The sensitivity of Swiss forest soils to acidification and the risk of aluminum toxicity

In the context of pollution‐control strategies to minimize the detrimental effects of soil acidification, there is a need to know how and to what extent soils respond to acidifying substances. The purposes of this study were to assess the sensitivity of soil to acidification, in particular to a decrease in pH and in base saturation (BS), and the risk of Al toxicity for vulnerable plants using chemical indicators. These indicators were derived from soil data (pH, exchangeable cations, amount of fine earth) measured in the mineral horizons of 257 soil profiles throughout Switzerland. Based on the analysis of the distribution of pH and BS values in the soil collective, we assessed the sensitivity of soils to a decrease in pH and in BS. Soils that were considered sensitive to a decrease in pH had pH values between 4.8 and 7.0. The degree of sensitivity was estimated with the proportion of fine earth in the critical pH range to a depth of 100 cm. Soils that were considered sensitive to a decrease in BS had pH values between 3.6 and 5.5 and a BS between 10% and 95%. Since the effective cation‐exchange capacity (CEC_eff) of the fine earth might dampen the decrease in BS when acidity is added, the disposition for a decrease in BS was related to the relative amount of fine earth in the sensitive BS and to the mean CEC_eff of this fine‐earth fraction. The risk of Al toxicity for vulnerable plants was estimated using the ratio of base cations to Al at the cation‐exchange sites (BC : Al_exc). A BC : Al_exc of 0.2 was taken as a threshold value below which the risk for sensitive plants increases. The degree of risk was based on the proportion of fine earth in the critical BC : Al range (≤0.2) in the soil profile. These indicators taking into account the various aspects of soil acidification are derived from usually available data and represent therefore a cost‐effective tool to assess the sensitivity of soils to an input of acidity.     

Calcium requirements of citrus

Abstract

A close relationship was found between the pH of soil suspensions in the SMP buffer solution (pH_smp) and the potential acidity of soils (H + Al) extracted by a neutral calcium acetate solution (r = 0.98), for twenty six soil samples of the State of Sao Paulo, Brazil, This relationship was represented by the equation lnY = 7.76 ‐ 1.053X, which allowed for the calculation of H + Al directly from the values of pH_smp.

With the values of H + Al and the sum of bases, calcium, magnesium and potassium, the cation exchange capacity (CEC), and the base saturation (V) were calculated. Relationships between the base saturation of the soils and the active acidity of soil suspensions were close, both for pH determined in water (r=0.94) and pH determined in 0.01M CaCl₂ solution (r ‐ 0.97). Thus the lime requirement (LR) of soils could be calculated, for given values of pH or base saturation, using the equation LR = CEC (V₂ ‐ V₁)/100, in which V₁ is the base saturation of the soil and V₂ is the expected value upon liming.

The predicted values for lime required to increase the soil pH in water to either 5.5 or 6.0 were comparable to those obtained by the direct use of the SMP buffer method, and were, respectively, two and four times higher than the amounts required to neutralize exchangeable aluminum, considering the criterion LR = Al × 1.5.

The proposed method to determine lime requirement of soils is described in detail and the advantages of its use are discussed.     

Effects of changes in pH, ionic strength, and sulphate concentration on the CEC of temperate acid forest soils

As the acidity of rain diminishes, changes in the pH, ionic strength, and ion activities of the soil solution will influence the charge characteristics of soil. We have investigated the response of cation exchange capacity (CEC) of three acid forest soils of variable charge to small changes in pH, ionic strength, and SO^2?₄ concentration. The variable charge for these temperate soils has the same significance as for tropical soils and those from volcanic ash. Maximum absolute increase in CEC on increasing pH by 0·2–0·5 units reached 5 cmol_c kg^-1 in O horizons. The increase in CEC on doubling ionic strength in EA and Bsh horizons of a Cambic Podzol was about half that amount, but relative gains compared to effective CEC were 65 and 46%, respectively. For other soil horizons, absolute changes were smaller, and relative changes were between 10 and 30%. Halving the SO^2?₄ concentration significantly influenced CEC only in some samples. Both pH and ionic strength must be adjusted with care when determining CEC_c of acid forest soils. Decreasing acid deposition will not inevitably increase CEC_c because in some soils pH effects may be balanced by simultaneous decrease in ionic strength.     

