Organo-mineral Colloids Research Articles

Migration of dissolved trace elements in the mixing zone between Volga River water and Caspian seawater: Results of observations over many years

Based on natural observations over many years, the distribution of dissolved nutrients and trace elements was analyzed in the mixing zone between the freshwater of the Volga River and Caspian seawater. Most of the trace elements (Li, Rb, Cs, B, F, Br, I, Ga, Sc, Y, Co, Ni, Cu, Cd, Ag, V, As, Sb, Bi, Mo, W, and U) show a conservative behavior. During the period of the highest bioproductivity, dissolved phosphates and silica are intensely removed from solution (up to 60–90 and 46–82% of their supply by river runoff, respectively) mostly owing to uptake by aquatic organisms. The distribution of dissolved strontium was assigned to the weakly nonconservative type, because a minor excess of its content above the lines of conservative mixing (8–18%) was observed in some years; perhaps, this is related to different water transformation at the areas of moving and stagnant water in the delta and offshore mouth zone. Barium is characterized by additional input into the solution (up to 52%) in the regions of medium salinity owing to ion exchange reactions in the absorbed complex of river suspended material. The migration of dissolved species of aluminum, manganese, and iron in the mixing zone of Volga and Caspian waters is probably controlled by the coagulation and flocculation of organic and organo-mineral colloids, which is indicated by a sharp decrease in the content of these elements during the initial stage of salinization (59, 91, and 74%, respectively) followed by a plateau. The most complicated distribution was observed for titanium, lead, and rare earth elements (REE), the concentrations of which showed intense removal from the solution (up to 64–88% Ti, 52–87% Pb, and 66–83% REE) followed by a gradual increase, which is probably related to the elevated contents of these elements in the water of the northern Caspian above a local minimum in the zone of active flocculation of colloids.

Biogeochemistry of stable Ca and radiogenic Sr isotopes in a larch-covered permafrost-dominated watershed of Central Siberia

Stable Ca and radiogenic Sr isotope compositions were measured in different compartments (stream water, soil solutions, rocks, soils and soil leachates and vegetation) of a small permafrost-dominated watershed in the Central Siberian Plateau. The Sr and Ca in the area are supplied by basalt weathering and atmospheric depositions, which significantly impact the Sr isotopic compositions. Only vegetation significantly fractionates the calcium isotopes within the watershed. These fractionations occur during Ca uptake by roots and along the transpiration stream within the larch trees and are hypothesised to be the result of chromatographic processes and Ca oxalate crystallisations during Ca circulation or storage within plant organs. Biomass degradation significantly influences the Ca isotopic compositions of soil solutions and soil leachates via the release of light Ca, and organic and organo-mineral colloids are thought to affect the Ca isotopic compositions of soil solutions by preferential scavenging of 40Ca. The imprint of organic matter degradation on the δ44/40Ca of soil solutions is much more significant for the warmer south-facing slope of the watershed than for the shallow and cold soil active layer of the north-facing slope. As a result, the available stock of biomass and the decomposition rates appear to be critical parameters that regulate the impact of vegetation on the soil–water system in permafrost areas. Finally, the obtained δ44/40Ca patterns contrast with those described for permafrost-free environments with a much lower δ44/40Ca fractionation factor between soils and plants, suggesting specific features of organic matter decomposition in permafrost environments. The biologically induced Ca isotopic fractionation observed at the soil profile scale is not pronounced at the scale of the streams and large rivers in which the δ44/40Ca signature may be controlled by the heterogeneity of lithological sources.

Using FLOWFFF and HPSEC to determine trace metal–colloid associations in wetland runoff

