Correlations between different acidity forms in amorphous loamy soils of the tundra and taiga zones

Pair correlation coefficients (r) between the acidity parameters for the main genetic horizons of soddy-podzolic soils (SPSs), typical podzolic soils (TPSs), gley-podzolic soils (GPSs), and tundra surfacegley soils (TSGSs) have been calculated on the basis of a previously developed database. A significant direct linear correlation has been revealed between the pH_water and pH_KCl values in the organic and eluvial horizons of each soil, but the degree of correlation decreased when going from the less acidic SPSs to the more acidic soils of other taxons. This could be related to the fact that, under strongly acid conditions, extra Al³⁺ was dissolved in the KCl solutions from complex compounds in the organic horizons and from Al hydroxide interlayers in the soil chlorites. No significant linear correlation has been found between the exchangeable acidity (H _exch) and the activity of the [H]⁺ ions in the KCl extract (a(H⁺)_KCl) calculated per unit of mass in the organic horizons of the SPSs, but it has been revealed in the organic horizons of the other soils because of the presence of the strongest organic acids in their KCl extracts. The high r values between the H _exch and a(H⁺)_KCl in all the soils of the taiga zones have been related to the common source and composition of the acidic components. The correlation between the exchangeable and total (H _tot) acidities in the organic horizons of the podzolic soils has been characterized by high r values because of the common source of the acidity: H⁺ and probably Al³⁺ ions located on the functional groups of organic acids. High r values between the H _exch and a(H⁺)_KCl have been observed in the mineral horizons of all the soils, because the Al³⁺ hydroxo complexes occurring on the surface and in the interlayer spaces of the clay minerals were sources of both acidity forms.     

Forms of soluble aluminium in acidic topsoils estimated by ion chromatography and 8-hydroxyquinoline and their correlation with growth of subterranean clover

Labile Al in the soil solution measured by 8-hydroxyquinoline (Al_HQ) was a better predictor of plant growth than trivalent Al (Al_IC³⁺) measured by ion chromatography (IC). HQ reacted with some organic Al complexes which did not separate during chromatography. In the presence of oxalic acid, Al_HQ was greater than Al_IC³⁺, which was the same as the greater than Al³⁺ (Al³⁺_Calc), whereas in the presence of citric acid, Al_HQ was greater than Al_IC³⁺, and both were greater than Al⁺³_Calc, In extracts of soils that had been acidified, Al³⁺_IC was less than Al_HQ, which was similar to Al³⁺_Calc, when it was assumed that the only complexing ligands were OH^? and F^?. The proportion of Al³⁺_IC in the soil solutions decreased more than Al_HQ as the pH increased. Organic ligands appeared to form complexes with Al at the expense of AIF complexes. Forms of Al detected by IC differed in CaCl₂ extracts and soil solutions. Al_HQ in the CaCl₂ extracts and soil solution were closely correlated, although the proportion of Al_HQ was higher in the CaCl₂ extracts. And soil solutions. Al_HQ in the CaCl₂ extracts and soil solution were closely correlated, although the proportion of Al_HQ was higher in the CaCl₂ extracts.     

Aluminium chemistry in two contrasted acid forest soils and headwater streams impacted by acid deposition,Vosges mountains,N.E. France

Al chemistry was studied in two acidic watersheds, one with a podzol, the other with an acid brown soil, in the Vosges mountains (N.E. France), by analysing both leaching and centrifugation soil solutions and spring waters over 3 yr. In the podzol, Al was mobilized in the eluvial horizons under the predominant influence of organic acidity, then leached down the profile as organic and F-bound Al. Strong undersaturation with respect to proto-imogolite and imogolite showed that the proto-imogolite theory of podzolization could not apply. Al was transferred from the soil to spring water mostly as Al³⁺ and Al-F. Al³⁺, as well as additional minor species (AlOH²⁺, AlSO₄ ⁺), originated from the redissolution of the top of the spodic horizons under the influence of both soil solution acidity and the occurrence of mobile anions derived from atmospheric deposition. Conversely, in the acid brown soil, Al mobilization was regulated by nitrate and occurred mainly as Al³⁺. Most of Al was retained in the deep soil and only traces of monomeric Al reached spring water. In the podzol eluvial horizons, soil solutions were undersaturated with respect to all relevant mineral phases and their chemical composition agree with the concept of a mobilization of Al from the solid soil organic Al and a control of Al³⁺ activity by complexation reaction with the solid and soluble soil organic matter and F. In the acid brown soil, soil solutions were found to be in equilibrium with natural alunite, and the formation of this mineral, if confirmed, would account for the occurrence of 'open' vermiculites instead of the expected hydroxy-Al interlayered vermiculites. Al solubility control in surface water of both watersheds remains unclear. The Al-F species in both watersheds and the likely control of Al solubility by alunite in the acid brown soil emphasize the influence of acid deposition on Al chemistry in acid watersheds.     

