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.     

Horizontal distribution of main hydroxyanthraquinones in soil

Six hydroxyanthraquinones (chrysophanol, chrysotalunin, microcarpin, physcion, 7,7′-biphyscion, and hinakurin) present in the samples of 26 surface soils were quantitatively analyzed, and the contents of HAQs in soil types were compared. The soil samples had been collected from 19 Umbric Andosols and seven Distric Cambisols, and the Andosols were further subdivided into those with allophanic soil materials (exchange acidity (y ₁<5 mL 100 g^-l) and nonallophanic soil materials (y _l≧5 mL 100 g^-l). The following results were obtained. (1) It was determined quantitatively for the first time that chrysotalunin was the major hydroxyanthraquinone in many soils. (2) The amounts of major dime ric hydroxyanthraquinones (chrysotalunin, 7,7′-biphyscion, and microcarpin) in non-allophanic soil materials were significantly larger than those in allophanic soil materials. As the contents of chrysotalunin in Andosols were positively correlated with y _l, which was reported to be positively correlated with aluminum toxicity and exchangeable aluminum in soil, it is suggested that toxic aluminum may be involved in the production of soil hydroxyanthraquinones.     

Investigation of soils developed on volcanic materials in Nisyros Island, Greece

Soils that are forming on volcanic parent materials have unique physical and chemical properties and in most cases, on wet and humid climates, are classified as Andisols. The main purpose of this study is to examine if the soils that are forming on volcanic materials under a dry Mediterranean climate, in Nisyros Island (Greece), meet the requirements to be classified as Andisols. Soils from seven sites were sampled and examined for their main physico-chemical properties and selective dissolution analysis. Dithionite–citrate–bicarbonate (DCB) extractable Al and Fe (Ál_d, Fe_d), acid ammonium oxalate extractable Al, Fe, and Si (Ál_o, Fe_o and Si_o), and sodium pyrophosphate extractable Al and Fe (Al_p, Fe_p) were measured. In addition, Al and Si were determined after reaction with hot 0.5 M NaOH, (Al_NaOH and Si_NaOH) and with Tiron-(C₆H₄Na₂O₈S₂), (Al_T and Si_T). P-retention was also measured. The soils are characterised by coarse texture, low organic matter content, low values of cation exchange capacity (CEC), and high pH values. Values of Si_o, Al_o and Fe_o are less than 0.022%, 0.09% and 0.35% respectively, highlighting the lack of noncrystalline components. The ratio (Fe_d–Fe_o)100/Fe_d is quite high expressing the degree of crystallisation of free iron oxides. For all samples tested, values of the Al_o + 1/2Fe_o index are extremely low (< 0.24%). High Si_NaOH and Si_T (arising 2.76% and 2.18% respectively) indicate the presence of silica in amorphous forms. P-retention values are very low (< 12.6%). The results indicated the absence of noncrystalline minerals except for amorphous silica, and do not exhibit andic or vitric soil characteristics to be classified as Andisols.     

Lability of soil organic carbon in tropical soils with different clay minerals

Soil organic carbon (SOC) storage and turnover is influenced by interactions between organic matter and the mineral soil fraction. However, the influence of clay content and type on SOC turnover rates remains unclear, particularly in tropical soils under natural vegetation. We examined the lability of SOC in tropical soils with contrasting clay mineralogy (kaolinite, smectite, allophane and Al-rich chlorite). Soil was sampled from A horizons at six sites in humid tropical areas of Ghana, Malaysian Borneo and the Solomon Islands and separated into fractions above and below 250 μm by wet sieving. Basal soil respiration rates were determined from bulk soils and soil fractions. Substrate induced respiration rates were determined from soil fractions. SOC lability was significantly influenced by clay mineralogy, but not by clay content when compared across contrasting clay minerals. The lability of SOC was lowest in the allophanic and chloritic soil, higher in the kaolinitic soils and highest in the smectitic soil. Our results contrast with conventional concepts of the greater capacity of smectite than of kaolinite to stabilize SOC. Contents of dithionite-citrate-bicarbonate extractable Fe and Al were inversely related to SOC lability when compared across soil types. A stronger inverse correlation between content of ammonium-oxalate extractable Fe and SOC lability was found when considering the kaolinitic soils only and we conclude that the content of active Fe (hydr-) oxides controls SOC stabilization in the kaolinitic soils. Our results suggest that the validity of predictive models of SOC turnover in tropical soils would be improved by the inclusion of soil types and contents of Fe and Al (hydr-) oxides.     

