A 13C-NMR study of the interactions of soil organic matter with aluminium and allophane in podzols

The stabilization of organic matter in soil by interaction with aluminium (Al) or allophane is important in maintaining soil quality, and in retarding the decomposition of soil organic matter. Complexation of Al by soil organic matter may also ameliorate Al toxicity. Here we use ¹³C-NMR spectroscopy to assess the interaction of soil organic matter with both Al and allophane in two poorly drained podzols containing only trace amounts of iron. The ¹³C-NMR spectrum of the subsoil of the allophane-rich One Tree Point podzol shows an intense peak at 179 p.p.m., assigned to carbon in carboxylic acids. This peak shifts to 177 p.p.m. after removal of allophane (11% of the soil mass) by treatment with HF. We infer that the carboxyl groups in the organic matter are bonded to structural Al on the surface of allophane spherules. In the non-allophanic Te Kopuru podzol, on the other hand, the organic matter apparently interacts with Al ions in the soil solution. This soil also has more aromatic carbon and fewer carbons in carboxyl and carbohydrate structures than the allophanic sample. There is an indication that allophane stabilizes carbohydrate groups as well as carboxyl groups.     

13C/12C Ratios of soil organic matter as indicators of vegetation changes in the congo

The ¹³C/¹²C ratios were determined for the organic matter of all horizons of a podzol profile and of the A₁ horizons of some ferrallitic soils, in some grass shoots and in a fossil root fragment from the B_2h horizon of the podzol. The isotope ratio in the organic matter of the A₁ horizon of the podzol matches those in grass shoots from the present savanna vegetation. The ratios in the lower horizons match those of organic matter in the A₁ horizons of soils under forest and that of the fossil root fragment in the B_2h horizon. The ratios thus demonstrate that the humus enrichment of the B_2h horizon of the podzol occurred while it was under forest vegetation and that the present grass vegetation did not take part in the podzolization process. The differences also indicate that savanna replaced forest vegetation after the profile had been formed.     

PARTITIONING OF HEAVY METALS IN PODZOL SOILS CONTAMINATED BY MINE DRAINAGE WATERS,DALARNA, SWEDEN

The discharge of acidic mine drainage waters onto a hillslope in Dalarna, central Sweden, has lead to the contamination of the podzol soils with Cu, Fe, Ni, Pb, Zn and sulfate. Samples from contaminated and reference soils have been collected for chemical and mineralogical analyses. Jarosite is identified by x-ray diffraction analysis as a precipitate in the upper horizons (A, E, B) of the contaminated soils, where the soil acidity (pH_KCl～2.6) promotes jarosite stability. The sequential chemical extraction of soil samples indicates that, in the reference A horizon, Cu, Pb, Ni and Zn are bound primarily to cation exchange sites and organic matter. In the A horizon of the contaminated soils closest to the rock dump, metal partitioning is dominated by the Fe oxide fractions, despite the high organic matter content; Pb is almost completely bound to crystalline Fe oxides, possibly adsorbed to Fe oxides or occuring in a jarosite solid solution. In the reference B and C horizons, Cu, Ni and Zn are primarily adsorbed/coprecipitated in the Fe oxide fractions, while Pb remains with a large fraction bound to organic matter. In the Fe-rich B horizon of the contaminated soils, the partitioning of the metals in cation exchange sites and to organic matter has greatly increased relative to the reference soils, resulting from the mobilization of organo-metal complexes down the profile.     

Distribution of allophane and organic matter in podzol B horizons: reply to Buurman & Van Reeuwijk

The macromorphology, micromorphology and chemical nature of illuvial material in podzol B horizons and subsoils can be explained by contributions from two different migrating species: (a) a positively-charged mixed Al₂O₃-Fe₂O₃-SiO₂-H₂O sol incorporating minor amounts of adsorbed organic matter and silicate clay, and (b) negatively charged organic sols and solutions, carrying minor amounts of Al, Fe and clay. These species can also be generated within B horizons of high root activity. An alternative theory, that requires allophane to be formed in situ in the B horizon by microbial decomposition of precipitated organic complexes, fails to predict the observed distribution of allophane.     