Acidity in organic horizons of arctic soils on the Barents Sea coast

Parameters of water and KCl extracts from organic horizons of arctic soils on the coast of Khaipudyr Bay of the Barents Sea, in which the values of pH are 3.8–4.3 and 2.7–3.5, respectively, have been compared. It has been found that the content of water-extractable organic carbon is 0.2–0.5 g/dm³; the contents of low-molecular-weight carbohydrates and acids are 1–24 and 6 mg/dm³, respectively, and the content of Fe³⁺ ions is 1–4 mmol/dm³. The increase in the ionic strength of solution reduces the extraction efficiency of total organic carbon in 1.2 times and that of acids and carbohydrates in 3 times on the average at the simultaneous increase in the content of iron ions in the liquid phase in 7–15 times. It has been shown that organic acids and iron compounds are the main sources of acidity in salt extracts from organic soil horizons. The low contents of Ca²⁺ and Mg²⁺, which participate in the neutralization of acids, favor the high acidity of the studied horizons.     

Toxicity factors in acidic forest soils: attempts to evaluate separately the toxic effects of excessive Al3+ and H+ and insufficient Ca2+ and Mg2+ upon root elongation

The acidic soils of temperate forests and some pastures on former forest land characteristically contain large amounts of aluminium and hydrogen ions and small amounts of calcium and magnesium ions. The relative importance of these potential toxicity factors are assessed from published data from soils collected in the United States and Europe. Activities of ions in the soil solutions and at the surfaces of root‐cell plasma membranes were computed with electrostatic models. Activities of Al³⁺ in soil solutions ({Al³⁺}) peaked at pH 4.1, and Al³⁺ activities at the surface of the plasma membrane ({Al³⁺}₀) achieved a broad maximum between pH 4.1 and 4.8; thus, Al³⁺ intoxication is likely to be more severe in soils at pH 4.1 than in more acidic ones. Intoxication (assessed by root elongation) correlated somewhat ambiguously with ion activities, but Al³⁺‐ and H⁺‐induced depletion of Ca²⁺ and Mg²⁺, or both, from the cell surface appears to play a role in toxicity. By contrast, experiments in solution culture, where intercorrelation among {Al³⁺}, {H⁺}, and {Ca²⁺} could be avoided, clearly demonstrated the following extrinsic and intrinsic effects. 1 The ions Al³⁺ and H⁺ are intrinsic toxicants. 2 They are also extrinsic toxicants because of the electrostatic displacement of Ca²⁺ from the surface of the plasma membrane. 3 They are extrinsic ameliorants because each electrostatically displaces the other from the surface of the plasma membrane. 4 The ion Ca²⁺ is an extrinsic ameliorant because of the electrostatic displacement of Al³⁺ and H⁺ from the surface of the plasma membrane. 5 It is an intrinsic ameliorant of intrinsic H⁺ toxicity, but not intrinsic Al³⁺ toxicity. 6 It meets an intrinsic requirement. 7 The ion Mg²⁺ resembles Ca²⁺ in item 4 but not items 5 and 6 in short‐term cultures. In acidic soils, Al³⁺ may prevent H⁺ from becoming an intrinsic toxicant (item 3) and may induce an insufficiency of Ca²⁺ and Mg²⁺ (item 2). These findings have implications for the mechanisms by which woodland plants tolerate very acidic soils.     

