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.     

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.

     

Retention of dissolved organic matter by illitic soils and clay fractions: Influence of mineral phase properties

The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N₂ method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m^–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m^–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.     

Adsorption and Desorption of Copper in Pasture Soils

Abstract

Copper (Cu) is bound strongly to organic matter, oxides of iron (Fe) and manganese (Mn), and clay minerals in soils. To investigate the relative contribution of different soil components in the sorption of Cu, sorption was measured after the removal of various other soil components; organic matter and aluminum (Al) and Fe oxides are important in Cu adsorption. Both adsorption and desorption of Cu at various pH values were also measured by using diverse pasture soils. The differences in the sorption of Cu between the soils are attributed to the differences in the chemical characteristics of the soils. Copper sorption, as measured by the Freundlich equation sorption constants [potassium (K) and nitrogen (N)], was strongly correlated with soil properties, such as silt content, organic carbon, and soil pH. The relative importance of organic matter and oxides on Cu adsorption decreased and increased, respectively, with increasing solution Cu concentrations. In all soils, Cu sorption increased with increasing pH, but the solution Cu concentration decreased with increasing soil pH. The cumulative amounts of native and added soil Cu desorbed from two contrasting soils (Manawatu and Ngamoka) during desorption periods showed that the differences in the desorbability of Cu were a result of differences in the physico‐chemical properties of the soil matrix. This finding suggests that soil organic matter complexes of Cu added through fertilizer, resulted in decreased desorption. The proportions of added Cu desorbed during 10 desorption periods were low, ranging from 2.5% in the 24‐h to 6% in the 2‐h desorption periods. The desorption of Cu decreased with increasing soil pH. The irreversible retention of Cu might be the result of complex formation with Cu at high pH.     

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.     

The Contrasting Effect of Goethite and Hematite on Phosphate Sorption and Desorption by Terre Rosse

Phosphate sorption and desorption in soils are markedly influenced by iron oxides, although little is known on how the common iron oxides differ in their behaviour towards added phosphate. In this study, we investigated phosphate sorption and desorption in the clay fractions of 12 Terre Rosse that ranged widely in Fe oxide content, had very low contents of oxalate-extractable Fe oxides and different hematite/goethite ratios. Phosphate sorption at an equilibrium concentration of 1 mg P 1^?1 was correlated with the goethite but not with the hematite content of the clay fractions. When phosphate was desorbed by electro-ultrafiltration, the difference in desorption half-time between untreated and deferrified clays was positively correlated with the goethite but not with the hematite content. These results suggest that goethite is more active than hematite in phosphate sorption and retention by soils.     

Short-term phosphorus sorption and desorption in contrasting cropped Vertisols

Vertisols are important cropping soils in tropical and subtropical areas, but in many regions, decades of cropping has substantially reduced concentrations of plant-available phosphorus (P), especially in the subsoil layers. Phosphorus behaviour in P-depleted Vertisols has received comparatively little attention, and the availability of P following the addition of inorganic P fertilisers at different concentrations is poorly understood. In this study, we evaluated short-term P sorption and desorption behaviour in cropped Vertisols in relation to specific soil physical and chemical properties. We collected the surface and subsurface of 15 Australian soils with a broad range of physical and chemical properties, comprising nine Vertisols, three Ferralsols, two Lixisols and one Calcisol. For each soil, we generated sorption and desorption curves (fitted with a Freundlich equation), determined soil physical and chemical properties likely to influence P sorption and evaluated the relationships between the measured soil properties and the Freundlich equation sorption coefficients. The P sorption curves differed drastically between soils, with the sorption equation coefficients (a_S × b) significantly correlated with the P buffering index (PBI) and clay content. Clay content itself was correlated with citrate-extractable Fe and Al oxides and BET surface area. Vertisols formed on basaltic parent materials had greater Fe and Al oxide concentrations, resulting in an overall greater P sorption capacity. Sorption and desorption hysteresis were mostly small. The reacting materials in these soils probably had limited ability to continue to react with P. The Vertisols differed in their capacity to replenish P in the soil solution by desorbing different proportions of previously sorbed P, although the proportion of desorbable P generally increased with greater concentrations of sorbed P. These results suggest that for fertiliser management in these soils, smaller volumes of P enrichment combined with higher P concentrations may result in a greater P recovery by the crop.     

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.     