Spatial and temporal variation in podzol organic matter studied by pyrolysis-gas chromatography/mass spectrometry and micromorphology

A well‐developed podzol hydrosequence that has been partially covered with drift sand, and partially subjected to improved drainage, provides new insights into the causes of variation in soil organic matter chemistry in such soils. While E horizons invariably move towards a dominance of aliphatic components reflecting residual accumulation, the chemistry of organic matter in well‐drained B horizons is determined mainly by decaying roots, which are transformed by microorganisms to humus aggregates. In poorly drained, stratified B horizons, humus coatings dominate and the chemistry is very close to that of dissolved organic carbon. When a sand cover inhibits the supply of fresh litter, microbial decomposition in the A horizon causes a shift in chemistry towards that of the E horizon. Similarly, upon improved drainage and removal of complexed metals from the top of the B horizon, microbial decomposition of all palatable organic matter in the top of the B horizon causes a shift towards E‐horizon chemistry. This is probably the mechanism by which most E horizons in podzols are formed, and not by re‐solution. Marked chemical changes upon improved drainage may take only decades. During microbial decay, small polysaccharide‐derived pyrolysis products (mainly furans, furaldehydes and acetic acid) remain abundant due to the contribution of microbial sugars. Both micromorphology and factor analysis on quantified results of pyrolysis‐gas chromatography/mass spectrometry contribute significantly to the interpretation of the humus chemistry of these profiles and thus to our understanding of soil genesis. Organic chemistry of the investigated podzols can be understood only in the context of their genesis.     

Mineralogy of some Italian andosols with special reference to the origin of the clay fraction

The mineralogy of four Italian Andosols - derived from volcanic material either oversaturated or undersaturated with respect to silica - has been investigated by XRD, EM and IR. The crystalline clay minerals in all four profiles are essentially similar, consisting of abundant halloysite with moderate illite and 14A intergrade material, minor kaolinite and occasional gibbsite. The soils also contain large amounts of imogolite and proto-imogolite allophane. With the exception of illite all these clay minerals are believed to be of pedogenic origin. Halloysite occurs in the dehydrated form in the surface horizons but becomes progressively more hydrated with depth. At depths of > 1.4 m the clay fraction consists almost entirely of fully hydrated halloysite, supporting the suggestion that halloysite forms best in a stagnant moisture regime where there is a depositional overburden acting as a silica source. EM observations show that the halloysite may have spherical morphology and may be intimately associated with gas vesicles in pumice grains where it probably forms by the transformation of allophanic material. It seems likely that dehydrated halloysite slowly converts to poorly crystallized kaolinite in the upper horizons of these profiles. The origin of the 2/1 minerals is more problematical. Illite is probably inherited from mica in the parent material but the 14A intergrade material is so poorly ordered that a pedogenic origin seems more likely than formation by inheritance or by transformation of pre-existing 2/1 silicates.     

Iron-bearing phases in a peat-derived duricrust from Brazil

The formation of aluminium‐substituted iron‐minerals is still subject to debate. We report a case study in a Humic Gleysol soil profile, developed on a sedimentary saprolite, from a basin floor on the Uberaba Plateau (Minas Gerais State, Brazil) where iron‐phases are crystallized by a ferruginization process. The mineralogical and chemical properties were investigated by X‐ray diffraction, thermogravimetric analysis, differential scanning calorimetry and Mössbauer spectroscopy. The specific surface area (BET method) and cation exchange capacity (CEC) were also determined. The soil profile is mainly composed of gibbsite, kaolinite and amorphous alumino‐silicate phases, the latter being more frequent in the H horizon where the organic carbon content is greater. The surface area and CEC values are also greater in the H horizon (58.6 m²g⁻¹ and 4.65 mol_ckg⁻¹, respectively) which indicates an increase in porosity caused by the presence of 20.8% of organic matter and amorphous materials. Goethite occurs as a secondary mineral in the H horizon and as the main mineral in the duricrust in association with haematite. The omnipresence of aluminium in the environment (24.6–46.2% of Al₂O₃) resulted in Al‐substitution in all iron‐bearing phases but the goethite from the H horizon has the greatest Al‐for‐Fe substitution, with at least 20 mole per cent of aluminium. In spite of the greater microporosity and wetness of the H horizon, the immediate contact with the richest Al‐source (gibbsite) favours the precipitation of unusually greatly Al‐substituted goethite instead of haematite in this horizon.     