THE EQUILIBRIA OF K:Al EXCHANGE IN CLAY MINERALS AND ACID SOILS1

Conventional K: Al exchange isotherms for montmorillonite showed that Al³⁺ was strongly preferred to K⁺ in o-oin solutions. The exchange coefficient, K', calculated using the isotopically exchangeable K, was greater than unity and did not vary with the Al-saturation or with the initial pH of the AlCl₃ solutions. Isotherms for vermiculite, illite, and soils in o·oin solutions also showed Al³⁺-preference but unlike those for montmorillonite were not asymptotic to q_Al/q_o= 1, q_Al being the amount of adsorbed Al and q_o the total adsorbed (Al + K), indicating that some of the isotopically exchangeable K could not easily be exchanged by Al³⁺ ions; this difficultly exchangeable K (DEK) was estimated for each exchanger. K' values for vermiculite, illite, and soils were less than unity and did not vary with Al-saturation or initial pH if the isotopically exchangeable K was corrected for DEK. This showed that K⁺ was adsorbed more strongly than Al³⁺. Strengths of K⁺ adsorption referred to Al³⁺ as the counter-cation were in order: soils > vermiculite, illite > montmorillonite.     

华南红壤的交换性碱和交换性酸

本文提出了一个同时测定土壤的交换性酸和交换性碱的简易方法。将土壤的交换性酸和交换性碱区分为:Na-交换性酸、Ba-交换性酸和SO₄-交换性碱、F-交换性碱。用推荐的方法,在野外对华南地区由不同母质发育的砖红壤、赤红壤、红壤等10个剖面进行了测定。结果表明,红壤类土壤含有相当量的交换性碱,但其数量比交换性酸少。酸性母质发育的土壤的交换性酸和交换性碱量大于由基性岩发育的土壤者。红壤的交换性酸和碱的量随电性盐浓度的增高而增大,浓度大于0.1N后,数量基本不变。     

Influence of Different Forms of Iron and Aluminum on the Nature of Soil Acidity of Some Inceptisols,Alfisols, and Ultisols

Abstract

Fifteen acid soils of Mizoram representing Ultisols and Inceptisols, and Madhya Pradesh, representing Alfisols, were studied to characterize the nature of acidity in relation to different forms of iron (Fe) and aluminum (Al). The mean contents of Fe and Al were extracted by various extracting reagents and were found to be in descending order as followed: dithionite>oxalate>pyrophosphate>ammonium acetate>KCl. The electrostatically bonded EB‐H⁺ and EB‐Al³⁺ acidity comprised 28.3 and 71.7% of exchangeable acidity whereas EB‐H⁺, EB‐Al³⁺, exchangeable, and pH‐dependent acidities comprised 9.8, 30.7, 40.5, and 59.5% of total potential acidity. All forms, of acidity showed significant correlation with pH_k and organic carbon. Among the different forms, Fe and Al caused most of the variations in different forms of soil acidity but the effect of different forms of Al are more active and directly participate in the formation of EB‐H⁺, EB‐Al³⁺, and exchangeable acidity.     

Solution chemistry in acid forest soils: Are the BC : Al ratios as critical as expected in Switzerland?

The molar ratio of base nutrient cations to total dissolved aluminum (BC : Al_tot) in the soil solution was measured at six forest sites in Switzerland in acid mineral soils to determine whether the ratio measured in the field was lower than the critical value of 1, as predicted by the mapping of exceedances of critical loads of acidity. The soil chemistry was then related to the soil solution composition to characterize the typical effective base saturation (BS) and BC : Al ratio in soil leading to critical BC : Al_tot in the soil solution. The median BC : Al_tot ratio in the soil solution never reached the critical value in the root zone at any sites for the whole observation period (1999–2002), suggesting that the BC : Al_tot ratios measured in the field might be higher than those modeled for the determination of critical loads of acidity. The gibbsite model usually applied for the calculation of critical loads was a poor predictor of the Al³⁺ activity at the study sites. A curvilinear pH‐pAl³⁺ relationship was found over the whole range of pH (3.8–6.5). Above a pH of 5.5, the slope of the pH‐pAl³⁺ relation was close to 3, suggesting equilibrium with Al(OH)₃. It decreased to values smaller than 1.3 below a pH of 5.5, indicating complexation reactions with soil organic matter. The BS and the BC : Al ratios in the soils were significantly correlated to the BC : Al_tot ratios in the soil solution. The soil solutions with the lowest BC : Al_tot ratios (≤ 2) were typically found in mineral soils with a BS below 10 % and a BC : Al ratio in the soil lower than 0.2. In acid pseudogleyed horizons overlying a calcareous substrate, the soil solution chemistry was strongly influenced by the composition of the underlying soil layers. The soil solutions at 80 cm had pH values and BC : Al_tot ratios much higher than expected. This situation should be taken into account for the calculations of critical loads of acidity.     

