Aggregation in soils with small amounts of swelling clays. II. Chemistry and surface properties of Na resin stable soil aggregates

Stable aggregates of soils with small amounts of swelling clays were characterized after 16 h shaking with Na resin. Different kinds of organic material operate at various levels of micro-aggregate size, being more aromatic in the coarser aggregates and combined with poorly-ordered Al and Fe hydrous oxides.
Effects on aggregate surface properties are described. For each size of resin stable aggregate, the mesopore volume increased with both increasing aggregating organic materials and poorly-ordered Al and Fe hydrous oxides.     

铵、钾同时存在时, 土壤对铵的优先吸附

The water stability of aggregates in various size classes separated from 18 samples of red soils under different managements, and the mechanisms responsible for the formation of water-stable soil aggregates were studied. The results showed that the water stability of soil aggregates declined with increasing size, especially for the low organic matter soils. Organic matter plays a key role in the formation of water-stable soil aggregates. The larger the soil aggregate size, the greater the impact of organic matter on the water stability of soil aggregates. Removal of organic matter markedly disintegrated the large water-stable aggregates (> 2.0 mm) and increased the small ones (< 0.25-0.5mm) to some extent, whereas removal of free iron(aluminium) oxides considerably destroyed aggregates of all sizes, especially the < 0.25-0.5 mm classes. The contents of organic matter in water-stable aggregates increased with aggregate sizes. It is concluded from this study that small water-stable aggregates (< 0.25-0.5 mm) were chiefly cemented by Fe and Al oxides whilst the large ones (> 2.0 mm) were mainly glued up by organic matter. Both free oxides and organic matter contribute to the formation and water stability of aggregates in red soils.     

VERTICAL DISTRIBUTION OF EXTRACTABLE IRON AND ALUMINIUM IN SOIL PROFILES FROM A BROWN EARTH-PEATY PODZOL ASSOCIATION

Fe and Al extractable by 3 per cent oxalic acid and by 0.1M potassium pyrophosphate at pH 10 have been determined in horizon samples of two soil profiles of each of three subgroups (Brown Earth, Brown Podzolic Soil, and Peaty Podzol) developed in North Wales on parent materials derived from Silurian shales. The vertical distribution of Fe and Al together with the relationship between pyrophosphate-extractable (‘fresh’ hydrous oxides) and oxalic-extract-able Fe or Al (‘fresh’+‘aged’ hydrous oxides) can assist classification and interpretation of the course of podzolization in these soils. If podzolization is defined as sesquioxide transport, then its degree of development in the soils studied differs according to whether Al or Fe are used as the index element. The evidence supports continued recognition of soils of Brown Podzolic type as an intergrade subgroup.     

Water stability of aggregates in subtropical and tropical soils (Georgia and China) and its relationships with the mineralogy and chemical properties

Water-stable aggregates isolated from three subtropical and one tropical soil (Western Georgia and China) were studied for their organic carbon, cation exchange capacity (CEC), specific surface area, magnetic susceptibility, and total chemical elements. The soils were also studied for their particle-size distribution, mineralogy, and nonsilicate Fe and Al oxides. Describe the water stability, three indices have been used: the content of water-stable macroaggregates (>0.25 mm), the mean weighted diameter of the aggregates, and the numerical aggregation index. The yellow-cinnamonic soil (China) was neutral, and the three other soils were acid. The soils were degraded with a low content of organic matter. The yellow-cinnamonic soil was characterized by the lowest water stability due to the predominantly vermiculite composition of the clay. The high water stability of the Oxisol structure was determined by the kaolinites and high content of oxides. In three out of the four soils studied, the hierarchical levels of the soil structure organization were defined; they were identified by the content of organic matter and the Ca + Mg (in Oxisols). Iron oxides mainly participated in the formation of micro-aggregates; Al and Mn contributed to the formation of macroaggregates. The water-stable aggregates acted as sorption geochemical barriers and accumulated Pb, Zn, Cd, Cs, and other trace elements up to concentrations exceeding their levels in the soil by 5 times and more. The highest correlations were obtained with CEC, Mn, and P rather than with organic carbon and Fe.     