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.     

Addition of Leucaena-KX2 mulch in a shaded coffee agroforestry system increases both stable and labile soil C fractions

Agroforestry systems have the potential to increase sequestration of atmospheric carbon dioxide (CO₂) as soil organic carbon (SOC) because of the increased rates of organic matter addition and retention. However, few studies have characterized the relative stability of sequestered SOC in soil. We characterized SOC storage in aggregate size and chemical stability classes to estimate the relative stability of SOC pools after the addition of Leucaena-KX2 pruning residues (mulch) from 2006 to 2008 in a shaded coffee agroforestry system in Hawaii. Soil samples were separated by microaggregate isolation, density flotation and dispersion, and acid hydrolysis, resulting in five distinct fractions that differed in relative stability: coarse particulate organic matter (POM), fine POM, microaggregate-protected POM, silt + clay hydrolyzable soil organic matter (SOM), and silt + clay non-hydrolyzable SOM. With mulch addition, the fine POM fraction increased. There was also a shift in the proportion of SOC to more stable silt + clay fractions. In the absence of mulch there was no significant change in SOC fractions. Given that the turnover time of SOC in silt + clay fractions is on the order of decades to centuries, the potential benefits of active shade management and mulching compensate for the loss of C sequestration in tree biomass from pollarding.     

水溶性有机碳在各种粘土底土中的吸附：土壤性质的影响

Clay-rich subsoils are added to sandy soils to improve crop yield and increase organic carbon (C) sequestration; however, little is known about the influence of clay subsoil properties on organic C sorption and desorption. Batch sorption experiments were conducted with nine clay subsoils with a range of properties. The clay subsoils were shaken for 16 h at 4 ^oC with water-extractable organic C (WEOC, 1 224 g C L^-1) from mature wheat residue at a soil to extract ratio of 1:10. After removal of the supernatant, the residual pellet was shaken with deionised water to determine organic C desorption. The WEOC sorption was positively correlated with smectite and illite contents, cation exchange capacity (CEC) and total organic C, but negatively correlated with kaolinite content. Desorption of WEOC expressed as a percentage of WEOC sorbed was negatively correlated with smectite and illite contents, CEC, total and exchangeable calcium (Ca) concentrations and clay content, but positively correlated with kaolinite content. The relative importance of these properties varied among soil types. The soils with a high WEOC sorption capacity had medium CEC and their dominant clay minerals were smectite and illite. In contrast, kaolinite was the dominant clay mineral in the soils with a low WEOC sorption capacity and low-to-medium CEC. However, most soils had properties which could increase WEOC sorption as well as those that could decrease WEOC sorption. The relative importance of properties increasing or decreasing WEOC sorption varied with soils. The soils with high desorption had a low total Ca concentration, low-to-medium CEC and low clay content, whereas the soils with low desorption were characterised by medium-to-high CEC and smectite and illite were the dominant clay minerals. We conclude that WEOC sorption and desorption depend not on a single property but rather a combination of several properties of the subsoils in this study.     

Behavior of soil boron and boron uptake by M.26 apple rootstock as affected by application of different forms and nitrogen rates

Abstract

The changes in availability and uptake of boron (B) by M.26 apple rootstocks as affected by applications of different forms and rates of nitrogen (N) were examined. The study was carried out in a greenhouse using soil with low contents of organic matter, clay, calcium carbonate, NH₄‐oxalate soluble aluminum (Al) and iron (Fe), NH₂OH·HCl extractable manganese (Mn), poor cation exchange capacity and low pH. Soil N application was in the form of urea, calcium nitrate, ammonium sulphate, or ammonium nitrate at rates of 0, 17, 34, and 51 mg N kg^?1. After 1, 3, and 5 days of N application, soil B fractions were determined: B in soil solution, B specifically and non‐specifically adsorbed on soil surfaces, B occluded in Mn oxyhydroxides, and B occluded in crystalline Al and Fe oxides. The results showed that N as calcium nitrate and ammonium nitrate increased B both in soil solution and non‐specifically adsorbed on soil surface and decreased B concentration on Al and Fe oxides. This indicates that N‐NO₃ inhibited B sorption on Fe and Al oxides. Maximum B desorption from Fe and Al oxides was obtained within one day after N‐NO₃ was supplied. Nitrogen application as calcium nitrate and ammonium nitrate increased availability and uptake of B by plant roots. Thus, it was concluded that apple trees planted on coarse‐textured soils where risk of B deficiency is high, calcium nitrate or ammonium nitrates would be appropriately to apply to keep B more available.     