Aluminum solubility of strongly acidified allophanic Andosols from Kagoshima Prefecture,southern Japan

Abstract

The aluminum solubility of acidified soils both from furrows and under tree canopies of a tea garden was studied using equilibrium experiments in 0.01 mol L^?1 CaCl₂ solution systems. The soils were originally classified as allophanic Andosols. The furrow soils were more severely acidified because of the heavy application of nitrogen fertilizer, especially in the upper soil horizons (pH[H₂O] of 3.6–3.8 in the A1 and 2A2 horizons). These acidified soils were characterized by the dissolution of allophanic materials (allophane, imogolite and allophane-like materials) and by an increase in Al–humus complexes. Ion activity product (IAP) values of the strongly acidified soil horizons were largely undersaturated with respect to imogolite (allophanic clay) or gibbsite. Plots of p(Al³⁺) as a function of pH strongly indicated that Al solubility of the soils was largely controlled by Al–humus complexes, especially in the A1 horizon. In the canopy soils, which were more weakly acidified (pH[H₂O] 4.9–5.0), Al solubility was close to that of gibbsite and allophanic materials, indicating that the solubility is partly controlled by these minerals.     

DISTRIBUTION OF PYROPHOSPHATE-EXTRACTABLE IRON AND ORGANIC CARBON IN SOILS OF VARIOUS GROUPS

Potassium pyrophosphate (0.1m ) removes very little Fe from crystalline Fe oxides at pH 10, but peptizes finely divided hydrous amorphous oxides and organic matter in soils. Fe and C contents of extracts from each horizon of twenty-six British soil profiles show distinctive patterns, independent of the residual dithionite-soluble Fe. Thus extracts of humus Fe podzols have maximum Fe and C in the B horizon, peaty gley podzol has maximum Fe in the B horizon but maximum C in the surface. These groups are differentiated from non-podzols which have maximum pyrophosphate extractable Fe and C in the surface horizon, decreasing with depth. Intermediate patterns help to quantify differences in soils of classes having properties of more than one soil group.     

Podzolization and clay migration in spodosols of eastern France

Field observations and laboratory analyses of podzols developed on sandy Triassic parent material in the Vosges have demonstrated clay accumulation in the upper parts of spodic horizons, especially in the B_h horizons. To see whether clay accumulation corresponds to real clay illuviation, two types of podzol profiles have been studied. The first is an iron podzol, called “podzol forestier”, because it has been entirely developed under climax forest environment. The second, an iron-humus podzol, called “podzol de dégradation”, was first developed under forest and more recently (the last 1000 to 2000 years) under heath vegetation. Methods used in the study of the two profiles were the “isoquartz” alteration balance, clay mineral identification by X-ray analyses and micromorphholigical examination.For the podzol forestier, the data strongly support a hypothesis of illuviation of very fine micaceous clays (vermiculite), especially the ferriargillans in the B_h horizon. Consequently, it is believed that illuviation of the greatest part of clays promoted differentiation of podzol horizons. Podzolization is strongly redistributive.In the podzol de dégradation, the identified clay minerals are the same as in the podzol forestier but the pedological features in the B_h horizon correspond to those of classic spodic horizons (mixed concentration and grain coatings). Moreover, podzolization is geochemically strongly subtractive in this second type of podzol.Inasmuch as the podzols de dégradation are developed from the podzols forestiers, the authors define an evolutionary time-sequence: the first phase of forest soil genesis is regulated by the double process of clay illuviation and redistributive podzolization. The following degradation phase connected to the particular nature of heath vegetation and to abundant chelating organic compounds induces the disruption of the ferriargillans previously formed in the B_h horizon, the formation of an agglomeroplasmic fabric microstructure and above all, the elimination of hydrolyzed products of minerals from the profile. During this last phase, a strongly subtractive podzolization prevails over clay illuviation.     