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.     

Organo-mineral associations in sandy acid forest soils: importance of specific surface area, iron oxides and micropores

Organo-mineral associations stabilize soil organic matter, though the mechanisms by which they do so are unclear. We used particle-size fractions < 6.3 μm of two soils to examine the importance of Fe oxides, short-range order Al silicates and the surface areas of minerals and micropores on the formation of organo-mineral associations. In the subsoil Fe oxides were most strongly statistically correlated with the mineral-bound organic carbon. We therefore assume that they are the most important substrates for the formation of organo-mineral associations. There is no indication that this is caused by physical protection of organic matter in their micropores (< 2 nm). In the Haplic Podzol, dithionite–citrate–bicarbonate-soluble short-range order Al silicates may also play a role. Fe oxide particles were calculated to offer specific surface areas of ∼ 200 m² g⁻¹ (goethite) and ∼ 800 m² g⁻¹ (ferrihydrite), corresponding to crystal diameters of only a few nm. We assume that the resulting large amount of oxide-specific reactive surface sites (conditionally charged hydroxyl groups) is responsible for their dominant role as sorbents. With maximum C loadings of 1.3 mg C per m² Fe oxide for the Dystric Cambisol and 1.1 mg C per m² Fe oxide + short-range order Al silicates for the Haplic Podzol the subsoils of both soils seem to have reached saturation with respect to organic matter sorption. In contrast to subsoil horizons, organo-mineral associations from topsoils contain much larger amounts of organic matter. Here a larger C loading on Fe oxides or a greater importance of other sorbents in addition to the oxides must be assumed.     

Phosphorus sorption by Andepts from the Southern Highlands of Papua New Guinea

P sorption curves (18 hours, 0.01 M CaCl₂) were determined for various A, AB, B and C horizons of six Andepts. Two of these soils were formed in alluvially sorted and redeposited volcanic ash. P buffer capacity (PBC) and equilibrium solution P concentration (EPC) were derived from the curves. PBC was high for all samples indicating large sorption capacities. Soils formed in alluvial ash had lower PBC than those developed in airfall ash. In the latter soils, PBC was affected by degree of weathering. Multiple regression indicated that most variation in PBC was accounted for by citrate-dithionite minus pyrophosphate extractable Al, oxalate minus pyrophosphate extractable Al, and pyrophosphate extractable Fe. This suggests that allophane, crystalline and non-crystalline aluminium hydrous oxides, and Fe associated with organic matter, account for the predominant P-sorbing sites. The low EPC figures, which were correlated with Olsen extractable P, indicate potential P deficiency as a limitation to crop production.     

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.     

Transformations and Availability of Iron to Wheat as Influenced by Phosphorus and Manganese Fertilization in a Typic Haplustept Soil

An investigation was conducted using Typic Haplustept, sandy loam soil, to investigate the interactive effects of phosphorus (P) and manganese (Mn) fertilization on native iron (Fe) pools in soil and their availability to wheat (cv. PBW-343) crop. Phosphorus fertilization moved Fe from residual mineral fraction of Fe to manganese oxides (MnOX), organic matter (OM), amorphous (AMPOX), and crystalline (CRYOX) Fe and Al oxide fractions. However, Mn application decreased specifically adsorbed (SAD)–Fe and CRYOX–Fe but increased OM–Fe and mineral fraction of Fe. Available Fe in soil decreased as Olsen P and P:Mn ratio increased in the soil. Higher Olsen P (>60 mg P kg^?1soil) reduced mean Fe uptake by shoot. P content and P:Mn ratio in soil as well as in root and shoot were inversely related to Fe concentration in both the plant parts. The role of soil Fe associated with oxides and organic matter was found most notable in Fe nutrition of wheat.     