Soil and sediment properties affecting the accumulation of mercury in a flood control reservoir

Mercury accumulations in some fish species from Grenada Lake in north Mississippi exceed the Food and Drug Administration standards for human consumption. This large flood control reservoir serves as a sink for the Skuna and Yalobusha River watersheds whose highly erodible soils contribute to excessively high sediment yields and impaired water quality. This study was conducted to characterize the distribution of total Hg in watershed soils and determine the relationship between the easily transportable clay, organic C (OC), and Fe oxide fractions and the movement of Hg from upland sources to reservoir sinks. Cores were collected from soils, of different land-use, representative of the three soil orders (Alfisols, Entisols, and Vertisols) found in the watersheds. Sediment cores were collected from the Yalobusha River and Grenada Lake. In the laboratory, soil cores were sampled by horizon while sediment cores were sampled in 10 cm increments. These samples were characterized for total Hg, particle size distribution, OC, Fe oxide contents, and pH. Mercury concentrations ranged from 10 to 112 µg kg^− 1 in the soil profiles, with average regression coefficient (r²) values of 0.104, 0.362, and 0.06 for Hg versus clay, OC, and Fe oxides, respectively. River sediment cores had Hg concentrations ranging from 0 to 38 µg kg^− 1, and significant (1% level) r² values of 0.611, 0.447, and 0.632 versus clay, OC, and Fe oxides, respectively. Mercury concentrations in the lake sediment ranged from 0 to 125 µg kg^− 1. The r² values for Hg versus clay, OC, and Fe oxides in the lake sediment were 0.813, 0.499, and 0.805, respectively, all significant at the 1% level. These results indicate that total Hg is poorly correlated with the clay, OC, and Fe oxide fractions at depth in the soil profiles because maximum Hg concentrations occur in the surface horizons due to atmospheric in-fall. The statistically significant r² values for Hg versus these components in the sediment cores are the result of particulate clay, Fe oxides, and finely divided OC sorption of Hg from solution during the runoff and sediment transport process. The higher correlations for the lake sediment reflect an enrichment of the Hg-laden clay fraction relative to stream sediment through flocculation and sedimentation processes in the slack-water environment of the reservoir.     

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.     

Challenges in modelling dissolved organic matter dynamics in agricultural soil using DAISY

Because dissolved organic matter (DOM) plays an important role is terrestrial C-, N- and P-balances and transport of these three components to aquatic environments, there is a need to include it in models. This paper presents the concept of the newly developed DOM modules implemented in the DAISY model with focus on the quantification of DOM sorption/desorption and microbial-driven DOM turnover. The kinetics of DOM sorption/desorption is described by the deviation of the actual DOM concentration in solution from the equilibrium concentration, C_eq. The C_eq is soil specific and estimated from pedotransfer functions taking into account the soil content of organic matter, Al and Fe oxides. The turnover of several organic matter pools including one DOM pool are described by first-order kinetics.The DOM module was tested at field scale for three soil treatments applied after cultivating grass–clover swards. Suction cups were installed at depths 30, 60 and 90 cm and soil solution was sampled for quantification of dissolved organic C (DOC) and dissolved organic N (DON). In the topsoil, the observed fluctuations in DOC were successfully simulated when the sorption/desorption rate coefficient k was low. In the subsoil, the observed concentrations of DOC were steadier and the best simulations were obtained using a high k. The model shows that DOC and DON concentrations are levelled out in the subsoils due to soil buffering. The steady concentration levels were based on the C_eq for each horizon and the kinetic concept for sorption/desorption of DOC appeared a viable approach. If C_eq was successfully estimated by the pedotransfer function it was possible to simulate the DOC concentration in the subsoil. In spite of difficulties in describing the DOC dynamics of the topsoil, the DOM module simulates the subsoil concentration level of DOC well, and also—but with more uncertainty—the DON concentration level.     