Aluminum toxicity of synthetic aluminum–humus complexes derived from non-allophanic and allophanic Andosols and its amelioration with allophanic materials

Natural non-allophanic Andosols often show aluminum (Al) toxicity to Al-sensitive plant roots. The significance of Al–humus complexes to Al toxicity has been emphasized. Allophanic Andosols also possess Al–humus complexes, but they rarely show any toxicity. In the present study, using model substances, we tested the toxicity of Al–humus complexes and its amelioration with allophanic materials. We extracted humic substances from the A horizons of a non-allophanic Andosol and an allophanic Andosol using a NaOH solution, and reacted the humic substances and partially neutralized AlCl₃ solution at pH 4. Allophanic material was purified from commercial Kanuma pumice. Plant growth tests were conducted using a medium containing the Al–humus complexes (50 g kg⁻¹), the allophanic material (0, 90, 180 and 360 g kg⁻¹) and perlite. The root growth of barley ( Hordeum vulgare L.) and burdock ( Arctium lappa ) was reduced in the media containing the Al–humus complexes derived from both the non-allophanic and allophanic Andosols when the allophanic material was not added. With the addition of the allophanic materials, particularly in the 360 g kg⁻¹ treatment, the growth of the barley roots was improved markedly. Although the root growth of the burdock tended to improve with allophanic materials, the effect was weaker than that for barley. Monomeric Al in a solution of the medium was not detected (< 0.05 mg L⁻¹) following the addition of 360 g kg⁻¹ of allophanic materials, whereas 0.8–1.7 mg L⁻¹ Al was recorded without the allophanic material.     

Aluminum status of synthetic Al–humic substance complexes and their influence on plant root growth

Abstract

Aluminum (Al)–humus complexes are abundant in the A horizons of non-allophanic Andosols and contribute to the unique properties of volcanic ash soils, such as high reactivity with phosphate ions and a low bulk density. Natural non-allophanic Andosols commonly show Al toxicity to plant roots. There have been very few studies examining the contribution of Al–humus complexes to the Al toxicity of plant roots, although the complexes are the probable source of the toxic Al. We extracted humic substances from the A horizon of a non-allophanic Andosol using NaOH solution and reacted the humic substances and partially neutralized the AlCl₃ solution at three pH conditions (pH 4.0, 4.5 and 5.5) to prepare pure Al–humic substance complexes. The Al solubility study (equilibrium study in 10^?2 mol L^?1 CaCl₂) and the Al release study (a stirred-flow method using 10^?3 mol L^?1 acetate buffer solution adjusted to pH 3.5) indicated that all the synthetic complexes easily and rapidly release monomeric Al into the liquid phase with slight changes in pH and ion strength, although the Al contents and their extent of polymerization are considerably different among the complexes. A plant growth test was conducted using a medium containing the Al–humic substance complexes and perlite mixture. Root growth in burdock (Arctium lappa) and barley (Hordeum vulgare L.) was reduced equally by all three complex media, and the roots showed the typical injury symptoms of Al toxicity. These results indicate that in soils dominated by Al–humus complexes the Al released from the Al–humus complexes, as well as the exchangeable Al adsorbed by soil minerals, is definitely toxic to plant roots.     