Significance of hydrous iron oxides in enhancing P sorption of soils with the addition of sodium hydrosulfite (Na2S2O4)

Phosphorus sorption (P_sor) of soils is affected by redox conditions. It has been shown that P_sor of lowland soils at a pH value of about 4.3 increases when a small amount of sodium hydrosulfite (Na₂S₂O₄) is added and decreases when an excess amount of (Na₂S₂O₄) is added to the mixture of a soil and P solution. Hydrous Fe-Al oxides, manganese dioxide (MnO₂) exchangeable Ca, models of reactive components with P in soils, were examined to identify the factors responsible for the increase of P_sor in lowland soils when a small amount of Na₂S₂O₄ was added. For clarifying the contribution of the hydrous Fe-Al oxides, goethite and 7 hydrous Fe-Al oxides (Fe/Al atomic ratio: 1/0, 5/1, 2/1, 1/1, 1/2, 1/5, and 0/1) were used. The P_sor of all these materials increased when they were treated with a small amount of Na₂S₂O₄ although the increase was the smallest for the hydrous Al oxide among the 7 oxides. Thus, the hydrous Fe oxides, and Al oxide to a smaller extent, play an important role in the increase in P_sor of the lowland soils treated with a small amount of Na₂S₂O₄ The P_sor of the hydrous Fe oxides was not appreciably affected by the addition of MnO₂. The increase in P_sor of the Ca-saturated Hachirogata soil was almost the same as that of the Nasaturated Hachirogata soil, indicating that exchangeable Ca did not affect appreciably the increase of P_sor in reduced soils at a pH value of about 4.3.     

Poorly crystalline mineral phases protect organic matter in acid subsoil horizons

Soil minerals are known to influence the biological stability of soil organic matter (SOM). Our study aimed to relate properties of the mineral matrix to its ability to protect organic C against decomposition in acid soils. We used the amount of hydroxyl ions released after exposure to NaF solution to establish a reactivity gradient spanning 12 subsoil horizons collected from 10 different locations. The subsoil horizons represent six soil orders and diverse geological parent materials. Phyllosilicates were characterized by X-ray diffraction and pedogenic oxides by selective dissolution procedures. The organic carbon (C) remaining after chemical removal of an oxidizable fraction of SOM with NaOCl solution was taken to represent a stable organic carbon pool. Stable organic carbon was confirmed as older than bulk organic carbon by a smaller radiocarbon (¹⁴C) content after oxidation in all 12 soils. The amount of stable organic C did not depend on clay content or the content of dithionite–citrate-extractable Fe. The combination of oxalate-extractable Fe and Al explained the greatest amount of variation in stable organic C (R² = 0.78). Our results suggest that in acid soils, organic matter is preferentially protected by interaction with poorly crystalline minerals represented by the oxalate-soluble Fe and Al fraction. This evidence suggests that ligand exchange between mineral surface hydroxyl groups and negatively charged organic functional groups is a quantitatively important mechanism in the stabilization of SOM in acid soils. The results imply a finite stabilization capacity of soil minerals for organic matter, limited by the area density of reactive surface sites.     

Characteristics of non-allophanic Andisols derived from low-activity clay regoliths in the Nilgiri Hills (Southern India)

Low‐activity clay soils on old planation surfaces of the tropics are generally considered as stable end points of soil formation. It is therefore surprising to find Andisols on them. We characterized the properties of six profiles representative of these soils in the western part of the Nilgiri Hills (2000–2500 m above mean sea level), Southern India, where the present climatic conditions are cool (mean annual temperature 15°C) and humid (mean annual rainfall 2500 mm). Thick (50–80 cm) dark‐reddish brown topsoil overlies strongly desilicated yellowish‐red materials. This horizon has andic properties to a sufficient depth and the carbon content requirement of the melanic epipedon to place these soils in the Andisol order. Our data as well as the history of the Nilgiri Hills suggest that the formation of these non‐allophanic Andisols resulted from the succession of two main steps. First, a ‘lateritic’ weathering cycle led to the relative accumulation of secondary Al and Fe oxides. Later, the accumulation of organic matter favoured by a more recent climatic change induced complexation by organic acids of Al and Fe oxides, and the production of enough metal–humus complexes to give rise to andic properties. Such soils, in which secondary Al and Fe oxides, generally considered as indicators of an advanced weathering stage, are involved in a new cycle of soil formation, are original Andisols.     

