Arsenic redox transformation by humic substances and Fe minerals

The toxicity and mobility of the redox-active metalloid As strongly depends on its oxidation state, with As(III) (arsenite) being more toxic and mobile than As(V) (arsenate). It is, therefore, necessary to know the biogeochemical processes potentially influencing As redox state to understand and predict its environmental behavior. The first part of this presentation will discuss the quantification of As redox changes by pH-neutral mineral suspensions of goethite [α-Fe^IIIOOH] amended with Fe(II) using wet-chemical and synchrotron X-ray absorption (XANES) analysis (Amstaetter et al., 2010). First, it was found that goethite itself did not oxidize As(III). Second, in contrast to thermodynamic predictions, Fe(II)–goethite systems did not reduce As(V). However, surprisingly, rapid oxidation of As(III) to As(V) was observed in Fe(II)–goethite systems. Iron speciation and mineral analysis by Mössbauer spectroscopy showed rapid formation of ⁵⁷Fe–goethite after ⁵⁷Fe(II) addition and the formation of a so far unidentified additional Fe(II) phase. No other Fe(III) phase could be detected by Mössbauer spectroscopy, EXAFS, scanning electron microscopy, X-ray diffraction or high-resolution transmission electron microscopy. This suggests that reactive Fe(III) species form as an intermediate Fe(III) phase upon Fe(II) addition and electron transfer into bulk goethite but before crystallization of the newly formed Fe(III) as goethite.The second part of the presentation will show that semiquinone radicals produced during microbial or chemical reduction of a humic substance model quinone (AQDS, 9,10-anthraquinone-2,6-disulfonic acid) can react with As and change its redox state (Jiang et al., 2009). The results of these experiments showed that these semiquinone radicals are strong oxidants and oxidize arsenite to arsenate, thus decreasing As toxicity and mobility. The oxidation of As(III) depended strongly on pH. More arsenite (up to 67.3%) was oxidized at pH 11 compared to pH 7 (12.6% oxidation) and pH 3 (0.5% oxidation). In addition to As(III) oxidation by semiquinone radicals, hydroquinones that were also produced during quinone reduction, reduced As(V) to As(III) at neutral and acidic pH values (less than 12%) but not at alkaline pH. In an attempt to understand the observed redox reactions between As and reduced/oxidized quinones present in humic substances, the radical content in reduced AQDS solutions was quantified and Eh-pH diagrams were constructed. Both the radical quantification and the Eh-pH diagram allowed explaining the observed redox reactions between the reduced AQDS solutions and the As.In summary these studies indicate that in the simultaneous presence of Fe(III) oxyhydroxides, Fe(II), and humic substances as commonly observed in environments inhabited by Fe-reducing microorganisms, As(III) oxidation can occur. This potentially explains the presence of As(V) in reduced groundwater aquifers.     

Unique properties of humic substances from sapropel

Doklady Earth Sciences - Sapropel from inland Russian water reservoirs is becoming a popular raw material for medicinal purposes, production of sorbents, organomineral fertilizers, and food...     

Interactions between magnetite and humic substances: redox reactions and dissolution processes

Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe₃O₄) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.

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The relationship between molecular composition and fluorescence properties of humic substances

The quantity and quality of dissolved organic matters have been widely characterized by fluorescence spectroscopy, yet the relationship between the fluorescence properties of dissolved organic matters and its molecular composition remains poorly described in the literature. Here, we measured the fluorescence excitation–emission matrix of 17 well-characterized humic substance standards to determine a range of fluorescence parameters, including classical fluorescence indices (e.g., fluorescence index, biological index and humification index) and parameters derived from parallel factor analysis (e.g., component contribution). Relationships between humic substance’s fluorescence and compositional parameters were then statistically examined using canonical correspondence and simple correlation analyses. The canonical correspondence analysis generally suggested that most fluorescence parameters determined here are highly associated with the amount of aliphatic and aromatic compounds in humic substances. However, the correlation analysis between single molecular and fluorescence parameters indicated that the fluorescence properties of humic substances including the parallel factor analysis component contribution also significantly correlate well with several aspects of the molecular composition of humic substances, such as elemental composition, carbon species, acidic functional group and iron complexation. Overall, our results suggest that measurement of humic substance’s fluorescence is beneficial in understanding the molecular composition and environmental functions of dissolved organic matters in natural and engineered waters.     

Aggregation of aquatic humic substances

Humic substances (HS) were isolated from Penwhirn Reservoir (PR) and Esthwaite Water (EW) and their removal from solution by centrifugation was studied as a function of pH, humic concentration and molecular weight, and CaCl₂ concentration. Large amounts (up to 50%) of PR HS could be removed but only small amounts (? 3%) of EW HS. At pH ? 5 removal of PR HS by Ca²⁺ can be explained satisfactorily in terms of decreases in humic solubilities induced by complexation with the cation. However, removal induced by protonation of the PR HS is unusual in that it decreases with increasing humic concentration.The results suggest that PR HS comprise a range of molecules differing in solubility, with the high-molecular-weight (40,000) components being the least soluble. The EW HS consist of molecules of weight-average molecular weight 5000 and resemble similarly sized PR HS in that they remain unaggregated in solution even when highly complexed with Ca²⁺.     