Natural organic matter (NOM) and iron colloids can coexist in surface water. These colloids might exhibit different affinities to metals and metalloids. Previously it has been shown, that organic and inorganic colloids in the low nanometer range can be fractionated using Flow Field-Flow Fractionation analyzes (FlowFFF), but it is not yet understood how the presence of inorganic colloids influences results obtained by High Performance Size Exclusion Chromatography (HPSEC). Studies that compare the use of these size-separation techniques for the analyzes of organic and inorganic colloids and associated elements are needed in order to interpret results obtained by either of these methods. Therefore, associations between colloids from a small stream draining a wetland area and a selected range of elements (Fe, Al, Ti, Pb, Cu, Ni, As, U, and Rare Earth Elements (REE)) have been investigated. FlowFFF analyzes and HPSEC analyzes were combined with ultrafiltration, functional group titration and arsenic speciation analysis.NOM and, in a sample with a pH > 5.2, slightly larger iron organo-mineral colloids, were present in the <0.2 μm fraction in the surface water. Both exhibited notably different affinities for trace elements. Cu, Ni, Al, and the REE all showed similar modes (i.e. peak maxima) and size distributions to the NOM, while Pb and As showed a preferential association with iron organo-mineral colloids. It was not possible to differentiate between NOM and iron-organo mineral colloids with HPSEC. The differences in the results regarding the apparent molecular mass distributions obtained by FlowFFF and HPSEC are discussed.

Diurnal variations of dissolved and colloidal organic carbon and trace metals in a boreal lake during summer bloom

This work describes variation of element concentration in surface water of a subarctic organic-rich lake during the diurnal cycle of photosynthesis. An unusually hot summer 2010 in European part of subarctic Russia produced elevated surface water temperature (28–30 °C) and caused massive cyanobacterial bloom. Diurnal variation of ∼40 dissolved macro and trace elements and organic carbon were recorded in the humic Lake Svyatoe in the White Sea drainage basin. Two days continuous measurements with 3 h sampling steps at the surface (0.5 m) allowed tracing cyanobacterial activity via pH and O2 measurement and revealed constant concentrations (within ±20–30%) of all major elements (Na, Mg, Cl, SO4, K, Ca), organic and inorganic carbon and most trace elements (Li, B, Sc, Ti, Ni, Cu, Ga, As, Rb, Sr, Y, Zr, Mo, Sb, medium and heavy REEs, Hf, Pb, Th, U). The concentration of Mn demonstrated a factor of 3 decrease during the day following Mn adsorption onto cyanobacterial cells due to ∼1 pH unit raise during the photosynthesis and Mn release during the night due to desorption from the cell surface. The role of Mn(II) photo-oxidation by reactive oxygen species could be also pronounced, although its contribution to Mn diurnal variation was much smaller than the adsorption at the cell surfaces. Similar pattern, but with much lesser variations (c.a., 10–20%), was recorded for Ba and Fe. On-site ultrafiltration technique allowed to distinguish between low molecular weight (LMW) complexes (<1 kDa) and high molecular weight (HMW) colloids (1 kDa–0.22 μm) and to assess their diurnal pattern. Colloidal Al and Fe were the highest during the night, when the contribution of HMW allochthonous colloids was maximal. Typical insoluble trivalent and tetravalent elements exhibited constant complexation (>80–90%) with HMW allochthonous organics, independent on the diel photosynthetic cycle. Finally, biologically-relevant metals (Cu, Co, Cr, V, and Ni) demonstrated significant variations of colloidal fractions (from 10 to 60%) not directly related to the photosynthesis. The majority of possible metal nutrients, being strongly associated with organic and organo-mineral colloids do not exhibit any measurable concentration variation during photosynthesis. The two types of element behavior during cyanobacterial bloom in the water column – constant concentration and sinusoidal variations – likely depend on element speciation in solution and their relative affinity to surfaces of aquatic microorganisms and complexation with authochthonous and allochthonous organic matter.

Organic matter mineralization and trace element post-depositional redistribution in Western Siberia thermokarst lake sediments

Abstract. This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 ± 2 kg m−2 is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions was suggested. This shift was likely promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development, the sediments were a source of dissolved Co, Ni and As to the water column. However, the concentrations of these trace elements remained low in the bottom waters, indicating that sorption processes on Fe-bounding particles and/or large-size organo-mineral colloids could mitigate the impact of post-depositional redistribution of toxic elements on the water column.

