Carin Sjöstedt

Chromium(III) Complexation to Natural Organic Matter: Mechanisms and Modeling

Chromium is a common soil contaminant, and it often exists as chromium(III). However, limited information exists on the coordination chemistry and stability of chromium(III) complexes with natural organic matter (NOM). Here, the complexation of chromium(III) to mor layer material and to Suwannee River Fulvic Acid (SRFA) was investigated using EXAFS spectroscopy and batch experiments. The EXAFS results showed a predominance of monomeric chromium(III)-NOM complexes at low pH (<5), in which only Cr···C and Cr-O-C interactions were observed in the second coordination shell. At pH > 5 there were polynuclear chromium(III)-NOM complexes with Cr···Cr interactions at 2.98 Å and for SRFA also at 3.57 Å, indicating the presence of dimers (soil) and tetramers (SRFA). The complexation of chromium(III) to NOM was intermediate between that of iron(III) and aluminum(III). Chromium(III) complexation was slow at pH < 4: three months or longer were required to reach equilibrium. The results were used to constrain chromium-NOM complexation in the Stockholm Humic Model (SHM): a monomeric complex dominated at pH < 5, whereas a dimeric complex dominated at higher pH. The optimized constant for the monomeric chromium(III) complex was in between those of the iron(III) and aluminum(III) NOM complexes. Our study suggests that chromium(III)-NOM complexes are important for chromium speciation in many environments.

Chemical Equilibrium Modeling of Organic Acids, pH. Aluminum, and Iron in Swedish Surface Waters

A consistent chemical equilibrium model that calculates pH from charge balance constraints and aluminum and iron speciation in the presence of natural organic matter is presented. The model requires input data for total aluminum, iron, organic carbon, fluoride, sulfate, and charge balance ANC. The model is calibrated to pH measurements (n = 322) by adjusting the fraction of active organic matter only, which results in an error of pH prediction on average below 0.2 pH units. The small systematic discrepancy between the analytical results for the monomeric aluminum fractionation and the model results is corrected for separately for two different fractionation techniques (n = 499) and validated on a large number (n = 3419) of geographically widely spread samples all over Sweden. The resulting average error for inorganic monomeric aluminum is around 1 µM. In its present form the model is the first internally consistent modeling approach for Sweden and may now be used as a tool for environmental quality management. Soil gibbsite with a log *Ks of 8.29 at 25°C together with a pH dependent loading function that uses molar Al/C ratios describes the amount of aluminum in solution in the presence of organic matter if the pH is roughly above 6.0.

Arsenic adsorption by iron–aluminium hydroxide coated onto macroporous supports: Insights from X-ray absorption spectroscopy and comparison with granular ferric hydroxides

This paper evaluates the arsenic adsorption characteristics of a macroporous polymer coated with coprecipitated iron-aluminium hydroxides (MHCMP). The MHCMP adsorbent-composite fits best with a pseudo-second order model for As(III) and a pseudo-first order kinetic model for As(V). The MHCMP shows a maximum adsorption capacity of 82.3 and 49.6 mg As/g adsorbent for As(III) and As(V) ions respectively, and adsorption followed the Langmuir model. Extended X-ray absorption fine structure showed that binding of As(III) ions were confirmed to take place on the iron hydroxides coated on the MHCMP, whereas for As(V) ions the binding specificity could not be attributed to one particular metal hydroxide. As(III) formed a bidentate mononuclear complex with Fe sites, whereas As(V) indicated on a bidentate binuclear complex with Al sites or monodentate with Fe sites on the adsorbent. The column experiments were run in a well water spiked with a low concentration of As(III) (100 μg/L) and a commercially available adsorbent (GEH(®)102) based on granular iron-hydroxide was used for comparison. It was found that the MHCMP was able to treat 7 times more volume of well water as compared to GEH(®)102, maintaining the threshold concentration of less than 10 μg As/L, indicating that the MHCMP is a superior adsorbent.