Organisation of the soil mantle in tropical southeastern Brazil (Serra do Mar) in relation to landslides processes

The Serra do Mar complex in southeastern Brazil is subject to frequent landslides especially on the Atlantic coast. The three-dimensional organisation of the soil was studied in a 56-ha representative catchment. Upslope in situ soil material has developed from the parent rock, and downslope the soil has resulted from landslide processes. The soil mantle upslope is mainly characterised by slowly permeable kaolinitic horizons within a thick gibbsitic weathering horizon. The field and microscopic relationships between the two suggest that the kaolinitic horizon has evolved at the expense of the gibbsitic material. Resilication of gibbsite to form kaolinite is postulated in this environment. The kaolinitic horizons are overlain by a microaggregated horizon. The difference in porosity and water movement between these two horizons was estimated by density measurements, mercury porosimetry, image processing and calculation of water retention and shrinkage curves. The results indicate that water is retained briefly within the microaggregated horizon during intensive rainfall. Because of the inclination of the kaolinitic horizon, any excess water within it flows laterally downslope and accumulates in the lowest part of the slope. This leads to landslipping, the main process of landform development in the region.     

Parent material and chemical weathering in alpine soils on Mt. Mansfield,Vermont, USA

We compared the elemental composition of soil and bedrock samples to determine the extent of chemical weathering and the nature of the soil parent material in alpine soils on Vermont's highest summit. Previously it was unclear whether these soils formed through weathering of bedrock, glacial till, or eolian sediment, or solely through the accumulation of organic matter. In eighteen profiles, no evidence was found to indicate that soils have developed in glacial till, despite evidence that the mountain was completely inundated by the Laurentide Ice Sheet. In contrast, results strongly support the theory that pedogenesis in this environment involves in situ bedrock weathering under a thickening blanket of acidic organic litter. Weathering indices reveal an increase in weathering intensity upwards from the bedrock, and trends of normalized rare earth elements demonstrate a strong similarity between bedrock and soil samples. Leaching has concentrated less mobile elements such as Al, Cr, La, P, Pb, and Ti in soil horizons and removed mobile elements such as Co, Fe, K, Mg, Mn, Si, and Zn. X-ray diffraction reveals that chlorite, which is present in all bedrock samples and some saprolites, has weathered completely from upper soil horizons, and that hydrobiotite, vermiculite, kaolinite, gibbsite, and goethite have formed in the soil. Ratios of immobile elements (Ce, Cr, Nb, Ta, Ti, Y, and Zr) in soil and bedrock samples are, however, notably different. Furthermore, the moderately mobile trace elements Cu, Mo, and Sr are actually more abundant in soil than in bedrock, and soil concentrations of Zr are up to an order-of-magnitude greater than in bedrock samples. Together these data argue for at least a modest eolian influx, which may have arrived during the regression of Lake Vermont during the latest Pleistocene or from an outwash source in the immediate post-glacial period. Similarly, increased Ca and Na concentrations in soil samples may signify modern deposition of dust bearing Ca (from agricultural fields) and Na (from roads).     

Multiple forms of acetyl-naphthyl-esterase activity in soil organic matter

Acetyl-naphthyl-esterase activity has been identified and characterized in organic matter extracted from an A₁ horizon of an Alpine podzol. The temperature optimum of the esterase is about 75° C and its activity rises with increasing pH, without reaching a maximum value in the tested range. The Michaelis constant has been determined as Km = 2.950 mM. Pronase does not disrupt esterase activity. Electrofocusing in acrylamide gel shows several peaks of enzyme activity, which correspond with humic isoelectric bands. The location of acetyl-esterase activity in organic matter is discussed.     