Interactions of aluminium and fulvic acid in moderately acid solutions: stoichiometry of the H+/Al3+ exchange

Complexation with organic matter controls the activity of dissolved Al³⁺ in many soils. The buffering intensity of these soils is largely dependent on the H⁺/Al³⁺ exchange ratio, i.e. the number of protons consumed by the solid phase when one Al³⁺ is released. Here, the H⁺/Al³⁺ exchange ratio was determined from batch titrations using solutions of fulvic acid (FA) as a model for soil organic matter. Aluminium was added, from 1.04 to 6.29 mmol Al per g FA, which is within the range of humus‐bound Al found in the upper B horizon of podzolized soils. Furthermore, pH was varied with NaOH to give values between 3.5 and 5.0. The H⁺/Al³⁺ exchange ratio ranged between 1.49 and 2.23 with a mean of 1.94. It correlated positively with pH and the total concentration of Al present. Theoretically, this can be explained with a partial hydrolysis of bound Al. The slope of logAl (log₁₀ of Al³⁺ activity) against pH generally underestimated the actual exchange ratio, which can partly be attributed to the systems being diluted (100 mg FA l^?1). However, where 4 mmol Al or more had been added per g FA, the logAl slope gradually approached ?3 between pH 4.5 and 5.0. This might be the result of a shift from Al³⁺ activity control by humus complexation to control by Al(OH)₃(s).     

pH and solubility of aluminium in acidic forest soils: a consequence of reactions between organic acidity and aluminium alkalinity

Data from two Podzol O and E horizons, sampled in 1-cm layers at 13 points within 2 m × 2 m plots, were used to test the hypothesis that the composition of hydrogen ions (H) and aluminium (Al) adsorbed to the solid-phase soil organic matter (SOM) determines pH and Al solubility in organic-rich acidic forest soils. Organically adsorbed Al was extracted sequentially with 0.5 m CuCl₂ and organically adsorbed H was determined as the difference between total acidity titrated to pH 8.2 and Al extracted in 0.5 m CuCl₂. The quotient between fractions of SOM sites binding Al and H (N_Al/N_H) is shown to determine the variation in pH and Al solubility. It is furthermore shown that models in which pH and Al solubility are linked via a pH-dependent solubility of an Al hydroxide and in which cation exchange between Al³⁺ and Ca²⁺, rather than cation exchange between Al³⁺ and H⁺, is the main pH-buffering process cannot be used to simulate pH or Al solubility in O and E horizons. The fraction of SOM sites adsorbing Al increased by depth in the lower O and throughout the E horizon at the same magnitude as sites adsorbing H decreased. The fraction of sites binding the cations Ca²⁺ + Mg²⁺ + K⁺ + Na⁺ remained constant. It is suggested that a net reaction between Al silicates (proton acceptors) and protonated functional groups in SOM (proton donors) is the long-term chemical process determining the composition of organically adsorbed H and Al in the lower part of the O and in the E horizon of Podzols. Thus, in the long term, pH and Al solubility are determined by the interaction between organic acidity and Al alkalinity.     

Salts and acids as determinants of the solution composition of acidic forest soils — anion effects

The study aimed at evaluating whether salt-induced mobilization of acidity may be modified by the type of anion. For this purpose, the effects of different neutral salts on the solution composition of acid soils were investigated. The results were compared with those of the addition of acids. Two topsoil (E and A) and two subsoil horizons (Bs and Bw) were treated with NaCl, Na₂SO₄, MgCl₂, MgSO₄, HCl, and H₂SO₄ at concentrations ranging from 0 to 10 mmol dm^?3. With increasing inputs of Cl^? the pH of the equilibrium soil solution dropped, the concentrations of Al and Ca increased, and the molar Ca/(Al³⁺ + AlOH²⁺ + Al(OH)₂⁺) ratios decreased. These effects were the least pronounced when NaCl was added and the most at the HCl treatments. According to the release of acidity, the topsoils were more sensitive for salt-induced soil solution acidification whereas on base of the molar Ca/(Al³⁺ + AlOH²⁺ + Al(OH)₂⁺) ratios, the salt effect seems to be more important for the subsoils. Addition of S0₄^2? salts and H₂SO₄ induced higher pH and lower Al concentrations than the corresponding Cl^? treatments due to the SO₄^2? sorption, especially in the subsoils. The Ca/(Al³⁺ + AlOH²⁺ + Al(OH)₂⁺) ratios were higher than those of the corresponding Cl^? treatments. In subsoils even after H₂SO₄ additions these ratios were not higher than those of the NaCl treatments. The results indicate (I) that speculation about the effects of episodic salt concentrations enhancement on soil solution acidification not only need to consider the ionic strength and the cation type but also the anion type, (II) that salt-induced soil solution composition may be more crucial in subsoils than in topsoils, and (III) that in acid soils ongoing input of HNO₃ due to the precipitation load may induce an even more acidic soil solution than the inputs of H₂SO₄ of the last decade.     