Molecular size of aquatic humic substances

Aquatic humic substances, which account for 30 to 50% of the organic carbon in water, are a principal component of aquatic organic matter. The molecular size of aquatic humic substances, determined by small-angle X-ray scattering, varies from 4.7 to 33 Å in their radius of gyration, corresponding to a molecular weight range of 500 to greater than 10,000. The aquatic fulvic acid fraction contains substances with molecular weights ranging from 500 to 2000 and is monodisperse, whereas the aquatic humic acid fraction contains substances with molecular weights ranging from 1000 to greater than 10,000 and is generally polydisperse.     

Assessing the redox properties of iron-bearing clay minerals using homogeneous electrocatalysis

Iron-bearing clay minerals are ubiquitous in the environment and have been shown to play important roles in several biogeochemical processes. Previous efforts to characterize the Fe²⁺–Fe³⁺ redox couple in clay minerals using electrochemical techniques have been limited by experimental difficulties due to inadequate reactivity between clay minerals and electrodes. The current work overcomes this limitation by utilizing organic electron transfer mediators that rapidly transfer electrons with both the Fe-bearing clay minerals and electrodes. Here, an Fe-rich source clay mineral (ferruginous smectite, SWa-1) is examined with respect to what fraction of structural Fe participates in oxidation/reduction reactions and the relationship between bulk Fe²⁺/Fe³⁺ ratios to the reduction potential (E_h).     

The luminescent humic substances in speleothems

Calcite speleothems deposited in caves by seepage waters derived from the overlying soils of the epikarst are typically coarsely crystalline, colored various shades of brown through orange and white, and strongly luminescent. For most speleothems, the color and luminescence is due to humic substances incorporated in the calcite crystals. For a quantitative assessment of the luminescent properties of these materials, the organic content of the dissolved speleothems was separated by gel chromatography and spectra measured as a function of molecular weight. The most intense luminescence was obtained from molecular weight fractions in the range of 4000–6000 daltons, a range characteristic of fulvic acids. In addition, there was considerable variation in detail from sample to sample that would merit further investigation.     

Phosphorus in marine and non-marine humic substances

The phosphorus content of marine humic acids (HA) is in the range of 0.1–0.2%. The C/P ratios of the HA are 300 to 400. Marine fulvic acids (FA) contain 0.4–0.8% P and have C/P ratios of 80 to 100. High molecular weight organic matter dissolved in pore waters (DOM) contains 0.5% P and has C/P of 90. The data suggest that during the formation sequence: Plankton → DOM → FA → HA → Kerogen, phosphorus is lost, mainly in the FA → HA (and possibly also in the HA → Kerogen) step. Diagenesis of sedimentary humic acids is accompanied by loss of phosphorus (as well as of nitrogen) to form HA with C/P ratios of 1000.Soil humic substances resemble marine humates in P content (0.3%) and soil FA's are about three to fivefold enriched in P relative to HA. C/P ratios are lower in soil HA (ca. 200) as compared with marine HA. Humic acids from diagenetic products such as peat and lignite are highly depleted in P. Rough calculations indicate that humate bound P may account for 20–50% of the organic phosphorus reservoir in sediments. The chemical speciation of this P is unknown, but lack of correlation with ash, Fe, Ca or Al content (in marine humates, at least) indicates that it is organically bound.     

Thermal characterization of natural and synthetic humic substances

Thermogravimetric technique was used for the characterization of natural (humic) and synthetic (melanoidins) substances. The influence of pH on the thermal stability of humic substances was studied. A similarity in thermal behaviour of natural humic substances and of melanoidins (prepared from an excess of sugar) and the unique thermal properties of melanoidins (prepared from basic amino acids) was observed. Thermal behavior of natural and synthetic substances was compared with model compounds of sugar, peptide and kerogen types.     

