Titratable Acidity and Alkalinity of Red Soil Surfaces

The surfaces of red soils have an apparent amphotenc character, carrying titratable acidity and titratable alkalinity simultaneously. The titratable acidity arises from deprotonation of hydroxyl groups of hydrous oxide-type surfaces and dissociation of weak-acid functional groups of soil organic matter, while the titratable alkalinity is derived from release of hydroxyl groups of hydrous oxide-type surfaces. The titratable acidity and titratable alkalinity mainly depended on the composition and content of iron and aluminum oxides in the soils. The results showed that the titratable acidity and titratable alkalinity were in significantly positive correlation not only with the content of amorphous aluminum oxide(Alo) and iron oxide(Feo) extracted with acid ammonium oxalate solution, free iron ox-ide(Fed) extracted with sodium dithionite-citrate-bicarbonate (DCB) and clays, but also with the zero point of charge (ZPC) of the samples. Organic matter made an important contribution to the titratable acidity.     

Clay minerals and humus complexes in five Kenyan soils derived from volcanic ash

Clay minerals and humus complexes and their effects on soil chemical properties were studied for five profiles around the Longonot and Susua volcanoes in Kenya. Morphologically, all profiles have some resemblance to Andepts, but there were clear-cut differences in clay contents and mineral composition as well as pH between profiles 1 through 4 and profile 5, which occur under semi-arid to subhumid and under humid climatic conditions, respectively. Profiles 1 through 4 contained embryonic halloysites with X-rays amorphous iron oxide and silica, whereas profile 5 contained a kaolin mineral, chloritized 2:1 layer silicates, gibbsite and hematite. These mineral associations probably represent early and advanced stages of weathering of volcanic ash under weak and strong leaching conditions, respectively. Embryonic halloysites consisted of more or less poorly ordered halloysite and “1.0- and 0.7-1.0-nm minerals”. The carbon contents of A horizons ranged from 100 to 112 g/kg in profiles 2, 3 and 5. Humus complexes increased in the order; Fehumus ⩽ Al-humus ⩽ Ca-humus in profiles 2 and 3, whereas Al- and Fe-humus were found exclusively in profile 5. The pH (NaF), phosphate retention and acid oxalate extractable Al qualify only profile 5 as an Andept or Andisol.     

Interaction of aluminum and iron oxides and clay minerals and their effect on soil physical properties: A review

Abstract

Amorphous and crystalline aluminum and iron oxide minerals play a major role in stabilizing soil structure as measured by aggregate stability and clay dispersion. Aluminum and iron oxide interactions with clays are pH dependent. At low pH, where the oxides carry sufficient positive charge, they precipitate on clay surfaces. These coatings, once formed, are stable at higher pHs. Precipitation of oxides at high pH occurs as phases separate from the clays. Aluminum and iron oxides stabilize clay minerals by decreasing critical coagulation concentration, clay dispersion, water uptake, and clay swelling and by increasing microaggregation. The presence of aluminum and iron oxide minerals in soils has a favorable effect on soil physical properties, increasing aggregate stability, permeability, friability, porosity, and hydraulic conductivity, and reducing swelling, clay dispersion, bulk density, and modulus of rupture.     

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.     

Speciation and sorption structure of diphenylarsinic acid in soil clay mineral fractions using sequential extraction and EXAFS spectroscopy

Purpose

The mobility of arsenic (As) in soils is fundamentally affected by the clay mineral fraction and its composition. Diphenylarsinic acid (DPAA) is an organoarsenic contaminant derived from chemical warfare agents. Understanding how DPAA interacts with soil clay mineral fractions will enhance understanding of the mobility and transformation of DPAA in the soil-water environment. The objective of this study was to investigate the speciation and sorption structure of DPAA in the clay mineral fractions.

Materials and methods

Twelve soils were collected from nine Chinese cities which known as chemical weapons burial sites and artificially contaminated with DPAA. A sequential extraction procedure (SEP) was employed to elucidate the speciation of DPAA in the clay mineral fractions of soils. Pearson’s correlation analysis was used to derive the relationship between DPAA sorption and the selected physicochemical properties of the clay mineral fractions. Extended X-ray absorption fine structure (EXAFS) L_III-edge As was measured using the beamline BL14W1 at Shanghai Synchrotron Radiation Facility (SSRF) to identify the coordination environment of DPAA in clay mineral fractions.