设施土壤盐分的累积、迁移及离子组成变化特征

通过对我国不同地区设施栽培现状的野外调查和取样分析,研究了设施栽培条件下土壤盐分的累积、迁移及离子组成变化特点。结果表明:1)设施栽培条件下,土壤含盐量的变化幅度大,且均明显高于露地土壤,各研究区域内已有40%8～9%的土壤含盐量超过了作物正常生长的临界浓度。2)设施栽培的可持续利用周期较短,连续种植到4年左右的设施土壤,其耕层盐分的累积量可达到作物的生长障碍临界点,之后因设施使用率的下降以及采取的措施而有所降低,但仍高于露地土壤。设施连续使用会导致土壤环境质量的不断恶化。3)设施土壤剖面(0100.cm)盐分含量均高于相邻露地,盐分含量随土层深度增加而降低,其中耕层(020.cm)的盐分含量显著高于其下各层;盐分离子在土壤剖面的运移同时存在着明显的向底层迁移和向表层聚集两种方式,但以表聚为主;此外,盐分离子的大量累积和向底层迁移,特别是NO3-的淋溶已严重影响到部分地区的地下水水质。4)设施栽培后,土壤中的NO3-、SO42-、Cl-、Ca2+、Mg2+、K+、Na+均有不同程度的累积,阴离子以NO3-和SO42-为主,阳离子以Ca2+为主。盐分的大量累积以及某些离子的相对富集在一定程度上引起了作物养分的供需失衡、土壤酸化、棚室内CO2供应不足等生产问题。     

The role of sea-salts in enhancing and mitigating surface water acidity

Enhancement of the acidity of fresh waters due to sea-salt “episodes” has been reported in western regions of Scotland, Ireland and Norway and eastern regions of Canada and the United States of America. In all cases these short-term pH depressions have been ascribed to cation-exchange processes in catchment soils whereby sodium ions displace acidic cations (H⁺, Al³⁺) resulting in a lowering of the Na/Cl ratio in run-off water. Studies of sea-salt episodes in different catchment types of similar sensitivity in Scotland show significant variations in chemical responses, especially in terms of acidification status. Catchments with high background salt content, in a low sulphur deposition area, show only a small increase in acidity with negligible aluminium release and most of the sodium retention matched by Ca and Mg release. Catchments in intermediate deposition areas, with low background salt levels, exhibit smaller sodium retention with increased leaching of acidity and labile aluminium. High non-marine S deposition sites, with intermediate background salt levels, reveal high levels of acidity and aluminium leaching associated with some calcium leaching and evidence of Mg retention. Mitigation of acidification occurs at sites with high background sea-salt levels (eg north west Scotland) where acidic deposition is selectively retained in catchment soils. Non-marine sulphate values in run-off are therefore much lower (often producing negative values) than those predicted from current S deposition values. Consequently such sites are presently producing false exceedances of freshwater Critical Loads when current S deposition values are used. Future reductions in S deposition will probably affect the adsorption characteristics at these sites with consequent effects on sulphate leaching.     

CALCIUM: ALUMINIUM EXCHANGE EQUILIBRIA IN CLAY MINERALS AND ACID SOILS1

Exchange reactions between 0.0in AlCl₃ solutions of different pH and Ca-saturated montmorillonite, vermiculite, illite, and soils from the Park Grass Experiment at Rothamsted and the Deerpark Experiment, Wexford, Ireland, showed that Al³⁺ and Al(OH)₂⁺ were adsorbed from solutions of pH > 4.0 and Al³⁺ and H⁺ from solutions of pH < 3.0. When Al was adsorbed, the cation exchange capacity of Ca-saturated soils and clays increased. Conventional Ca: Al exchange isotherms showed that Al³⁺ was strongly preferred to Ca²⁺ on all soils and clays. The equilibrium constant for Ca: Al exchange, K, was identical for soils before and after oxidizing their organic matter and did not vary, for any exchanger, with Al-saturation or the initial pH of the AlCl₃ solution. This proved the validity of the procedure used for calculating exchangeable Al³⁺. K values for Ca:Al exchange favoured Al³⁺ in the order: vermiculite > Park Grass soil > Deerpark soil > illite > montmorillonite. The influence of surface-charge densities of the clay minerals on this order is discussed and a method proposed and tested for calculating the K value of a soil from its mineralogical composition.     