The adsorption of aquatic humic substances by iron oxides

The interactions of humic substances from Esthwaite Water with hydrous iron oxides (α-FeOOH, α-Fe₂O₃, amorphous Fe-gel) have been examined by measuring adsorption isotherms and by microelectrophoresis. In Na⁺-Cl^?-HCO₃^?at I = 0.002 M (medium I) the extent of adsorption decreases with increasing pH. The results are consistent with a mechanism involving ligand exchange of humic anionic groups with H₂O and OH^?of surface Fe-OH₂⁺and Fe-OH groups respectively, with an increasing degree of protonation of the adsorbed humics as the adsorption density increases at constant pH.At pH 7 in a medium containing Mg²⁺, Ca²⁺ and SO₄^2?, at their Esthwaite Water concentrations and at I= 0.002 M (medium II) the adsorption capacity of goethite (α-FeOOH) is approximately twice that in medium I. Electrophoresis experiments show that the extra capacity is associated with coadsorption of Mg²⁺ and/or Ca²⁺ ions.When the iron oxides are added to samples of Esthwaite Water itself they become negatively charged and plots of electrophoretic mobility against pH for the natural water are identical to those in medium II plus humics.     

An application of soil humic substances to geochemical exploration

The wet temperate climate of Tasmania causes strong leaching of soils and conventional “B” horizon soil geochemistry yields unreliable results. For this reason, most surveys of recent times have been based on “C” horizon sampling which is expensive and often difficult to accomplish in the strongly dissected, heavily vegetated terrain of western Tasmania.A system has been developed based on sampling of the “A” soil horizon, extraction of the humic substances with 0.5 M NH₄OH and determination of the associated metals by atomic absorption spectrometry. The humic substances content of the extract is obtained from quantitative wet oxidation of an aliquot of the sample with 0.4N K₂ Cr₂ O₇.In trials to date this system has yielded results compatible with those obtained from the “C” horizon. It offers a cost effective method of exploration by soil geochemistry and can be carried out with minimal disturbance to the environment.     

Analytical constraints on the structural features of humic substances

A rigorous calculation of the maximum fraction of aromatic carbon in humus or any other complex mixture of organic compounds is described. Input parameters include elemental composition, carboxyl content, carbonyl content, and an estimate of number-average molecular weight. The calculated upper limit constrains structural models that are based on interpretations of ¹³C-NMR spectra or on the products of degradation reactions and also directly limits the phenolic content of a sample.Another computational method is described that yields good estimates of the actual levels of aromatic (and aliphatic) carbon in a humus sample. Even though the method is capable of estimating only the most probable level of aromatic carbon, the predicted values are surprisingly close to the experimental values that have been determined by ¹³C-NMR spectroscopy.     

Sources of sedimentary humic substances: vascular plant debris

A modern Washington continental shelf sediment was fractionated densimetrically using either an organic solvent, CBrCl₃, or aqueous ZnCl₂. The resulting low density materials (<2.06 g/ml) account for only 1% of the sediment mass but contain 25% of the sedimentary organic carbon and 53% of the lignin. The C/N ratios (30–40) and lignin phenol yields ($\text{Λ = 8}$) and compositions indicate that the low density materials are essentially pure vascular plant debris which is slightly enriched in woody (versus nonwoody) tissues compared to the bulk sediment. The low density materials yield approximately one-third of their organic carbon as humic substances and contribute 23% and 14% of the total sedimentary humic and fulvic acids, respectively. Assuming that the lignin remaining in the sedimentary fraction is also contained in plant fragments that yield similar levels of humic substances, then 50% and 30% of the total humic and fulvic acids, respectively, arise directly from plant debris.Base-extraction of fresh and naturally degraded vascular plant materials reveals that significant levels of humic and fulvic acids are obtained using classical extraction techniques. Approximately 1–2% of the carbon from fresh woods and 10–25% from leaves and bark were isolated as humic acids and 2–4 times those levels as fulvic acids. A highly degraded hardwood yielded up to 44% of its carbon as humic and fulvic acids. The humic acids from fresh plants are generally enriched in lignin components relative to carbohydrates and recognizable biochemicals account for up to 50% of the total carbon. Humic and fulvic acids extracted directly from sedimentary plant debris could be responsible for a major fraction of the biochemical component of humic substances.     

The adsorption of aquatic humic substances by two oxides of manganese

A study was made of the adsorption of humic substances (HS) by Mn₃O₄ and by oxide B, a preparation with the β-MnOOH diffraction pattern but having a manganese oxidation state of 3.4. The interactions follow trends found for other oxides. Thus in 0.01 mol dm^?3 NaCl adsorption decreases with increasing pH, while it is enhanced by Ca²⁺. The HS adsorb more strongly to the oxide with the higher zero point of charge (Mn₃O₄), while the effect of Ca²⁺ is greater for oxide B.Microelectrophoretic measurements show that the oxide particles take on the electrokinetic characteristics of the adsorbed HS. However it was found that the magnitude of the mobility depends on the underlying oxide surface and on the source of the HS. The electrokinetic properties of the two oxides dispersed in surface water samples of Esthwaite Water, Cumbria, England, can be accounted for by the adsorbed HS together with coadsorbed Ca²⁺.     