Apparent cation-exchange equilibria in podzolic forest soils

The Gaines–Thomas selectivity coefficient, K, was used to express the relation between the cations in solution and the cations in exchange sites in podzolic forest soils. Soil solution was obtained by centrifuging a fresh bulked soil sample. Exchangeable cations HX, AlX, CaX, MgX and KX and effective cation-exchange capacity, CEC_e, were determined with 0.1 m BaCl₂. Apparent values of K indicated a preference of Ca²⁺ over Mg²⁺ and over Al³⁺ in O, A and B horizons (log K_Al–Ca < 0 and log K_Mg–Ca < 0), whereas log K_K–Ca and log K_H–Ca exceeded zero. The horizons were similar with respect to log K_H–Ca, and the differences in log K_Mg–Ca were small. Log K_K–Ca and log K_Al–Ca increased in the horizons in the order O < A < B. Log K_Al–Ca was not significantly correlated with the fraction AlX/CEC_e. Log K_Mg–Ca was positively correlated with the fractions HX/CEC_e and AlX/CEC_e, and negatively correlated with log (CaX/MgX). The selectivity coefficient of binary cation exchange seemed to be applicable to in situ soil solutions. However, the fraction of each cation on exchange sites should be based on the CEC_e rather than on the sum of the two cations. The latter, also, seemed to be acceptable in cases of exchangeable cations with a large relative content in soil, e.g. in Al³⁺–Ca²⁺ exchange in A and B horizons, and in H⁺–Ca²⁺ exchange in O and A horizons.     

Vergleich zwischen Perkolation und Extraktion mit 1 M NH4Cl‐Lösung zur Bestimmung der effektiven Kationenaustauschkapazität (KAKeff) von Böden

Comparison between percolation and extraction with 1 M NH₄Cl solution to determine the effective cation exchange capacity (CEC_eff) of soils A simple method is proposed for the determination of the effective cation exchange capacity (CEC_eff). The soil is extracted with 1 M NH₄Cl‐solution, manually shaken for three times, and the exchangeable cations are determined by ICP‐OES and pH‐measurement. Comparison with corresponding results of the percolation method (n = 110 samples) shows good agreement in reproducibility, exchangeable cations (except Fe and Na), base saturation and CEC_eff.     

Adsorption complex,pH relationships in some acid mediterranean forest soil profiles

Acid soils in some mediterranean forests were investigated for the composition of the adsorption complex and the gradients in soil pH. The effective CEC (235–838 mmol_c kg^?1) and base saturation (93–98 %) are highest in ectorganic horizons. In the mineral horizons the effective CEC (23–52 mmol_c kg^?1) and base saturation (11–40 %) are much lower. The exchange complex of mineral horizons consists for 90 (AEh) to 40 percent (Bw2) of organic matter. The effective CEC of the mineral clay fraction is low (60 mmol_c kg^?1 clay). The clear trends in soil pH within the ectorganic layer of deciduous and sclerophyllous oak forests are attributed to vertical spatial separation of nitrogen mineralization (ammonification and strongly impeded nitrification) and nutrient uptake by roots (mainly NH₄). This leads to a high effective CEC in the fermentation layer and acidification of the uppermost part of the mineral soil. In contrast to the situation in temperate forests this process is impeded in mediterranean coniferous forests, where litter decomposition is extremely slow and both proton production and consumption take place in the organic rich mineral horizon.     

Apparent pH independence of charge in forest organic surface soil horizons

Conventional wisdom states that the source of negative charge in organic soil horizons is pH dependent and, therefore, acidification will decrease charge and the ability to retain nutrient cations. Using a variety of methods, we found that the native cation exchange capacity (CEC) of northeastern US forest soils varied with the amount of soil carbon (about 0.5 cmol per %C), independent of field pH. However, individual soil samples exhibited dramatic charge variability if the pH was adjusted during CEC measurement, as much as 20 cmol_c kg^? per pH unit change. These last two statements appear to be mutually exclusive. Extrapolating from pH-adjusted samples, the point of zero “base” cation capacity was consistently about 1.5 pH units below the native pH. We hypothesize the amount of charge is at a steady state with humification and decomposition processes. Response of soils to long-term acidification may be much different than that of short-term laboratory adjustments.     