Long-Term Evaluation of Acidic Atmospheric Deposition on Soils and Soil Solution Chemistry in the Daniel Boone National Forest,USA

Combustion of fossil fuels has contributed to many environmental problems including acid deposition. The Clean Air Act (CAA) was created to reduce ecological problems by cutting emissions of sulfur and nitrogen. Reduced emissions and rainfall concentrations of acidic ions have been observed since the enactment of the CAA, but soils continue to receive some acid inputs. Many soils sensitive to acid deposition are found to have low pH, a loss of base cations, and a shift in the mineral phase controlling the activity of Al³⁺ and/or SO₄ ^2?. If inputs continue, soil may be depleted of base cations and saturated with Al and could cause low forest productivity. Soil samples and soil solutions from pan lysimeters were taken on ridge-tops in the Daniel Boone National Forest to evaluate potential impacts of acid deposition recently and in the future. Sample results were compared to historical data from identical locations. Physicochemical characteristics of the soils revealed that sites were very low in base saturation and pH and high in exchangeable acidity, illustrating change since previously sampled. Soil solution data indicated that sites periodically received high acid inputs leading to saturation of Al in soils and the formation of Al-hydroxy-sulfate minerals. Given these conditions, long-term changes in soil chemistry from acid deposition are acknowledged.     

Field application of industrial by-products as Al toxicity amendments: chemical and mineralogical implications

Lime, gypsum and various gypsum‐like by‐products have long been applied to soil surfaces as ameliorants of soil acidity and aluminium and manganese toxicity. We examined changes in chemical and mineralogical properties at two different depths in two acid soils one year after the application of gypsum, phosphogypsum + dolomitic residue, red gypsum + dolomitic residue, sugar foam, and sugar foam + mined gypsum. All treatments were found to increase the proportion of Ca²⁺ and decrease those of Al³⁺ and Mn²⁺ in the exchange complex of the surface and subsurface horizons, thus reducing its effective Al and Mn saturation. However, the mined gypsum treatment resulted in losses of Mg²⁺ from the Ap horizon of the soils, and the sugar foam treatment was not so effective with the AB horizons as the other treatments. The combined application of both gypsum‐like by‐products and the dolomitic residue proved the most effective choice with a view to reducing the effective Al and Mn saturation of the exchange complex in the Ap and AB horizons. In addition, both treatments reduced Mg²⁺ losses at both depths. Finally, all treatments resulted in the formation and retention on mineral and organic surfaces of a large fraction of the Al³⁺ released by exchange with Ca²⁺ as Al polymers. This is quite consistent with the observed changes in the CuCl₂‐, oxalate‐ and DTPA‐extractable Al contents as well as by SEM and EDS analyses. Based on these results, the use of the appropriate mixtures of these by‐products is an effective alternative to that of mined gypsum and lime to alleviate soil acidity and reduce toxic concentrations of Al³⁺ and Mn²⁺ in agricultural acid soils.     

Soil solution aluminium activity related to theoretical A1 mineral solubilities in four Australian soils