Results and discussion

The SEP results showed that DPAA predominantly existed as specifically fraction (18.3–52.8%). A considerable amount of DPAA was also released from non-specifically fraction (8.2–46.7%) and the dissolution of amorphous, poorly crystalline, and well-crystallized Fe/Al (hydr)oxides (20.1–46.2%). A combination of Pearson’s correlation analysis and SEP study demonstrated that amorphous and poorly crystalline Fe (hydr)oxides contributed most to DPAA sorption in the clay mineral fractions of soils. The EXAFS results further demonstrated that DPAA formed inner-sphere complexes on Fe (hydr)oxides, with As-Fe distances of 3.18–3.25 Å. It is likely that the steric hindrance caused by phenyl substitution and hence the instability of DPAA/Fe complexes explain why a substantial amount of DPAA presented as weakly bound forms.

Conclusions

DPAA in clay mineral fractions predominantly existed as specifically, amorphous, poorly crystalline, and crystallized Fe/Al (hydr)oxides associated fractions. Amorphous/poorly crystalline Fe rather than total Fe contributed more to DPAA sorption and DPAA formed inner-sphere complexes on Fe (hydr)oxides.

     

土壤中水合氧化物型表面的化学区分——Ⅱ.电荷零点

本文研究了氧化物对红壤、高岭土和合成无定形铝硅酸盐的电荷零点的影响,并讨论了土壤中水合氧化物型表面的区分。结果表明,水合氧化物型表面可进一步区分为电荷性质完全不同的两类亚表面。在所研究的土壤和粘土样本中,有高ZPC的氧化铁(Fe-OH)和氧化铝(Al-OH)表面,是带可变正电荷的亚表面,使样本的ZPC趋于上升;而有低ZPC的氧化硅(Si-OH)表面,是带可变负电荷的亚表面,使样本的ZPC趋于下降。合成无定形铝硅酸盐的电荷零点与样本的Al₂O₃/Si₂,摩尔比呈显著的正相关。     

Changes in aluminum pools of andisols due to soil acidification

Abstract

Aluminum concentrations in soil solutions are not only controlled by inorganic clay minerals but also by organically bound aluminum. The objective of this study was to determine which pools contribute to Al dissolution. Soil samples were taken at various distances from tree trunks and at various depths at the Rolling Land Laboratory (RLL), Hachioji, Tokyo. Selective dissolution techniques were used to analyze the changes in pools of solid-phase aluminum. Soil pH values around Hinoki cypresses were in the aluminum buffer range. Exchangeable aluminum contents in soils under Hinoki cypresses were 104 mmol_c kg-^?1 on the average. This value was similar to that of the cation exchange capacity (CEC) of Andisols at RLL at a soil pH of 4. The relationship between the soil pH and exchangeable, organically bound, and amorphous aluminum pools showed that dissolved aluminum ions in the soil solution were primarily derived from the amorphous Al pool. Dissolved aluminum ions were substituted with base cations of soils, resulting in the increase of the content of exchangeable Al and/or the formation of complexes with organic matter which increased the proportion of organically bound Al pools. Increase in the proportion of organically bound Al pools indicated the importance of complexation with soil organic matter for controlling the aluminum concentration in the soil solution.     

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.     