Potential Adverse Effects of Applying Phosphate Amendments to Immobilize Soil Contaminants

Seven-day batch equilibrium experiments were conducted to measure the efficacy of four phosphate amendments (trisodium trimetaphosphate [TP3], dodecasodium phytate [Na-IP6], precipitated calcium phytate [Ca-IP6], and hydroxyapatite [HA]) for immobilizing Ni and U in organic-rich sediment. Using the eight-step modified Miller's sequential extraction procedure and the USEPA's Toxicity Characteristic Leaching Procedure, the effect of these amendments on the distribution of Ni and U was assessed. Relative to unamended controls, equilibrium aqueous-phase U concentrations were lower following HA and Ca-IP6 additions but higher following TP3 and Na-IP6 amendments, whereas aqueous Ni concentrations were not decreased only in the Na-IP6 amended treatment relative to the control. The poor rates of contaminant immobilization following TP3 and Na-IP6 amendments correlate with the dispersion of organic matter and organo-mineral colloids, which probably contain sorbed U and Ni. While all amendments shifted the U distribution toward more recalcitrant soil fractions, Ni was redistributed to more labile soil fractions. This study cautions that the addition of orthophosphates and organophosphates as contaminant immobilizing amendments may in fact have adverse effects, especially in high-organic soils. Particular attention is warranted at sites with mixed contaminants with varying geochemical behaviors.

Seasonal variability of element fluxes in two Central Siberian rivers draining high latitude permafrost dominated areas

In order to constrain the origin and fluxes of elements carried by rivers of high latitude permafrost-dominated areas, major and trace element concentrations as well as Sr and U isotopic ratios were analyzed in the dissolved load of two Siberian rivers (Kochechum and Nizhnyaya Tunguska) regularly sampled over two hydrological cycles (2005–2007). Large water volumes of both rivers were also collected in spring 2008 in order to perform size separation through dialysis experiments. This study was completed by spatial sampling of the Kochechum watershed carried out during summer and by a detailed analysis of the main hydrological compartments of a small watershed. From element concentration variations along the hydrological cycle, different periods can be marked out, matching hydrological periods. During winter baseflow period (October to May) there is a concentration increase for major soluble cations and anions by an order of magnitude. The spring flood period (end of May-beginning of June) is marked by a sharp concentration decrease for soluble elements whereas dissolved organic carbon and insoluble element concentrations strongly increase. When the spring flood discharge occurs, the significant increase of aluminum and iron concentrations is related to the presence of organo-mineral colloids that mobilize insoluble elements. The study of colloidal REE reveals the occurrence of two colloid sources successively involved over time: spring colloids mainly originate from the uppermost organic-rich part of soils whereas summer colloids rather come from the deep mineral horizons. Furthermore, U and Sr isotopic ratios together with soluble cation budgets in the Kochechum river impose for soluble elements the existence of three distinct fluxes over the year: (a) at the spring flood a surface flux coming from the leaching of shallow organic soil levels and containing a significant colloidal component (b) a subsurface flux predominant during summer and fall mainly controlled by water–rock interactions within mineral soils and (c) a deep groundwater flux predominant during winter which enters large rivers through unfrozen permafrost-paths. Detailed study of the Kochechum watershed suggests that the contribution of this deep flux strongly depends on the depth and continuous nature of the permafrost.

Effect of permafrost thawing on organic carbon and trace element colloidal speciation in the thermokarst lakes of western Siberia

Abstract. To examine the mechanisms of carbon mobilization and biodegradation during permafrost thawing and to establish a link between organic carbon (OC) and other chemical and microbiological parameters in forming thermokarst (thaw) lakes, we studied the biogeochemistry of OC and trace elements (TEs) in a chronosequence of small lakes that are being formed due to permafrost thawing in the northern part of western Siberia. Twenty lakes and small ponds of various sizes and ages were sampled for dissolved and colloidal organic carbon, metals and culturable heterotrophic bacterial cell number. We observed a sequence of ecosystems from peat thawing and palsa degradation due to permafrost subsidence in small ponds to large, km-size lakes that are subject to drainage to, finally, the khasyrey (drained lake) formation. There is a systematic evolution of both total dissolved and colloidal concentration of OC and TEs in the lake water along with the chronosequence of lake development that may be directly linked to the microbial mineralization of dissolved organic matter and the liberation of the inorganic components (Fe, Al, and TEs) from the organo-mineral colloids. In this chronosequence of lake development, we observed an apparent decrease in the relative proportion of low molecular weight &lt;1 kDa (1 kDa ~ 1 nm) OC concentration along with a decrease in the concentration of total dissolved (&lt;0.45 μm) OC. This decrease was accompanied by an increase in the small size organic ligands (probably autochthonous exometabolites produced by the phytoplankton) and a simultaneous decrease in the proportion of large-size organic (humic) complexes of allochthonous (soil) origin. This evolution may be due to the activity of heterotrophic bacterioplankton that use allochthonous organic matter and dissolved nutrients originating from peat lixiviation. Most insoluble TEs demonstrate a systematic decrease in concentration during filtration (5 μm, 0.45 μm) exhibiting a similar pattern among different samples. At the same time, there is an increase in the relative proportion of large size particles over the &lt;1 kDa fraction for most insoluble elements along the chronosequence of lake evolution. TEs are likely to be bound to colloidal OC and coprecipitate with the mineral (Fe, Al) part of the colloids. Upon progressive consumption of dissolved OC by the heterotrophic bacteria, there is liberation of Fe, Al, and insoluble TEs in the water column that may be subjected to coagulation in the form of particles or large-size mineral colloids.