Four soils were treated with HNO₃, CaCO₃ and K₂SO₄ to enable observation of the response of the soil solution composition and the solution A1 ion activity (Al³⁺) to the treatments and to time. The clay fraction of three of the soils was dominated by illite, kaolinite and quartz. The fourth was minated by kaolinite and iron oxides. The initial pH in 0.01 M CaCl₂ varied between 4.0 and 5.0 and the organic carbon content from 0.7 to 1.1%. The soil solutions from soils dominated by kaolinite, illite and quartz were generally supersaturated with respect to quartz and well ordered kaolinite, and unsaturated with respect to illite. The soil solutions from the soil dominated by kaolin and iron oxide were generally unsaturated with respect to quartz but still saturated with respect to ell crystallized kaolin. Within mineral groups such as Al₂SiO₅ compounds, A1₂Si₂O₅(OH)₄ (kaolinite group), and Al(OH)₃ (A1 oxide) minerals, the more soluble forms became less supersaturated or unsaturated with time for many treatments. Lime treatment usually increased the ion activity product of AI(OH)₃ in all soils, and of minerals with the composition, Al₂SiO₅, in the illite/kaolinite soils. Acid treatment reduced the apparent solubility of Al(OH)₃, and the A1 silicates in the Al₂SiO₅, and Al₂, Si₂, O₅,(OH)₄, mineral groups on all soils. These results are interpreted to indicate that lime treatment led to the formation of trace quantities of more soluble A1 minerals that subsequently controlled (Al³⁺), whereas acid treatment dissolved trace quantities of such minerals leaving less soluble minerals to control (Al³⁺). The results suggest that, in mineral soils such as these, (Al³⁺) is under the control of inorganic dissolution and precipitation processes. These processes conform to expectations given the free energy of various inorganic aluminium compounds. Furthermore the sequence of dissolution and formation processes appears to be governed by the Gay-Lussac—Ostwald step rule.     

Sorption of cupric,dichromate and arsenate ions in some New Zealand soilds

Concentrated solutions of copper (Cu²⁺), dichromate (Cr₂O^2? ₇) and aresenate (AsO₄ ^3?) ions (CCA solutions) are used extensively in the New Zealand timber preservation industry. These ions are therefore, potential soil pollutants at timber treatment sites. Sorption of these three ions was examined by the surface and sub-surface horizons of two free-draining New Zealand soils over a range of soil solution pH values. Copper sorption by both soils increased substantially with increasing pH and was greater in the surface compared with the sub-surface horizons. Less dichromate was sorbed than the other two ions and wa similar in both surface and sub-surface horizons for each soil. Dichromate sorption increased with decreasing pH. Arsenate sorption from solutions containing all three ions was not greatly different to influenced by changes in soil solution pH. Arsenate sorption was generally greater in the sub-surface horizons of both soils. Sorption from solutions containing all three ions was not greatly different to sorption from solutions containing the single metal ions. Sorption behaviour for each ion is related to its chemistry and the soil chemical properties of each horizon. Results suggest that in the event of soil contamination by CCA solution, the immediate leaching potential of the initial ions species present would increase in the following order: Cu²⁺ < HAsI ₄ ^? ? Cr₂O ₇ ^2? .     

DOWNWARD MOVEMENT OF DOLOMITE,KIESERITE OR A MIXTURE OF CaCO3 AND KIESERITE THROUGH THE UPPER LAYERS OF AN ACID FOREST SOIL

Liming and fertilization are important tools for improving the chemical status of acid, base poor forest soils. The downward movement of dolomite, kieserite and a mixture of CaCO₃ and kieserite was investigated by monitoring the leachates and exchangeable cation composition from single and combined horizon columns, reconstructed from an acid brown forest soil profile (0–15 cm). Upon entering the soil, Mg ions from kieserite displaced base cations and acidity (H and Al ions) from exchange sites, which subsequently moved down with the mobile SO₄ ^2- anions. Total leaching during the initial SO₄ ^2- pulse was similar with the CaCO₃ + kieserite mixture. Compared to the single kieserite treatment, the joint application of CaCO₃ greatly increased the proportion of Ca in the leachates from all horizons. It also decreased the leaching of acidity from the surface Oe horizon and prevented pH from dropping under this layer. With both treatments, the redistribution of magnesium with SO₄ ^2- anions resulted in a rapid increase in exchangeable Mg contents throughout the studied columns. Due to the important charge increase in the Oe horizon and to kinetic restraints imposed on dissolution, downward movement of Ca and Mg ions from dolomite was very limited. Mg was however much more mobile than Ca. In the CaCO₃ + kieserite and dolomite treatments, the migration of alkalinity and base cations with time was associated with a decrease in exchangeable acidity and an increase in ECEC in the two upper soil layers. By the end of the monitoring period, overall net Mg retention in the 0–15 cm columns increased in the order kieserite < CaCO₃ + kieserite << dolomite with respectively 20, 35 and 85% of cumulated inputs remaining in the columns. The corresponding net Ca retention amounted to 82 and 96% of cumulated inputs for the CaCO₃ + kieserite and dolomite treatments, respectively. Results from this study complement those obtained in the field by clearly demonstrating the mechanisms involved in the downward movement of some fertilizers commonly used to increase the base saturation of acid forest soils.