Speciation of aluminium, arsenic and molybdenum in excessively limed lakes

The possible existence of the potentially toxic oxyanions of Al (Al(OH)(4)(-)), As (HAsO(4)(2-)), and Mo (MoO(4)(2-)) was examined in excessively limed lakes. In-situ dialysis (MWCO 1 kDa) was performed in the surface and bottom waters of two excessively limed lakes (pH 7.1-7.7) and one acidic lake (pH approximately 5.4). The dialysable metal concentrations were compared to the equilibrium distribution of species as calculated with the geochemical code Visual MINTEQ incorporating the CD-MUSIC and Stockholm Humic models for complexation onto colloidal ferrihydrite and dissolved organic matter. Arsenic and molybdenum in the excessively limed lakes were to a large extent present in the dialysable fraction (>79% and >92% respectively). They were calculated to exist as free or adsorbed oxyanions. Most of the Al was observed to reside in the colloidal fraction (51-82%). In agreement with this, model predictions indicated aluminium to be present mostly as colloids or bound to dissolved organic matter. Only a small fraction was modelled as Al(OH)(4)(-) ions. In most cases, modelled values were in agreement with the dialysis results. The free concentrations of the three oxyanions were mostly low compared to toxic levels.

Vanadate complexation to ferrihydrite: X-ray absorption spectroscopy and CD-MUSIC modelling

Environmental context Vanadium, a metal pollutant from fossil fuels and slags, may be toxic, thereby necessitating an understanding of its environmental chemistry. One important factor that controls the mobility and bioavailability of vanadium is its binding to iron oxides. This study focuses on the characterization and modelling of vanadium adsorption onto ferrihydrite. The new model can be used to simulate the transport and bioavailability of vanadium in the environment. Abstract The mobility of vanadium in the environment is influenced by sorption to metal (hydr)oxides, especially those containing iron. The aim of this study is to understand the adsorption behaviour of vanadium on poorly ordered (two-line) ferrihydrite (Fh). A further objective was to determine the binding mechanism of vanadate(V) to ferrihydrite surfaces in aqueous suspension to constrain the CD-MUSIC surface complexation model. Vanadium adsorption to ferrihydrite was evaluated by batch experiments which included series with different Fh-to-V ratios and pH values. Vanadate(V) adsorption was also evaluated in the presence of phosphate to compete with vanadate(V) for the available surface sites on ferrihydrite. In agreement with earlier studies, vanadate(V) was strongly adsorbed to ferrihydrite and the adsorption increased with decreasing pH. In the presence of phosphate, less vanadate(V) was adsorbed. Analysis by X-ray absorption near-edge structure spectroscopy revealed that the adsorbed vanadium was tetrahedral vanadate(V), VO4, regardless of whether vanadate(V) or vanadyl(IV) was added to the system. Spectra collected by extended X-ray absorption fine structure spectroscopy showed that vanadate(V) is bound primarily as an edge-sharing bidentate complex with V⋯Fe distances around 2.8A. Based on this information, a surface complexation model was set up in which three bidentate vanadate(V) complexes with different degrees of protonation were included. The model provided a satisfactory description of vanadate(V) adsorption over most of the pH and concentration ranges studied, also in the presence of competing phosphate ions.

Release of Si from silicon, a ferrosilicon (FeSi) alloy and a synthetic silicate mineral in simulated biological media.

Unique quantitative bioaccessibility data has been generated, and the influence of surface/material and test media characteristics on the elemental release process were assessed for silicon containing materials in specific synthetic body fluids at certain time periods at a fixed loading. The metal release test protocol, elaborated by the KTH team, has previously been used for classification, ranking, and screening of different alloys and metals. Time resolved elemental release of Si, Fe and Al from particles, sized less than 50 µm, of two grades of metallurgical silicon (high purity silicon, SiHG, low purity silicon, SiLG), an alloy (ferrosilicon, FeSi) and a mineral (aluminium silicate, AlSi) has been investigated in synthetic body fluids of varying pH, composition and complexation capacity, simple models of for example dermal contact and digestion scenarios. Individual methods for analysis of released Si (as silicic acid, Si(OH)4) in synthetic body fluids using GF-AAS were developed for each fluid including optimisation of solution pH and graphite furnace parameters. The release of Si from the two metallurgical silicon grades was strongly dependent on both pH and media composition with the highest release in pH neutral media. No similar effect was observed for the FeSi alloy or the aluminium silicate mineral. Surface adsorption of phosphate and lactic acid were believed to hinder the release of Si whereas the presence of citric acid enhanced the release as a result of surface complexation. An increased presence of Al and Fe in the material (low purity metalloid, alloy or mineral) resulted in a reduced release of Si in pH neutral media. The release of Si was enhanced for all materials with Al at their outermost surface in acetic media.