Phosphate sorption by red mediterranean soils from Greece

Abstract

In nineteen surface horizons of red Mediterranean soils from various locations of Greece, phosphorus (P) sorption experiments were conducted and the sorption characteristics were studied in relation to soil properties. Phosphate sorption data were fitted both to the Langmuir and Freundlich equations. From these equations, the following P sorption parameters were determined from the Freundlich equation, X = ACⁿ, the parameters A (the phosphate sorbed at C = 1 mg P/L), n (the P sorption intensity), the P sorption index (PS = X/log C) and maximum P sorption (Xmfr). From the Langmuir equation, C/X = 1/KXm + C/Xm, the parameters K (showing the bonding energy), maximum P sorption (Xmla), the quantity of P adsorbed at a standard concentration of 0.2 mg P/L (P0.2), and P maximum buffering capacity (PMBC). The Freundlich parameter A was strongly correlated to the clay and sesquioxides ("free”; iron and aluminum oxides and amorphous iron oxides) content. Seventy‐four percent of the variance of this parameter was explained by clay and “free”; iron (Fe) content. The Freundlich parameter n was significantly correlated with pH and amorphous iron oxides content, while 52% of its variance was explained by amorphous Fe and dithionite extrac‐table aluminum (Al). The P sorption maxima calculated from the Freundlich equation were in general lower than those calculated by the Langmuir equation. Both these parameters were strongly correlated with clay and more slightly with sesquioxides content. About 50% of their variance was explained by clay content of the soils. The P sorption index was strongly correlated with the clay content and less strongly with dithionite‐extractable Fe and Al. The P‐buffering capacity calculated from the data of Langmuir equation was also strongly correlated with these two parameters. In addition, clay content and dithionite‐extractable Fe and Al were well correlated to the amounts of P required to obtain an equilibrium concentration of 0.2 mg P/L while 61% of the variation of this parameter was explained by the clay and the dithionite‐extractable Fe content. From these findings, it seems that for the red Mediterranean soils from Greece, P sorption is affected by clay content and iron and aluminum oxide contents.     

Assessment of potentially reactive pools of aluminum in Andisols using a five-step sequential extraction procedure

A five-step sequential extraction procedure was developed for the partitioning of soil aluminum (Al) into five fractions: exchangeable, weakly organic bound, strongly organic bound, inorganic non-crystalline and crystalline. The results obtained by the sequential extraction method for Al were compared with those estimated from single extractions using identical operating conditions applied in each individual sequential fraction. The Al content in the extracts was measured by inductively coupled plasma optical emission spectrometry. The results indicated that the first four steps [potassium chloride (KCl), copper chloride (CuCl₂), sodium pyrophosphate (Na₄P₂O₇), acid ammonium oxalate ((NH₄)₂C₂O₄)] in the sequential procedure could be as effective as single extraction methods at estimating exchangeable Al, weakly organic bound Al, strongly organic bound Al, and non-crystalline Al. However, the crystalline Al content by sequential procedure was not in agreement with single extraction procedures. Further, the sequential extractions resulted in more consistent estimates of the aluminum/silicon (Al/Si) molar ratio and allophane and crystalline Al contents than single extractions method. Results of X-ray diffraction on the soil samples confirm the presence of appreciable amounts of at least three types of crystalline minerals, including gibbsite, vermiculite or halloysite. Our result implies that the sequential method can be more reliable in estimating the various Al forms in Andisols.     

Surface chemical properties and pedogenesis of tropical soils derived from basalts with different ages in Hainan,China

Limited information is available on the changes of surface chemical properties of tropical soils with time during the pedogenesis. Soil samples of three profiles derived from basalts of 10, 1330 and 2290 kilo annum (ka) in age were collected from adjacent locations in a tropical region of Hainan Province, China. The changes in soil surface chemical properties and the mineralogy of the soil clay fraction with time were investigated using ion adsorption, micro-electrophoresis, and X-ray diffraction analysis. The content of 2:1-type clay minerals decreased, while those of kaolinite and gibbsite increased with increasing basalt age and degree of soil development. The content of pedogenic free iron (Fe) oxides and the ratio of free Fe oxides/total Fe oxides increased with soil development stage, while soil poorly crystalline Fe and aluminum (Al) oxides had an opposite trend. The positive surface charge of the soils increased with increasing basalt age and degree of soil development; this was consistent with the change in their contents of free Fe/Al oxides. However, the value of negative surface charge had an opposite behavior. The soil derived from 10-ka-basalt had much more negative charge than soils derived from 1330- and 2290-ka-basalt. Soil net surface charge and zeta potential of the soil clay-fraction decreased with the increase in basalt age. Both net charge–pH curves and zeta potential–pH curves shifted to positive values with increased basalt age and degree of soil development. Increasing age also elevated the point of zero net charge of the soil and the isoelectric point of soil colloids.     