Soil organic matter chemistry in allophanic soils: a pyrolysis-GC/MS study of a Costa Rican Andosol catena

Soil organic matter (SOM) in allophanic soils is supposed to accumulate due to protection caused by binding to allophane, aluminium and iron. We investigated a catena of allophanic and non‐allophanic soils in Costa Rica to determine the effect of such binding mechanisms on SOM chemistry. These soils contain no contribution of black carbon. Molecular characterization of litter, extractable and dispersed organic matter was done by Curie‐point pyrolysis‐GC/MS. The molecular chemistry of the organic fractions indicates a strong decomposition of plant‐derived organic matter and a strong contribution of microbial sugars and N‐compounds to SOM. Both the decomposition of plant‐derived SOM – including that of relatively recalcitrant compounds – and the relative contribution of microbial SOM were greater in allophanic samples than in non‐allophanic ones. This suggests that chemical protection does not act on primary OM, although it may influence the accumulation of secondary OM in these soils. The effect of allophane on SOM contents in such perhumid soils is probably through incorporation of decomposition products and microbial SOM in very fine aggregates that – in a perhumid environment – remain saturated with water during much of the year. Greater concentrations of aliphatics are found in allophanic residues, but there is no evidence of any specific mineral‐organic binding. The results do not support the existing theory of chemical protection of plant‐derived components through binding to allophane, iron and aluminium.     

Identification of podzols and podzolised soils in New Zealand by relative absorbance of oxalate extracts of A and B horizons

A method for separating podzols and podzolised soils from other New Zealand soils is proposed. The method is based on measurement of the optical density of acid oxalate extracts of soils. A number of soil leaching sequences and some individual soils are examined.It is assumed that the optical density of the oxalate extracts is due mainly to extracted fulvic acid and that detection of appreciable quantities of this material in the B horizon indicates that podzolisation is an active process in the soil.The technique separated the soils of the leaching sequences well, following the observable increase of podzolic characteristics with increased leaching.When the B horizon/A horizon ODOE (optical density of the oxalate extracts) ratios were compared with the criteria for the spodic horizon in “Soil Taxonomy” (Soil Survey Staff, 1975), it was found that all soils with a ratio of less than 1.0 did not satisfy spodic horizon criteria and were not classified as podzol/podzolised. All the soils examined with ratios > 1.0 satisfied spodic horizon criteria or were classified as podzol/podzolised, usually both.     

Organic matter retention in an upland humic podzol; the effects of pH and solute type

This paper discusses the effects of different horizons and soil solution compositions on dissolved organic matter retention in a moorland podzol and compares the results with previous studies of forest podzols. Adsorption isotherms were constructed for each of the major horizons of a freely draining, upland, moorland, humic podzol from north-east Scotland, to investigate processes of retention and release of dissolved organic matter (DOM). Carbon retention of a range of solute types was studied, and phthalate was chosen as a model compound to measure carbon retention at three different pH values (3, 4.5 and 6). Retention and release of DOM was related to chemical, physical and mineralogical characteristics of the different soil horizons. All the mineral horizons retained DOM, with the Bs horizon most retentive. Solution pH did not significantly affect DOM retention in the O and A horizons. At pH 3 and 4.5 organic matter was weakly retained in the Bhs horizon, but strongly retained in the Bs and the Cx horizons. At pH 6 reversal of surface charge occurred in the Bs and Cx horizons resulting in the release of similar amounts of organic matter to that released from the O horizon at the same pH. The results demonstrate how podzols act as a ‘valve’ in controlling the input of dissolved organic compounds into surface and ground water, and how sensitive the controlling mechanisms are to pH change.     

The control of aluminium solubility in some acidic Australian soils

The variation in the solubility of aluminium in some acid soils of south-eastern Australia has been investigated. The hypothesis was that leaching of silicic acid influenced the extent of clay decomposition, and hence aluminium solubility, in accord with Le Chatelier's principle. In lower rainfall areas (< 800 mm) control of Al solubility was consistent with a poorly crystalline kaolinite as the source phase, while at higher rainfall (> 1200 mm) it was consistent with gibbsite control. However, soluble silica concentrations were too high for gibbsite and kaolinite to be thermodynamically stable phases. The hypothesis was modified to take account of a quasi-equilibrium in the open soil system, in which clay dissolution and A1 solubility appear to depend on the relative rates of H⁺ input and of silica leaching. These may result in a supersaturated, or possibly even undersaturated system, at any point in time. The relative sizes of the organic sink and mineral Al source determine the influence of organic matter on Al solubility.     

