goethite surface structure has been extensively studied, but no convincing quantitative description of its highly variable surface reactivity as inversely related to its specific surface area (SSA) has been found. The present study adds experimental evidence and provides a unified macroscopic explanation to this anomalous behavior from differences in average adsorption capacities, and not in average adsorption affinities. We investigated the chromate anion and lead(II) cation adsorption behavior onto three different goethites with SSA varying from 50 to 94 m(2)/g, and analyzed an extensive set of published anion adsorption and proton charging data for variable SSA goethites. Maximum chromate adsorption was found to occupy on average from 3.1 to 9.7 sites/nm(2), inversely related to SSA. Congruency of oxyanion and Pb(II) adsorption behavior based on fractional site occupancy using these values, and a site density analysis suggest that: (i) ion binding occurs to singly and doubly coordinated sites, (ii) proton binding occurs to singly and triply coordinated sites (ranging from 6.2 to 8 total sites/nm(2), in most cases), and (iii) a predominance of (210) and/or (010) faces explains the high reactivity of low SSA goethites. The results imply that the macroscopic goethite adsorption behavior may be predicted without a need to investigate extensive structural details of each specific goethite of interest.

Globalization, binational communities, and imported food risks: results of an outbreak investigation of lead poisoning in Monterey County, California.

OBJECTIVES: Although the burden of lead poisoning has decreased across developed countries, it remains the most prevalent environmental poison worldwide. Our objective was to investigate the sources of an outbreak of lead poisoning in Monterey County, California. METHODS: An investigation in 3 county health department clinics in Monterey County, California, was conducted between 2001 and 2003 to identify risk factors for elevated blood lead levels (> or = 10 microg/dL) among children and pregnant women. RESULTS: The prevalence of elevated blood lead levels was significantly higher in 1 of the 3 clinics (6% among screened children and 13% among prenatal patients). Risk factors included eating imported foods (relative risk [RR]=3.4; 95% confidence interval [CI]=1.2, 9.5) and having originated from the Zimatlan area of Oaxaca, Mexico, compared with other areas of Oaxaca (RR=4.0; 95% CI=1.7, 9.5). Home-prepared dried grasshoppers (chapulines) sent from Oaxaca were found to contain significant amounts of lead. CONCLUSIONS: Consumption of foods imported from Oaxaca was identified as a risk factor for elevated blood lead levels in Monterey County, California. Lead-contaminated imported chapulines were identified as 1 source of lead poisoning, although other sources may also contribute to the observed findings. Food transport between binational communities presents a unique risk for the importation of environmental hazards [corrected]

Spatially resolved characterization of biogenic manganese oxide production within a bacterial biofilm.

Pseudomonas putida strain MnB1, a biofilm-forming bacterial culture, was used as a model for the study of bacterial Mn oxidation in freshwater and soil environments. The oxidation of aqueous Mn+2 [Mn+2(aq)] by P. putida was characterized by spatially and temporally resolving the oxidation state of Mn in the presence of a bacterial biofilm, using scanning transmission X-ray microscopy (STXM) combined with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at the Mn L2,3 absorption edges. Subsamples were collected from growth flasks containing 0.1 and 1 mM total Mn at 16, 24, 36, and 48 h after inoculation. Immediately after collection, the unprocessed hydrated subsamples were imaged at a 40-nm resolution. Manganese NEXAFS spectra were extracted from X-ray energy sequences of STXM images (stacks) and fit with linear combinations of well-characterized reference spectra to obtain quantitative relative abundances of Mn(II), Mn(III), and Mn(IV). Careful consideration was given to uncertainty in the normalization of the reference spectra, choice of reference compounds, and chemical changes due to radiation damage. The STXM results confirm that Mn+2(aq) was removed from solution by P. putida and was concentrated as Mn(III) and Mn(IV) immediately adjacent to the bacterial cells. The Mn precipitates were completely enveloped by bacterial biofilm material. The distribution of Mn oxidation states was spatially heterogeneous within and between the clusters of bacterial cells. Scanning transmission X-ray microscopy is a promising tool for advancing the study of hydrated interfaces between minerals and bacteria, particularly in cases where the structure of bacterial biofilms needs to be maintained.

Mechanisms of Pb(II) sorption on a biogenic manganese oxide.

Macroscopic Pb(II) uptake experiments and Pb L3-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to examine the mechanisms of Pb(II) sequestration by a biogenic manganese oxide and its synthetic analogues, all of which are layer-type manganese oxides (phyllomanganates). Relatively fast Pb(II) sorption was observed, as well as extremely high sorption capacities, suggesting Pb incorporation into the structure of the oxides. EXAFS analysis revealed similar uptake mechanisms regardless of the specific nature of the phyllomanganate, electrolyte background, total Pb(II) loading, or equilibration time. One Pb-O and two Pb-Mn shells at distances of 2.30, 3.53, and 3.74 A, respectively, were found, as well as a linear relationship between Brunauer-Emmett-Teller (BET; i.e., external) specific surface area and maximum Pb(II) sorption that also encompassed data from previous work. Both observations support the existence of two bonding mechanisms in Pb(II) sorption: a triple-corner-sharing complex in the interlayers above/ below cationic sheet vacancies (N theoretical = 6), and a double-corner-sharing complex on particle edges at exposed singly coordinated -O(H) bonds (N theoretical = 2). General prevalence of external over internal sorption is predicted, but the two simultaneous sorption mechanisms can account for the widely noted high affinity of manganese oxides for Pb(ll) in natural environments.

Variability in goethite surface site density: evidence from proton and carbonate sorption.

Goethite is a representative iron oxide in natural environments due to its abundance and thermodynamic stability and may be responsible for many surface-mediated processes, including ion retention and mobility in aqueous settings. A large variability in morphologies and specific surface areas of goethite crystals exists but little work has been done to compare surface reactivity between them. The present work offers experimental evidence for the existence of an inverse relationship between sorption capacity for protons and carbonate ions and specific surface area of goethite for three synthetic goethite preparations spanning surface area differences by a factor of 2. An explanation for this was found by assuming a variable reactive site density between preparations in direct relationship to their sorption capacity based on congruency of carbonate sorption computed on a per-site basis. Previous evidence of maximum sorption capacities supports this explanation, and site density ratios between the goethites studied here were obtained. Triple layer surface complexation modeling was successful in describing adsorption data for all goethite preparations using equal stoichiometries. A new formulation of standard state for activities of surface species based on a 1.0 mole fraction of sites on the solid allowed transformation of the conventional molar concentration-based affinity constants to values based on site occupancy. In this fashion, by applying the appropriate site density ratios, a single set of affinity constant values was found that described accurately the adsorption data for all preparations.