The nature and composition of amorphous material and free oxides in some temperate region and tropical soils

Abstract

Amorphous clay separated from pedons of a highly weathered soil previously classified as Oxisol and an Ultisol of the Southern States and, from the surface horizons of an Oxisol and two Andepts of the tropics were studied by chemical, DTA, infrared and X‐ray analysis.

Considerable amounts of amorphous material, 20–37% in temperate region and 29–40% in tropical soils, were extracted by differential dissolution using 0.5 N NaOH. The molar SiO₂/Al₂O₃ ratios of the dissolved material varied from sesquioxidic to siliceous (0.36–9.1) in temperate region soils, whereas those of the Andepts were allophonic (1.5–1.7). DTA and infrared analysis confirmed these results, however the strong gibbsite peaks in the X‐ray analysis of temperate region soils suggested that the aluminum fraction dissolved was in part, if not all, crystalline in nature. Indications were obtained with DTA and infrared that Na‐dithionite treatment might have altered the nature of the clay.     

Fe and Al Sedimentation and their Importance as Carriers for P, N and C in a Large Humic Lake in Northern Sweden

The sedimentation of organic, amorphous oxides, crystalline oxides and crystalline silicate species of Fe and Al was investigated in humic Lake Örträsket. The covariation with C, N and P sedimentation also was studied. The results showed a strong temporal variation in the occurrence of different Fe species. During high discharge, such as in spring. Fe mostly occurred as crystalline Fe-silicate species, while the amorphous form dominated at other times of the year. Al generally sedimented as crystalline AI-silicate species (95%). Amorphous Fe species showed a strong relation with organic C and N, suggesting an association between organic material and amorphous Fe oxides. P was not as strongly related to amorphous Fe, probably as a result of apatite or clay bound-P species sedimentation.     

土壤中水合氧化物型表面的化学区分Ⅰ.表面电荷

本文研究了氧化物对土壤、粘土和合成无定形铝硅酸盐的表面电荷的贡献.结果表明,水合氧化物型表面可进一步区分为电荷性质完全不同的两类亚表面.在所研究的样本中,氧化铁和氧化铝是带可变正电荷的亚表面,而氧化硅是带可变负电荷的亚表面.     

Changes in the system of chemical bonds in gibbsite under the impact of NH<Subscript>4</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> solutions of different concentrations

The participation of anionic aluminum hydroxo complexes in the binding of phosphate anions on the surface of gibbsite has been shown. The succession of changes in the anionic aluminum phosphate complexes under increasing concentration of phosphate solution has been studied. It has been found that aluminum polyphosphate complexes responsible for the intensive dissolution of gibbsite are formed, along with aluminum orthophosphate complexes, at phosphate solution concentrations of 1 and 2 mol P/L. The decisive role of polyphosphate (P–O–P) groups in the ligand structure of anionic complexes in the transformation of gibbsite to a phosphate mineral (ammonium taranakite) has been revealed. The role of hydrogen bonds with the participation of ligand P(O)OH groups in the formation of ammonium taranakite crystals has been discussed.     

Aggregation in soils with small amounts of swelling clays. I. Aggregate stability

The respective role of organic materials and poorly-ordered Al and Fe hydrous oxides on soil aggregate stability was studied in silty soils with little swelling clay, using both multivariate analysis and physico-chemical approaches. Soil disaggregation is a function of the hydrophobic character of organic matter (OM), which depends on the nature of the organic materials, cationic environment and the aggregating effect of Al and Fe hydrous oxides.
Two kinds of aggregates >50 μm can be distinguished in organic soils, one being about six times more stable than the other. In soils poor in organic matter, weak aggregates dominate; the binding agents are Ca or Al OM rich in polysaccharides and peptides.     