Thermodynamic indices of active invertase from the buried soil horizons of Late Pleistocene age in northern Yakutia

New data on the enzymatic activity of the tundra peaty gleyey soil and permafrost sediments of Late Pleistocene age (11–25 thousand years) are analyzed. It is shown that invertase, protease, phosphatase, catalase, and peroxidase are well conserved in yedoma and in buried soil horizons; urease is conserved to a smaller extent. On the basis of the investigation of thermodynamic characteristics of active invertase, such as temperature coefficient and activation energy, it was established that this enzyme is present in soil in the free and bound forms (immobilized on the surface of organomineral colloids). The degree of immobilization of active invertase in the buried soil horizons is high, which plays an important part in the long-term conservation of its molecules at subzero temperatures.

Modeling vertical movement of organic matter in a soil incubated for 41 years with 14C labeled straw

The distribution of organic matter (OM) in the soil profile reflects the balance between inputs and decomposition at different depths as well as transport of OM within the profile. In this study we modeled movement of OM in the soil profile as a result of mechanisms resulting in dispersive and advective movement. The model was used to interpret the distribution of 14C in the soil profile 41 years after the labeling event. The model fitted the observed distribution of 14C well ( R 2=0.988, AIC c=−82.6), with a dispersion constant of D=0.71 cm 2 yr −1 and an advection constant of v=0.0081 cm yr −1. However, the model consistently underestimated the amount of OM in the soil layers from 27 to 37 cm depth. A possible explanation for this is that different fractions of OM are transported by different mechanisms. For example, particulate OM, organomineral colloids and dissolved OM are not likely to be transported by the same mechanisms. A model with two OM fractions, one moving exclusively by dispersive processes ( D=0.26 cm 2 yr −1) and another moving by both dispersive ( D=0.99 cm 2 yr −1) and advective ( v=0.23 cm yr −1) processes provided a slightly better fit to the data ( R 2=0.995, AIC c=−83.6). More importantly, however, this model did not show the consistent underestimation from 27 to 37 cm soil depth. This corroborates the assumption that differing movement mechanisms for different OM fractions are responsible for the observed distribution of 14C in the profile. However, varying dispersion, advection, and decay of OM with depth are also possible explanations.

Experimental study of germanium adsorption on goethite and germanium coprecipitation with iron hydroxide: X-ray absorption fine structure and macroscopic characterization