Soil organic carbon changes in particle-size fractions following cultivation of Black soils in China

Soil texture can be an important control on soil organic carbon (SOC) retention and dynamics. The (clay + silt)-sized SOC pool (SOC < 20 μm) in non-cultivated or grassland soils has been proposed to reach an equilibrium or maximum level named protective capacity. Proper knowledge of SOC in this size fraction in non-cultivated and cultivated Black soils is important to evaluate management-induced changes in SOC in NE China. Twenty-seven paired soil samples (non-cultivated vs. cultivated) were collected in the Black soil zone in Heilongjiang and Jilin provinces. Bulk soil was dispersed in water with an ultrasonic probe and then soil size fractions were collected using the pipette technique for SOC analyses. Soil organic carbon in bulk soil and size fractions was measured by dry combustion. Average content of SOC < 20 μm was 23.2 g C kg⁻¹ at the 0–30 cm depth for the non-cultivated soils, accounting for 75.1% of the total SOC at the same depth. There was significant positive relationship between soil clay plus silt content and SOC < 20 μm in non-cultivated soils. Accordingly, a model of the maximum SOC < 20 μm in 0–30 cm depth of non-cultivated Black soils was developed: y = 0.36x where y is the maximum SOC < 20 μm pool (g C kg⁻¹) and x is the percentage of clay + silt (<20 μm) content. The average content of SOC < 20 μm was 18.7 g C kg⁻¹ at 0–30 cm depth for cultivated soils, accounting for 81.5% of total SOC. This average value of SOC was 4.4 g C kg⁻¹ less than the maximum value (23.1 g C kg⁻¹) and accounted for 55.0% of the difference of SOC between non-cultivated and cultivated Black soils. Cultivation resulted in 45.0% loss of sand-sized (>20 μm) SOC concentration relative to SOC < 20 μm. This result indicates that SOC < 20 μm and sand-sized SOC both play important roles in SOC dynamics resulting from management practices. This model can be applied to calculate the actual potential to restore SOC for cultivated Black soils under conservation tillage in NE China.     

Land-use/cover change effects and carbon controls on volcanic soil profiles in highland temperate forests

The stabilization of SOM by Al–humus complexes and non-crystalline minerals is a key issue to explain the soil-C variability and the biogeochemical processes that determine the fate of soil C following land-use/cover change (LUCC) in volcanic landscapes. In an altitudinal gradient of volcanic soils (2550–3500 masl), we quantified the total soil C (C_T) concentrations and stocks in soil pits sampled by genetic horizons. We performed analyses at landscape and local scales in order to identify and integrate the underlying environmental controls on C_T and the effects of LUCC. We selected four sites, two on the upper piedmont, one on the lower mountain slope and one on the middle mountain slope at Cofre de Perote volcano (eastern central Mexico) where temperate forests are the natural vegetation. At each site we selected three to five units of use/cover as a chronosequence of the LUCC pathways. In each soil horizon chemical characteristics (i.e. N, C/N ratio, pH, exchangeable bases) were determined and mineralogical properties were estimated from selective Al, Fe and Si oxalate and pyrophosphate extractions (i.e. the Alp/Alo ratio, the active Al related to non-crystalline minerals as Al_o ? Al_p, the allophane concentration, and the non-crystalline Al and Fe minerals as Al_o + 1/2Fe_o). At landscape scale, the Al–humus complexes were strongly related to the C_T concentration in topsoil (A horizons) but this relationship decreased with depth. In turn, the non-crystalline minerals and the C/N ratio explained the variability of the C_T concentrations in C horizons. At local scale, C_T concentrations and stocks were depleted after conversion of forest to agriculture in Vitric Andosols at the upper piedmont but this was not observed in Silandic Andosols. However, in Vitric Andosols the reduction of the C_T stocks is partially recovered throughout the regeneration/reforestation processes. The results suggest that the lower vulnerability of Silandic Andosols than Vitric Andosols to changes in the C_T after LUCC is due to the higher levels of SOM stabilized by Al–humus complexes and non-crystalline minerals in the Silandic soils. Furthermore, the importance of the allophane to explain the C_T stocks in the Silandic Andosols of the middle slopes suggests that the C_T stabilized by this mineral fraction in the subsoil adds an important fraction of the C_T to the estimates of the stocks.     

