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Journal ArticleDOI

The crystallo-chemistry of oxide-humus complexes

14 Jul 2000-Soil Research (CSIRO PUBLISHING)-Vol. 38, Iss: 4, pp 789-806
Abstract: Complexation of humic substances with goethite, hematite, gibbsite, and boehmite has been explained from a viewpoint of crystal structure of the minerals. Theoretical analysis of crystal surface structures revealed the following. (i) Residual charge carried by O or OH on surfaces of gibbsite is –1/2; on boehmite it is –3/2 or –1/2; on goethite it is –4/3, –2/3, or –1/3; and on hematite it is –3/2, –1, or –1/2. Cations adsorbed to neutralise these charges can form bridging links with humic acid; higher charges form stronger links. (ii) Surfaces of goethite, hematite, and gibbsite also contain octahedral sites in which one O/OH position is vacant. These may provide centres for the formation of strong coordination bonds. (iii) Such vacant octahedral positions are absent in boehmite. It follows that in gibbsite, cation bridging links would be weak and vacant octahedral sites would be the dominant bonding sites; in goethite and hematite, both cation bridging and surface coordination sites would be present; in boehmite, cation bridging would be the only strong bonding mode. Derivations from crystallochemical analysis are supported by experimental observations. Infrared studies also show strong OH involvement in boehmite complexation in contrast to the weakness of OH involvement in gibbsite complexes.
Topics: Gibbsite (59%), Boehmite (54%), Hematite (51%), Goethite (50%)
Citations
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Journal ArticleDOI
Abstract: Mineral-associated organic matter (OM) represents a large reservoir of organic carbon (OC) in natural environments. The factors controlling the extent of the mineral-mediated OC stabilization, however, are poorly understood. The protection of OM against biodegradation upon sorption to mineral phases is assumed to result from the formation of strong bonds that limit desorption. To test this, we studied the biodegradation of OM bound to goethite (α-FeOOH), pyrophyllite, and vermiculite via specific mechanisms as estimated from OC uptake in different background electrolytes and operationally defined as ‘ligand exchange’, ‘Ca2+ bridging’, and ‘van der Waals forces’. Organic matter extracted from an Oa forest floor horizon under Norway spruce (Picea abies (L.) Karst) was reacted with minerals at dissolved OC concentrations of ∼5–130 mg/L at pH 4. Goethite retained up to 30.1 mg OC/g predominantly by ‘ligand exchange’; pyrophyllite sorbed maximally 12.5 mg OC/g, largely via ‘van der Waals forces’ and ‘Ca2+ bridging’, while sorption of OM to vermiculite was 7.3 mg OC/g, mainly due to the formation of ‘Ca2+ bridges’. Aromatic OM components were selectively sorbed by all minerals (goethite ≫ phyllosilicates). The sorption of OM was strongly hysteretic with the desorption into 0.01 M NaCl being larger for OM held by ‘Ca2+ bridges’ and ‘van der Waals forces’ than by ‘ligand exchange’. Incubation experiments under aerobic conditions (initial pH 4; 90 days) revealed that OM mainly bound to minerals by ‘ligand exchange’ was more resistant against mineralization than OM held by non-columbic interactions (‘van der Waals forces’). Calcium bridges enhanced the stability of sorbed OM, especially for vermiculite, but less than the binding via ‘ligand exchange’. Combined evidence suggests that the extent and rate of mineralization of mineral-associated OM are governed by desorption. The intrinsic stability of sorbed OM as related to the presence of resistant, lignin-derived aromatic components appears less decisive for the sorptive stabilization of OM than the involved binding mechanisms. In a given environment, the type of minerals present and the solution chemistry determine the operating binding mechanisms, thereby the extent of OM sorption and desorption, and thus ultimately the bioavailability of mineral-associated OM.

314 citations


Journal ArticleDOI
TL;DR: STXM-NEXAFS spectroscopy was used to investigate C associations with Ca, Fe, Al, and Si species in soil clay fractions from an upland pasture hillslope and showed similar correlation with Fe to Al and Si, implying a similar association of Fe oxides and aluminosilicates with organic matter in organo-mineral associations.
Abstract: There is a growing acceptance that associations with soil minerals may be the most important overarching stabilization mechanism for soil organic matter. However, direct investigation of organo-mineral associations has been hampered by a lack of methods that can simultaneously characterize organic matter (OM) and soil minerals. In this study, STXM-NEXAFS spectroscopy at the C 1s, Ca 2p, Fe 2p, Al 1s, and Si 1s edges was used to investigate C associations with Ca, Fe, Al, and Si species in soil clay fractions from an upland pasture hillslope. Bulk techniques including C and N NEXAFS, Fe K-edge EXAFS spectroscopy, and XRD were applied to provide additional information. Results demonstrated that C was associated with Ca, Fe, Al, and Si with no separate phase in soil clay particles. In soil clay particles, the pervasive C forms were aromatic C, carboxyl C, and polysaccharides with the relative abundance of carboxyl C and polysaccharides varying spatially at the submicrometer scale. Only limited regions in the...