Adsorption of germanium on goethite was studied at 25 °C in batch reactors as a function of pH (1–12), germanium concentration in solution (10 −7 to 0.002 M) and solid/solution ratio (1.8–17 g/L). The maximal surface site density determined via Ge adsorption experiments at pH from 6 to 10 is equal to 2.5 ± 0.1 μmol/m 2. The percentage of adsorbed Ge increases with pH at pH < 9, reaches a maximum at pH ∼ 9 and slightly decreases when pH is further increased to 11. These results allowed generation of a 2-p K Surface Complexation Model (SCM) which implies a constant capacitance of the electric double layer and postulates the presence of two Ge complexes, > FeO – Ge ( OH ) 3 0 and > FeO – GeO ( OH ) 2 − , at the goethite-solution interface. Coprecipitation of Ge with iron oxy(hydr)oxides formed during Fe(II) oxidation by atmospheric oxygen or by Fe(III) hydrolysis in neutral solutions led to high Ge incorporations in solid with maximal Ge/Fe molar ratio close to 0.5. The molar Ge/Fe ratio in precipitated solid is proportional to that in the initial solution according to the equation (Ge/Fe) solid = k × (Ge/Fe) solution with 0.7 ⩽ k ⩽ 1.0. The structure of adsorbed and coprecipitated Ge complexes was further characterized using XAFS spectroscopy. In agreement with previous data on oxyanions adsorption on goethite, bi-dentate bi-nuclear surface complexes composed of tetrahedrally coordinated Ge attached to the corners of two adjacent Fe octahedra represent the dominant contribution to the EXAFS signal. Coprecipitated samples with Ge/Fe molar ratios >0.1, and samples not aged in solution (<1 day) having intermediate Ge/Fe ratios (0.01–0.1) show 4 ± 0.3 oxygen atoms at 1.76 ± 0.01 Å around Ge. Samples less concentrated in Ge (0.001 < Ge/Fe < 0.10) and aged longer times in solution (up to 280 days) exhibit a splitting of the first atomic shell with Ge in both tetrahedral ( R = 1.77 ± 0.02 Å) and octahedral ( R = 1.92 ± 0.03 Å) coordination with oxygen. In these samples, octahedrally coordinated Ge accounts for up to ∼20% of the total Ge. For the least concentrated samples (Ge/Fe < 0.001–0.0001) containing lepidocrocite, 30–50% of total co-precipitated germanium substitutes for Fe in octahedral sites with the next-nearest environment dominated by edge-sharing GeO 6–FeO 6 linkages ( R Ge–Fe ∼ 3.06 Å). It follows from the results of our study that the largest structural change of Ge (from tetrahedral to octahedral environment) occurs during its coprecipitation with Fe hydroxide at Ge/Fe molar ratio ⩽0.0001. These conditions are likely to be met in many superficial aquatic environments at the contact of anoxic groundwaters with surficial oxygenated solutions. Adsorption and coprecipitation of Ge with solid Fe oxy(hydr)oxides and organo-mineral colloids and its consequence for Ge/Si fractionation and Ge geochemical cycle are discussed.

Fe–Al–organic Colloids Control of Trace Elements in Peat Soil Solutions: Results of Ultrafiltration and Dialysis

Size fractionation of ~40 major and trace elements (TE) in peat soil solutions from the Tverskaya region (Russia) has been studied using frontal filtration and ultrafiltration through a progressively decreasing pore size (5, 2.5, 0.22 μm, 100, 10, 5, and 1 kD) and in situ dialysis through 6–8 and 1 kD membranes with subsequent analysis by ICP-MS. In (ultra) filter-passed permeates and dialysates of soil solutions, Fe, Al, and organic carbon (OC) are well correlated, indicating the presence of mixed organo-mineral colloids. All major anions and silica are present in “dissolved” forms passed through 1 kD membrane. According to their behavior during filtration and dialysis and association with mineral or organic components, three groups of elements can be distinguished: (i) species that are weakly affected by size separation operations and largely (>50–80%) present in the form of dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, As, Mn) with some proportion of small (1–10 kD) organic complexes (Ca, Mg, Sr, Ba), (ii) biologically essential elements (Co, Ni, Zn, Cu, Cd) mainly present in the fraction smaller than 1 kD and known to form strong organic complexes with fulvic acids, and, (iii) elements strongly associated with aluminum, iron and OC in all ultrafiltrates and dialysates with 30–50% being concentrated in large (>10 kD) colloids (Ga, Y, REEs, Pb, Cd, V, Nb, Sn, Ti, Zr, Hf, Th, U). For most trace metals, the proportion in the colloidal fraction correlates with their first hydrolysis constant. This implies a strong control of negatively charged oxygen donors present in inorganic/organic colloids on TE distribution between aqueous solution and colloid particles. It is suggested that these colloids are formed during plant uptake of Al, Fe, and TE from mineral matrix of deep soil horizons and their subsequent release in surface horizons after litter degradation and oxygenation on redox or acid/base fronts. Dissolved organic matter stabilizes Al/Fe colloids and thus enhances trace elements transport in soil solutions.