Extraction of inorganic forms of translocated Al, Fe and Si from a podzol Bs horizon

A range of extractants commonly used in soil studies, both to clean up the crystalline clay minerals by dissolving poorly ordered phases, and to assist in the classification of soils, has been used to assess their efficiency in extracting inorganic forms of translocated Al, Fe and Si from a podzol Bs horizon. A 4 h extraction with ammonium oxalate pH 3 is the most efficient single procedure for these phases. It is concluded that satisfactory characterization of a podzol B horizon requires the use of two extractants: acid oxalate to assess the total amounts of Al, Fe and Si in non-crystalline weathering products, and pyrophosphate to assess the amounts in organic forms. Dithionite-citrate-bicarbonate gives a measure of total free iron oxides, but extracts only an ill-defined fraction of the allophane-imogolite complex.     

Sorption of chlorpyrifos to selected minerals and the effect of humic acid

Sorption of chlorpyrifos (CPF) from 2.85 microM (1 mg/L) aqueous solutions in 0.01 M NaCl to montmorillonite, kaolinite, and gibbsite was investigated at 25 degrees C. Uptake of CPF by kaolinite and gibbsite was generally <10%, with pH having at most a small effect. Sorption to montmorillonite was significantly greater, with approximately 50% of the initial CPF being removed from solution below pH 5. Above pH 5 the sorption decreased to about 30%. About 70% of CPF was sorbed to kaolinite and gibbsite after 30 min, whereas on montmorillonite only 50% sorbed in an initial rapid uptake (approximately 30 min) followed by slower sorption, with a maximum achieved by 24 h. Although CPF desorbed completely from kaolinite in methanol, only about two-thirds was desorbed from montmorillonite. CPF has only a weak affinity for the surfaces of kaolinite and gibbsite. In the case of montmorillonite, sorption is significantly stronger and may involve a combination of sorption to external surfaces and diffusion into microporous regions. At pH >6 increased negative surface charge results in a lower affinity of CPF for the external surface. In the presence of 50 mg/L humic acid (HA) the amount of CPF sorbed on gibbsite and kaolinite was 3-4 times greater than that in the binary systems. The HA forms an organic coating on the mineral surface, providing a more hydrophobic environment, leading to enhanced CPF uptake. The HA coating on montmorillonite may reduce access of CPF to microporous regions, with CPF tending to accumulate within the HA coating.     

Sorption of Water-Soluble Organic Substances by Mineral Horizons of Podzol

Transformation of water-soluble organic substances entering mineral horizons of podzol from the forest litter was studied in a model column experiment. The concentration of organic matter in the solution after its interaction with the E horizon increased by 10–44% due to the release of native soluble organic matter. This was accompanied by changes in the quality of water-soluble organic matter: the portion of hydrophobic components increased, the coefficients of extinction at 254–280 nm decreased, and the portion of low-molecular-weight compounds slightly decreased with a corresponding increase in the portion of high-molecular-weight compounds. Upon the interaction of water-soluble organic substances with the E horizon, the pH values first decreased and then slightly increased, which could be due to sequential desorption of organic acids of different strengths. Dissolved organic substances from the E horizon were partly sorbed in the BF horizon at the rate of about 65 mg С/100 g, or 22% of C_org in the BF horizon. The sorption resulted in the removal of mainly hydrophobic medium- and high-molecular-weight (>7000 Da) organic substances from the solution. As judged from the coefficients of extinction in the UV area, the sorbed substances were characterized by a higher aromaticity in comparison with the substances remaining in the solution. The sorption of organic substances in the BF horizon was accompanied by the rise in the pH of the solution, which corresponded to binding of organic anions on the surface of iron hydroxides according to the mechanism of ligand exchange with OH ions.