Evaluation of industrial by-products as soil acidity amendments: chemical and mineralogical implications

Lime, mined gypsum and some gypsum-like by-products have been frequently applied to soil to counter acidity. We have examined the changes in the chemical and mineralogical properties of three acid soils resulting from the application of three industrial by-products (phosphogypsum, red gypsum and sugar foam). We did so in laboratory experiments on suspensions of soil in saturated solutions of the by-products. A sizeable fraction of the Al released by exchange with Ca of the amendments remained on the mineral surfaces as Al polymers, as suggested by changes in the CuCl₂-, oxalic–oxalate- and DTPA-extractable Al contents. Polymerization of Al was promoted by corresponding neutral and basic pH of red gypsum and sugar foam saturated solutions, respectively. Sorption of these Al polymers was particularly favourable in those horizons with more clay fraction and variable-charge clay minerals. On the other hand, in most cases there was little or no detectable sorption of sulphate, thus excluding precipitation of crystalline or amorphous basic Al sulphates to alleviate Al toxicity. Based on the reduction of the Al saturation of the exchange complex in the soils, as well as on the small contents of heavy metals and natural radionuclides of the three by-products, these can be considered effective alternatives to mined gypsum and lime for alleviating soil acidity and reducing toxic concentrations of Al in agricultural, acid soils.     

Poorly crystalline iron and aluminium oxides contribute to the carbon saturation and sorption of dissolved organic carbon in the soil

Soil carbon (C) saturation implies an upper limit to a soil's capacity to store C depending on the contents of silt + clay and poorly crystalline Fe and Al oxides. We hypothesized that the poorly crystalline Fe and Al oxides in silt + clay fraction increased the C saturation and thus reduced the capacity of the soil to sorb additional C input. To test the hypothesis, we studied the sorption of dissolved organic carbon (DOC) on silt + clay fractions (<53 µm) of highly weathered oxic soils, collected from three different land uses (i.e., improved pasture, cropping and forest). Soils with high carbon saturation desorbed 38% more C than soils with low C saturation upon addition of DOC, whereas adsorption of DOC was only observed at higher concentration (>15 g kg^?1). While high Al oxide concentration significantly increased both the saturation and desorption of DOC, the high Fe oxide concentration significantly increased the desorption of DOC, supporting the proposition that both oxides have influence on the DOC sorption in soil. Our findings provide a new insight into the chemical control of stabilization and destabilization of DOC in soil.     

Origin of the pH-dependent cation exchange capacities of Irish soil clays

Values of cation exchange capacity determined at pH 4.8 and at pH 8.2 are reported for peroxidized clay separates from a group of Irish soils derived from a variety of parent materials. The correlation between the two measurements was poor. The differences between the values (pH-dependent CEC's) ranged from 0.1 to 58.6 mequiv./100 g, with a mean of 12.9 mequiv./100 g. The highest values were associated with clays from spodic horizons and clays from basalt-derived soils. CEC at pH 8.2 and pH-dependent CEC were highly correlated with citrate-dithionite-bicarbonate (CDB) extractable Al. In contrast, CEC at pH 4.8 was negatively correlated with this parameter, suggesting that hydrous oxides reduced CEC at low pH values.Values of CEC of pH 4.8 and pH 8.2 are also reported for a selection of 16 clays subjected to sequential extraction with CDB and NaOH. CDB treatment reduced mean pH-dependent CEC from 20.4 to 9.0 mequiv./100 g, which was reduced to 3.9 mequiv./100 g by subsequent extraction with NaCH. The material removed by CDB was apparently positively charged at pH 4.8 and negatively charged at pH 8.2. Most of the pH-dependent CEC remaining after CDB treatment was associated with the clays from spodic horizons. The material extracted by NaOH was apparently negatively charged at both pH 4.8 and pH 8.2. No direct evidence of the physical nature of this material was obtained but it was present in sufficient amounts to suggest that it existed in particular forms in some of the clays from the spodic horizons. Following the dissolution treatments, the correlation between CEC values at pH 4.8 and pH 8.2 was very good (r = 0.99).     

中国土壤胶体研究 Ⅵ.西藏高原几种主要土壤的粘土矿物组成和演变

西藏高原突起于我国西南,绝大部分地面的海拔高度在4000米以上,为世界上最高的大高原。它大致在第三纪开始形成,后来曾受第四纪冰川的深刻作用,高山顶部至今仍是冰川的活动场所^[1,2]。高原为昆仑山、唐古拉山、喜马拉雅山和横断山等大山脉所盘踞。