84 citations


Journal ArticleDOI
15 Apr 2004-Energy & Fuels
Abstract: The ability to stabilize water-in-oil (W/O) emulsions for six studied asphaltene subfractions is dependent on their solubility rather than on their concentration, polarity, molecular weight, or other parameters. Paraffinic froth treatment technology recently introduced in the oil sand industry yields a clean bitumen product (<0.1 wt % water and <0.1 wt % solids) at a solvent-to-bitumen ratio above a critical value, which corresponds to the onset of asphaltene precipitation. Six subfractions of Athabasca bitumen asphaltenes were obtained by precipitation with a gradually increasing heptane-to-bitumen (H/B) ratio, from 1.25 to 40. The properties of the asphaltene subfractions obtained were investigated by elemental analysis, Fourier transform infrared (FTIR) and ultraviolet-visible (UV−vis) spectroscopy, and vapor pressure osmometry (VPO). There were no significant differences in the molecular masses of the six asphaltene subfractions. However, the aromaticity and the metalloporphyrin (vanadyl) content in t...

84 citations


Journal ArticleDOI
TL;DR: The sorption of DOC (derived from mature wheat straw) was more strongly affected by SAR than by EC, andDOC sorption in salt-affected soil is more strongly controlled by CEC and Fe/Al concentration than by clay concentration per se except in sodic soils where DOC sorption is low due to the high sodium saturation of the exchange complex.
Abstract: Loss of dissolved organic matter (DOM) from soils can have negative effects on soil fertility and water quality. It is known that sodicity increases DOM solubility, but the interactive effect of sodicity and salinity on DOM sorption and how this is affected by soil texture is not clear. We investigated the effect of salinity and sodicity on DOM sorption in soils with different clay contents. Four salt solutions with different EC and SAR were prepared using combinations of 1 M NaCl and 1 M CaCl 2 stock solutions. The soils differing in texture (4, 13, 24 and 40% clay, termed S-4, S-13, S-24 and S-40) were repeatedly leached with these solutions until the desired combination of EC and SAR (EC 1:5 1 and 5 dS m − 1 in combination with SAR 20) was reached. The sorption of DOC (derived from mature wheat straw) was more strongly affected by SAR than by EC. High SAR (> 20) at EC1 significantly decreased sorption in all soils. However, at EC5, high SAR did not significantly reduce DOC sorption most likely because of the high electrolyte concentration of the soil solution. DOC sorption was greatest in S-24 (which had the highest CEC) at all concentrations of DOC added whereas DOC sorption did not differ greatly between S-40 and S-4 or S-13 (which had higher concentrations of Fe/Al than S-40). DOC sorption in salt-affected soil is more strongly controlled by CEC and Fe/Al concentration than by clay concentration per se except in sodic soils where DOC sorption is low due to the high sodium saturation of the exchange complex.

62 citations


Cites background from "The crystallo-chemistry of oxide-hu..."

  • ...This also highlights the importance of divalent cations such as Ca for DOC sorption (Baldock and Skjemstad, 2000; Mikutta et al., 2007; Varadachari et al., 2000)....

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  • ...This also highlights the importance of divalent cations such as Ca2+ for DOC sorption (Baldock and Skjemstad, 2000; Mikutta et al., 2007; Varadachari et al., 2000)....

    [...]


Journal ArticleDOI
01 Dec 2006-Chemosphere
TL;DR: It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the Humic substances (Type A complexes), cause the deviation from additivity.
Abstract: The study of Pb(II) binding to the system humic acid/goethite in acidic medium is reported in the present paper. From a macroscopic point of view, we have constructed the experimental sorption isotherms (using atomic absorption spectroscopy) and compared them with the prediction of the additivity rule. It is found that this system presents positive deviations, that is, the amount sorbed is about an order of magnitude higher than predicted. Apart from this, microscopic and structural aspects have also been studied using in situ and ex situ infrared spectroscopy. These results suggest that the presence of Pb(II) increases the amount of humic acid bound to the oxide. It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the humic substances (Type A complexes), cause the deviation from additivity.

34 citations


Cites background from "The crystallo-chemistry of oxide-hu..."

  • ...Also, it is possible that in the presence of Pb(II) HA adsorption to goethite would increase, as observed by Varadachari et al. (1997, 2000) for other systems....

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  • ...There are several studies on that interaction; particularly for humic substances–iron oxides showing the formation of complexes (Varadachari et al., 2000; Saito et al., 2004; Fu and Quan, 2005)....

    [...]


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Journal ArticleDOI
Abstract: 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 SO42−, 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.

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