Comparing NaOH‐extractable organic matter of acid forest soils that differ in their pedogenic trends: a pyrolysis‐GC/MS study

Soil organic matter (SOM) in Alu‐andic Andosols and Alu‐humic Umbrisols is believed to accumulate because of the protection caused by binding to aluminium (Al). We investigated soils that differed in the abundance of organo‐Al complexes to determine the effect of such binding on SOM chemistry. For this, the surface horizons of three types of acid soils in the Basque Country (northern Spain) under forest stands were studied: (i) Alu‐andic Andosols (AND soils) on basalts and trachytes, (ii) Umbrisols or so‐called ‘aluminic’(ALU) soils also on basalts and trachytes and (iii) soils with a podzolizing trend (POD), on quartzites. Values of Al extractable with sodium pyrophosphate (Al_p) in the surface horizons of these soils ranged between 8.5 and 13.1, 1.9 and 9.3, and 0.8 and 3.7 g kg^?1 dry weight, for the AND, ALU and POD soils respectively. For POD and ALU soils, surface horizons were sampled at two depths, 0–5 and 5–20 cm, whereas the AND soils were sampled at different depths down to the B horizon. NaOH‐extractable SOM from three AND soils, 12 ALU soils and 12 POD soils was studied by pyrolysis‐gas chromatography/mass spectrometry. The POD soils had the largest loads of plant‐derived markers (lignin, long‐chain alkanes and alkenes, methyl ketones, fatty acids); SOM of the AND soils had the smallest amounts of plant‐derived SOM and the largest amounts of microbial products (microbial sugars and N‐compounds) of the soils studied. ALU soils had an intermediate pattern, as expected. The results indicate that the SOM of Alu‐andic Andosols, developed from basalt and trachyte rocks, is essentially dissimilar to that of soils derived from quartz‐rich parent material, under the same climate conditions and similar forest stands. The dominance of secondary (microbial‐derived) SOM in Alu‐andic Andosols, also observed in previous research on Sil‐andic Andosols (these are dominated by short‐range ordered Si compounds in contrast to the dominance of organo‐Al complexes in Alu‐andic Andosols), reveals the small contribution of primary (plant‐derived) material to SOM in soils with andic properties.     

Influence of Soil Chemical Properties on Adsorption and Oxidation of Phenolic Acids in Soil Suspension

Relationships between abiotic oxidation and adsorption of phenolic acids added to soils and soil chemical properties were investigated by using 32 soil samples and ferulic, vanillic, and p-hydroxybenzoic acids. Soil properties studied were as follows: (as adsorption factors) contents of acid oxalate extractable Al (Alo), Fe (Feo), dithionite-citrate-bicarbonate (DCB) extractable Fe (Fed), total carbon and clay, and (as oxidation factors) level of soil oxidative activity (Cr oxidation) determined by the amount of Cr(VI) converted from Cr(III) added to soils. Soil samples were divided into 3 types based on chemical properties: Andosols A (A horizon of Andosols), Andosols B (B horizon of Andosols and light-colored Andosols), and non-Andosols.

The recovery of all phenolic acids (RPA) was negatively correlated with the total carbon and Feo contents in Andosols A and B, respectively, which suggested adsorption onto soil organic matter in Andosols A and onto Feo in Andosols B. It was considered that almost no oxidation of phenolic acids occurred in Andosols A, because a very small amount of Cr(VI) was obtained. The recovery of ferulic acid (RFA) and vanillic acid (RVA), however, was negatively correlated with Cr oxidation in non-Andosols, suggesting that these phenolic acids were oxidized, while almost all of the p-hydroxybenzoic acid was recovered.

These results were also supported by the comparison between RFA and recovery of dissolved organic carbon (RTOC). RFA was very similar to RTOC in Andosols A and B, which indicated that adsorption occurred, whereas RFA was lower than RTOC in the non-Andosols that showed a high level of Cr oxidation, indicating that oxidation took place. Manganese dissolution which occurred when phenolic acids were added to soils was also examined.