Copper retention by Danish Spodosols in relation to contents of organic matter and aluminum,iron, and manganese oxides

Abstract

The importance of various soil components on copper (Cu) retention by Spodosois was investigated. Copper sorption and extraction were conducted on samples from the B horizon from six Danish Spodosois. The investigation was conducted on untreated samples, on hydrogen peroxide‐treated samples (to remove organic matter), on oxalate‐treated samples [to remove amorphous to poorly crystalline aluminum (Al) and iron (Fe) oxides], on hydroxylamine‐treated samples [to remove manganese (Mn) oxides]. Subfractions treated with hydrogen peroxide (H₂O₂) were further treated with oxalate and citrate‐bicarbonate‐dithionite (CBD). Sorption of Cu from an initial 10^‐6 M solution after 48 hours was determined in the pH range 3 to 7 using 0.1M sodium nitrate (NaNO₃) as the background electrolyte. The pH‐dependent sorption curve (sorption edge) was shifted to a higher pH with decreasing Al oxide content in the soils, and for the treated sample after removal of organic matter and Al and Fe oxides. A negligible effect was seen after removal of the Mn oxides because of their low abundance. Extraction of sorbed Cu at pH 4 to 6 with 0.1M nitric acid (HNO₃) for 24 hours confirmed the sorption results, in inasmuch as removal of the Al (and Fe) oxides increased Cu extractability. Therefore, it was concluded that in the soils investigated, Cu retention is mainly determined by the oxalate‐extractable Al fraction with a minor contribution due to crystalline Fe oxides.     

鄂南第四纪粘土红壤团聚体的稳定性及其稳定机制初探

用湿筛法和LeBissonnais法研究了鄂南第四纪红粘土母质发育的两种侵蚀程度的红壤团聚体的稳定性,并且分析了影响供试土壤团聚体稳定性的土壤性质。结果表明,轻度侵蚀的耕作土壤团聚体的稳定性较低,在水的作用下易崩解成较小粒径的水稳性团聚体;强度侵蚀的土壤表层团聚体的稳定性较高,崩解后产生较多的水稳性大团聚体。引起土壤团聚体破坏的主要作用机制是土壤团聚体中的闭蓄空气爆破引起的消散作用;研究区第四纪红壤团聚体的主要胶结物质是土壤中的粘粒、游离氧化铁铝和无定形铁。由于供试土壤中有机质含量很低,在本研究中,有机质含量与土壤团聚体稳定性之间没有显著正相关关系。     

Stabilization of organic matter in temperate soils: mechanisms and their relevance under different soil conditions – a review

Mechanisms for C stabilization in soils have received much interest recently due to their relevance in the global C cycle. Here we review the mechanisms that are currently, but often contradictorily or inconsistently, considered to contribute to organic matter (OM) protection against decomposition in temperate soils: (i) selective preservation due to recalcitrance of OM, including plant litter, rhizodeposits, microbial products, humic polymers, and charred OM; (ii) spatial inaccessibility of OM against decomposer organisms due to occlusion, intercalation, hydrophobicity and encapsulation; and (iii) stabilization by interaction with mineral surfaces (Fe‐, Al‐, Mn‐oxides, phyllosilicates) and metal ions. Our goal is to assess the relevance of these mechanisms to the formation of soil OM during different stages of decomposition and under different soil conditions. The view that OM stabilization is dominated by the selective preservation of recalcitrant organic components that accumulate in proportion to their chemical properties can no longer be accepted. In contrast, our analysis of mechanisms shows that: (i) the soil biotic community is able to disintegrate any OM of natural origin; (ii) molecular recalcitrance of OM is relative, rather than absolute; (iii) recalcitrance is only important during early decomposition and in active surface soils; while (iv) during late decomposition and in the subsoil, the relevance of spatial inaccessibility and organo‐mineral interactions for SOM stabilization increases. We conclude that major difficulties in the understanding and prediction of SOM dynamics originate from the simultaneous operation of several mechanisms. We discuss knowledge gaps and promising directions of future research.     