Characterization of groundwater humic substances: influence of sedimentary organic carbon

A total of 35 groundwaters from 4 different aquifer systems in Germany are investigated for their physico-chemical properties, dissolved organic C (DOC) and humic and fulvic acids. Humic substances are isolated and characterized for their elemental composition, UV/Vis and fluorescence spectroscopic properties, size distribution by gel permeation chromatography (GPC) and ¹⁴C content. For isolation of sufficient quantities of humic substances a mobile sampling system is developed based on a combination of reverse osmosis (RO) and XAD–8 adsorption chromatography. One of the aquifer systems (Gorleben) covers a wide range of hydrogeochemical conditions, whereas the other 3 aquifer systems (Munich, Franconian Albvorland and Fuhrberg) have less diverse properties. One specific feature of the Gorleben aquifer system is the presence of a very high DOC, which, in contrast to other aquifer systems, contains considerable amounts of aquatic humic acid. This is attributed to the release of aquatic humic substances originating from sedimentary organic C (SOC) that is abundant in Gorleben sediments. The results show that aquatic humic substances from different aquifer systems have dissimilar properties which differ from one another. Systematic differences are found among humic substances from different regions of the Gorleben aquifer system. Such differences are considered to be caused by the mixing of humic substances from the SOC. However, exact quantification of such mixing appears difficult because overlapping effects of different geochemical processes feigning a dissolution of SOC cannot be excluded.     

Sedimentary humic acid and fulvic acid as surface active substances

Surface tension of sedimentary fulvic acid (FA) and humic acid (HA) with molecular weight from < 10,000 to > 300,000 was measured at 5°C and 25°C, over a wide range of concentrations (0.114-107.4 g/l) at pH 8. HA was in the form of sodium humate. Surface tension decreases with an increase in HA and FA concentration and both HA and FA were found to be surface active materials with FA exhibiting the lowest surface tension (31 dynes/cm).Plots of surface tension vs. log concentration gave two straight lines with a break at a certain concentration similar to surfactants. From the concentration at the break point, aggregation concentration (AGC) was determined. For HA with molecular weight above 10,000, the AGC decreased with an increase in molecular weight. The more hydrophobic the HA, the greater was the tendency to form aggregates. Surface excess (surface concentration) was determined (2.3 × 10^?10?5.5 × 10^?10mol/cn²) from the slope of the plot of surface tension vs. log concentration for concentrations lower than the AGC. Adsorption of HA into the surface layer increased with increasing molecular weight of HA.     

Rapid photo-oxidation of Mn(II) mediated by humic substances

The oxidation of Mn(II) by O₂ to Mn(III) or Mn(IV) is thermodynamically favored under the pH and pO₂ conditions present in most near surface waters, but the kinetics of this reaction are extremely slow. This work investigated whether reactive oxygen species, produced through illumination of humic substances, could oxidize Mn at an environmentally relavent rate. The simulated sunlight illumination of a solution containing 200 μM Mn(II) and 5 mg/L Aldrich humic acid buffered at pH 8.1 produced ∼19 μM of oxidized Mn (MnO_x where x is between one and two) after 45 minutes. The major oxidants reponsible for this reaction appear to be photoproduced superoxide radical anion, O₂⁻, and singlet molecular oxygen, ¹O₂. The dependencies of MnO_x formation on Mn(II), humic acid, and H⁺ concentration were characterized. A kinetic model based largely on published rate constants was established and fit to the experimental data. As expected, analysis of the model indicates that the key reaction rate controlling MnO_x production is the rate of decomposition of a MnO₂⁺ complex formed from the reaction of Mn(II) with O₂⁻. This rate is strongly dependent on the Mn(II) complexing ligands in solution. The MnO_x production in the seawater sample taken from Bodega Bay, USA and spiked with 200 μM Mn(II) was well reproduced by the model. Extrapolations from the model imply that Mn photo-oxidation should be a significant reaction in typical surface seawaters. Calculated rates, 5.8 to 55 pM h⁻¹, are comparable to reported rates of biological Mn oxidation, 0.07 to 89 pM h⁻¹. Four fresh water samples that were spiked with 200 μM Mn(II) also showed significant MnO_x production. Based on these results, it appears that Mn photo-oxidation could constitute a significant, and apparently unrecognized geochemical pathway in natural waters.     

Long-living free radicals study of stepwise pyrolyzed melanoidins and humic substances

ESR measurements of stepwise-pyrolyzed melanoidins and humic substances (at various temperatures, mesh size, and pH values) furnished the following information: the melanoidin structure stabilizes the long-living free radicals in a manner similar to humic substances; the g and Ng values of melanoidins are similar to those of the humic substances, the cleavage of CC and CX (X = heteroatom) bonds increases the Ng value. Thermogravimetric curves, weight loss by stepwise pyrolysis, and ¹³C-CP/MAS NMR were found to be in good correlation with ESR data regarding the structural features of melanoidins and humic substances.