The genesis and transformation of organo-mineral colloids in a drained peatland area

The spatial evolution of colloids from a drained peat bog to a river was studied in a karstic watershed (Jura Mountains, Switzerland) by bulk chemistry and electron microscopy. Raw waters (peat bog pore water, water from artificial drains and river water) were analyzed using ICP (Fe, Ca), Colorimetry (Fe 2+), TOC and UV (organic matter) and analytical electron microscopies (TEM-EDS, STEM-EDS, EF-TEM). Microscopic analyses correlate bulk sample results and highlight interesting features at the level of the individual colloids. In the peat, TEM-EDS shows the presence of individual globular entities made of carbon (0.4 to 1 μm), while in the river STEM-EDS reveals Fe-Ca-rich globular colloids with a core of carbon determined by EF-TEM. In parallel, bulk chemical analyses show that the ratio [Fe 2+]:[Fe] tot decreases from the peat to the river as an inverse function of pH and [O 2], while [Ca 2+] increases. We may thus postulate that Fe-Ca-C rich entities found in the river originate from the oxidation of Fe 2+ and adsorption of Ca 2+ at the surface of organic colloids, as they are transported by drains from the peat to the river.

Exchange equilibria of potassium in soils, V. Effect of natural organic matter on K-Ca exchange

Exchange equilibria of K-Ca were studied in five soil samples (Anglberg surface, ABS; Anglberg subsurface, ABSS; Ottenhofen surface, OHS; Ottenhofen surface limid, OHSL; Buchhofen surface, BHS) from the Federal Republic of Germany. These samples had a wide difference in their clay content, clay mineralogy, CEC, K-fixation capacity, organic matter (OM), specific surface area, and surface charge density (SCD). Untreated and H 2O 2-treated samples were Ca-saturated and equilibrated with KCl+CaCl 2 solutions at a constant chloride concentration of 0.025 M 1 −1 in the equilibrium solutions. The experimental results were described, using the Gaines and Thomas, and Babcock and Duckart thermodynamic approaches, and various selectivity quotients. Out of five, two soil samples showed a decrease in the Gapon ( K G ) and Vanselow ( K V ) selectivity quotients in the lower K-saturation (i.e., 0–15 exchangeable potassium percentage, EPP, in ABS; 0–30 EPP in ABBS) zone on oxidation of OM. In the remaining three soil samples, K G and K V increased with H 2O 2-treatment for the whole exchange isotherms. The Gaines and Thomas standard free energy for K-Ca exchange ( ΔGo) decreased in all but one (i.e., ABSS) and Babcock and Duckart ( ΔGo′) in all the soil samples on OM oxidation. The values of ΔGo were less negative than those of ΔGo′ for comparable soil samples. The positive or negative effect of OM on K-preference has been ascribed to the “resultant” of the two opposing phenomena, viz., an increase in SCD and “low K-specific adsorption sites” (causing a decrease in K-preference), and an increase in the internal: external surfaces due to organo-mineral colloids (causing an increase in K-preference).

CINÉTIQUE ET MÉCANISME DE L'HYDROLYSE ACIDE DE LA MATIÈRE ORGANIQUE D'UN SOL HUMIFÈRE DE MONTAGNE

From the surface horizon of an organic-rich mountain soil, humic and fulvic acids, and organo-mineral compounds including clay and hydroxy-metal colloids, were separated and purified. Each of these fractions was hydrolyzed in 3.0 M HCl under reflux, then the reaction parameters related to the solubilization of carbon and nitrogen and to the kinetics of hydrolysis were calculated. Acid hydrolysis was interpreted as the result of two successive steps: first a rapid electrophilic attack of heteroatomic C-O and C-N bonds by protons, then a slow nucleophilic hydration of the protonated bonds. Electron delocalization in these bonds, which increased with the polycondensation degree of organic compounds, and with their adsoprtion on mineral surfaces, resulted in an increase in their stability to hydrolysis. Fulvic acids were found to be the less stable material, and lead to predominantly anionic hydrolysis products. Clay-sized humin was the most stable material and yielded mainly cationic hydrolysates. The stability to hydrolysis and the humification degree of organic matter in the fractions generally coincided, and decreased in the following order: fine clay-sized humin &gt; alkali dispersible organo-mineral colloids &gt; &gt; humic acids &gt; hydroxy-ferric organic colloids &gt; hydroxy-aluminium organic colloids = fulvic acids. Key words: Organo-mineral complex, humic substances, acid hydrolysis, carbon, nitrogen

ALEXANDROVA, L. N.: Organo-mineral compounds and organo-mineral colloids in soil

ALEXANDROVA, L. N.: Organo-mineral compounds and organo-mineral colloids in soil