Speciation of phosphorus in temperate zone forest soils as assessed by combined wet‐chemical fractionation and XANES spectroscopy

Phosphorus availability in terrestrial ecosystems is strongly dependent on soil P speciation. Here we present information on the P speciation of 10 forest soils in Germany developed from different parent materials as assessed by combined wet‐chemical P fractionation and synchrotron‐based X‐ray absorption near‐edge structure (XANES) spectroscopy. Soil P speciation showed clear differences among different parent materials and changed systematically with soil depth. In soils formed from silicate bedrock or loess, Fe‐bound P species (FePO₄, organic and inorganic phosphate adsorbed to Fe oxyhydroxides) and Al‐bound P species (AlPO₄, organic and inorganic phosphate adsorbed to Al oxyhydroxides, Al‐saturated clay minerals and Al‐saturated soil organic matter) were most dominant. In contrast, the P speciation of soils formed from calcareous bedrock was dominated (40–70% of total P) by Ca‐bound organic P, which most likely primarily is inositol hexakisphosphate (IHP) precipitated as Ca₃‐IHP. The second largest portion of total P in all calcareous soils was organic P not bound to Ca, Al, or Fe. The relevance of this P form decreased with soil depth. Additionally, apatite (relevance increasing with depth) and Al‐bound P were present. The most relevant soil properties governing the P speciation of the investigated soils were soil stocks of Fe oxyhydroxides, organic matter, and carbonate. Different types of P speciation in soils on silicate and calcareous parent material suggest different ecosystem P nutrition strategies and biogeochemical P cycling patterns in the respective ecosystems. Our study demonstrates that combined wet‐chemical soil P fractionation and synchrotron‐based XANES spectroscopy provides substantial novel information on the P speciation of forest soils.     

Colloidal stability in some tropical soils of southeastern Nigeria as affected by iron and aluminium oxides

The stability of microaggregates in soils as opposed to its dispersion is a very important soil phenomenon that checks degradation arising from unguided tillage and soil erosion. Ten soils from southeastern Nigeria were sampled from their typical A and B horizons for the study. The aim was to identify the extent of colloidal stability of the soils and the forms of Fe and Al oxides in the soils contributing to their stability. The soils are mostly Ultisols and Inceptisols formed on sandstones and shale parent materials. The soils are low in soil basic cations including the soil organic carbon (SOC). The major clay mineral is kaolinite while the soil is acid in reaction. The various forms of soil Fe and Al oxides are high with the total forms of Fe and Al being most dominant and > dithionite extracted Fe and Al > oxalate extracted Fe and Al > pyrophosphate extracted Fe and Al. The water-dispersible clay and silt (WDC) and (WDSi) which are index of dispersion in most soils are low to medium thus reflecting in the low to medium dispersion ratio (DR). The clay flocculation index (CFI) and aggregated silt + clay (ASC) were moderate to high implying the high potential stability of the soils. Soil organic carbon did not seem to be contributing much to the stability of the microaggregates while oxalate and pyrophosphate extractable Fe (Fe_ox, Fe_p) and to some extent total Al (Al_t) were among the different forms of oxides that act as aggregating agents. We propose here that rather than SOC acting as a disaggregating agent in the soils, it might have acted in association with these oxides in a linkage or bridge such as C–P–OM–C to ensure stability of the soils.     