THE COVARIANCE OF PHOSPHATE SORPTION WITH OTHER SOIL PROPERTIES IN SOME BRITISH AND TROPICAL SOILS

Phosphate sorption capacity estimated by Piper's (1942) ‘anion exchange capacity’ and Bache and Williams's (1971) phosphate sorption index were correlated with soil pH, clay, organic matter, ‘free iron oxides’ and ‘extractable aluminium’ (McLean et al., 1958) for topsoil and subsoil samples from twenty tropical and twenty British acidic soil profiles. These two groups of soils did not differ significantly in phosphate sorption. Extractable aluminium and free iron oxide were well correlated with phosphate sorption, free iron oxide being superior to aluminium in freely drained British soils but not in poorly drained ones. Organic matter content correlated well with phosphate sorption for the poorly drained British soils, and for the tropical soils when sorption capacitywas measured using a high phosphate concentration.     

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.     

Modelling long-term phosphorus leaching and changes in phosphorus fertility in excessively fertilized acid sandy soils

The sound management of agricultural soils that are heavily loaded with phosphorus (P) involves minimizing the losses of P responsible for eutrophication of surface waters, while ensuring enough P for crops. This paper describes a simple model to examine the compatibility of these two objectives in acid sandy soils in a temperate humid climate. The model is based on several assumptions regarding reversible and irreversible P sorption by P-reactive soil compounds (mainly poorly crystalline Fe and Al oxides) and release of P to water (water-P test). Model inputs are amount of P leached, P uptake by crops, and contents of poorly crystalline Fe and Al oxides in soil. The model predicts that reducing the amount of leached P to what is environmentally acceptable (e.g. 0.44 kg P ha^–1 year^–1, equivalent to 1 kg P₂O₅ ha^–1 year^–1) results in the long run in available soil P test values below target concentrations for optimum crop growth. When the amount of leached P is set to a fixed value the model predicts that soils with large contents of Fe and Al oxides can maintain the initial soil P test values for longer periods than other soils. The content in available P decreases if fertilizer P is applied to the soil at a rate equal to P uptake by crops. These results stress the difficulties involved in trying to make agricultural and environmental needs compatible in acid sandy soils.     

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.     

Clay minerals,oxyhydroxide formation,element leaching and humus development in volcanic soils

A weathering sequence with soils developing on volcanic, trachy-basaltic parent materials with ages ranging from 100–115,000 years in the Etna region served as the basis to analyse and calculate the accumulation and stabilisation mechanisms of soil organic matter (SOM), the transformation of pedogenic Fe and Al, the formation and transformation of clay minerals, the weathering indices and, by means of mass-balance calculations, net losses of the main elements. Although the soils were influenced by ash depositions during their development and the soil on the oldest lava flow developed to a great extent under a different climate, leaching of elements and mineral formation and transformation could still be measured. Leaching of major base cations coupled with a corresponding passive enrichment of Al or Fe was a main weathering mechanism and was especially pronounced in the early stages of soil formation due to mineral or glass weathering. With time, the weathering indexes (such as the (K + Ca)/Ti ratio) tend to an asymptotic value: chemical and mineralogical changes between 15,000 and 115,000 years in the A and B horizons were small. In contrast to this, the accumulation of newly formed ITM (imogolite type materials) and ferrihydrite showed a rather linear behaviour with time. Weathering consisted of the dissolution of primary minerals such as plagioclase, pyroxenes or olivine, the breakdown of volcanic glass and the formation of secondary minerals such as ITM and ferrihydrite. The main mineral transformations were volcanic glass ? imogolite ? kaolinite (clay fraction). In the most weathered horizons a very small amount of 2:1 clay minerals could be found that were probably liberated from the inner part of volcanic glass debris. The rate of formation and transformation of 2:1 clay minerals in the investigated soils was very low; no major changes could be observed even after 115,000 years of soil evolution. This can be explained by the addition of ash and the too low precipitation rates. In general, soil erosion played a subordinate role, except possibly for the oldest soils (115,000 years). The youngest soils with an age < 2000 years had the highest accumulation rate of organic C (about 3.0 g C/m²/year). After about 15,000 years, the accumulation rate of organic C in the soils tended to zero. Soil organic carbon reached an asymptotic value with abundances close to 20 kg/m² after about 20,000 years. In general, the preservation and stabilisation of SOM were due to poorly crystalline Al- and Fe-phases (pyrophosphate-extractable), kaolinite and the clay content. These parameters correlated well with the organic C. Imogolite-type material did not contribute significantly to the stabilisation of soil organic matter.