An assessment of EDTA as an extractant of organic-complexed and amorphous forms of Fe and Al in soils

EDTA solutions proposed as selective extractants of amorphous and organic forms of Fe and Al in soils and synthetic materials were tested. Extraction of Fe and Al from some soil samples continued at a decreasing rate beyond 120 days. For some soil samples and synthetic materials the amounts of Fe and Al extractable by EDTA (90 days) were markedly lower than those extractable by acid ammonium oxalate (2 h). Extraction of samples for 1 h with EDTA was shown to release amounts of Fe and Al far below those considered to be complexed with organic matter. The EDTA extraction procedures tested should not replace either acid ammonium oxalate for estimating amorphous forms of Fe and Al or pyrophosphate for estimating organic forms of Fe and Al in soils.     

The influence of weathering processes on labile and stable organic matter in Mediterranean volcanic soils

The relationship and mechanisms among weathering processes, cation fluxes, clay mineralogy, organic matter composition and stability were studied in soils developing on basaltic material in southern Italy (Sicily). The soils were transitions between Phaeozems and Vertisols. Intense losses of the elements Na, Ca and Mg were measured indicating that weathering has occurred over a long period of time. The main weathering processes followed the sequence: amphibole, mica, volcanic glass or if ash was the primary source → smectite → interstratified smectite–kaolinite → kaolinite. Kaolinite formation was strongly related to high Al, Mg and Na losses. The good correlation between oxyhydroxides and kaolinite in the soils suggests that (macro)aggregates have formed due to physical or electrostatic interactions between the 1:1 clay minerals and oxides. The stability of organic matter was investigated with a H₂O₂-treatment that assumes that chemical oxidation mimics the natural oxidative processes. The ratio of C after the H₂O₂ treatment to the total organic C ranged from 1–28%. No correlation between clay content and organic matter (labile or stable fraction) was found. The refractory organic fraction was enriched in aliphatic compounds and did not greatly interact with the kaolinite, smectite or poorly crystalline Fe or Al phases. A part of this fraction (most probably proteins) was bound to crystalline Fe-oxides. In contrast, the oxidisable fraction showed a strong relationship with poorly crystalline oxyhydroxides and kaolinite. Surprisingly, smectite did not contribute to the stabilisation of any of the organic C fractions. The stabilisation of organic matter in the soils has, therefore, two main mechanisms: 1) the protection of labile (oxidisable with H₂O₂) organic matter, including also aromatic-rich compounds such as charcoal, by the formation of aggregates with oxyhydroxides and kaolinite and 2) the formation of a refractory fraction enriched in aliphatic compounds.     

淹水条件下施加石灰和有机质对酸性土壤性质和磷吸附的影响

每公斤土加入2克碳酸钙和(或)三叶草的5个老成土和1个氧化土,在淹水培育45天后风干,结果发现:(1)淹水土壤风干,其pH比淹水时低,但仍比未淹水的高;(2)淹水降低了土壤中0.5MCuCl₂提取的铝量,石灰和三叶草处理使3个轻质土中的铝量进一步降低,但3个粘质土则呈现相反的趋势;(3)改良剂使3个轻质土吸附的磷减少,而使3个粘质土吸附的磷增加。前者增加的原因是因为通过还原作用和氧化作用形成了较多的活性表面,而后者的减少则可能是粘粒表面所形成的水化氧化物胶膜堵塞了原有的吸附位,从而使吸附位减少(4)改良剂对磷解吸的影响,是降低了3个轻质土的磷解吸,而增加了3个粘质土的磷解吸;(5)经淹水风干处理土壤的磷吸附量与草酸盐提取的铁、铝、锰及CuCl₂溶液提取的铝有很高的相关性,表明控制淹水土壤磷吸持的土壤组分,不仅包括无定形铁,而且也包括羟基铝聚合物。