Cation exchange properties of soils derived from lignite ashes

In Saxony‐Anhalt, Germany, an area of about 6000 ha is covered by lignite‐ash‐derived substrates. In some cases, pollutants like heavy metals or toxic organic compounds had been disposed of together with the lignite ashes. For this reason, we assessed factors influencing the cation exchange capacity (CEC) of lignite‐ash substrates exposed to natural weathering. We chose four research sites reflecting the different methods of disposal: two dumped landfills and two lagooned ashes of different ages. After determining the CEC at pH 8.1 (CEC_pot), we evaluated the influence of the content of silt and clay and the content of total organic C. As lignite‐ash‐derived substrates are rich in oxalate‐extractable Si, Al, and Fe, we performed an oxalate extraction and determined afterwards the CEC_pot to assess the contribution of oxalate‐soluble compounds to the CEC_pot. Moreover, we determined the variable charge of selected samples at pH values ranging from 4 to 7. The lignite‐ash‐derived soils had a high CEC_pot with means ranging from 25.1 cmol_c kg^–1 to 88.8 cmol_c kg^–1. The influence of the parent material was more important than the degree of weathering. The content of total organic C consisting of pedogenic organic matter and coked lignite particles together with the content of silt and clay played a statistically significant role in determining the CEC. Another property that influenced the amount of CEC in medium textured lignite ashes was the content of oxalate‐soluble silica and aluminum. After oxalate extraction, they lost about 30% of their CEC due to the dissolution of oxalate‐soluble compounds. In coarse textured lignite ashes, oxalate extraction led to higher amounts of CEC, probably due to an increase of surface area resulting either from the disintegration of particles or from etching caused by insufficient dissolution of magnetite and maghemite. Moreover, lignite‐ash‐derived substrates exhibit a high amount of pH‐dependent charge. The CEC decreased by 40% in a topsoil sample and by 51% in a subsoil sample as the pH declined from 7 to 4.     

Short Communication Actual cation exchange capacity in lignite containing pyritic mine soils

The actual cation exchange capacity (CEC_act) in sandy mine soils from Tertiary sediments increases with the lignite contents of the substrates. Therefore, lignite is important for nutrient storage and availability in these soils. Base saturation varies over a wide range of 4 — 100% according to soil pH. For the determination of CEC_act, the high contents of soluble salts typical for these substrates have to be considered for reliable results.     

The influence of acid soil factors on the growth of snapbeans in major appalachian soils

Abstract

Acid soil limitations to plant growth were assessed In 55 horizons of 14 major Appalachian hill land soils. Aluminum sensitive “Romano” and Al‐tolerant “Dade” snapbeans (Phaseolus vulgaris L.) were grown for 5 weeks in limed and unlimed treatments of the 55 horizons. Shoot and root growth was depressed >20% in unlimed relative to limed treatments in approximately 2/3 of the horizons. Dade snapbeans were generally more tolerant of the acid soil conditions and had higher Ca concentrations in the shoots than Romano snapbeans. However, the sensitive‐tolerant snapbean pair could not consistently be used to identify horizons with soil Al problems. Growth of both snapbeans was generally best in A horizons and worst in E horizons. The E horizons in this study were characterized by low Ca saturation (exchangeable Ca x 100/cation exchange capacity) and high Al saturation (exchangeable Al x 100/cation exchange capacity). Exchangeable Ca, soil Ca saturation and total soil solution Ca were positively correlated (p<0.01) with snapbean root and shoot growth. Soil Al saturation, total soil solution Al and soil solution Al reacting in 15 seconds with 8‐hydroxyquinoline were negatively correlated (p<0.01) with growth. The ratio of Ca/Al in soil solution was more closely related to snapbean growth than the soil solution concentration of any individual element. Soil and soil solution Mn were, in general, not significantly correlated with snapbean growth. Many of the horizons in this study had both Al toxicity and Ca deficiency problems and interaction between Ca and Al affected both snapbean growth and Ca uptake. These findings confirm the importance of considering Ca as well as Al when investigating Al phytotoxicity.     

Soil base saturation affects root growth of European beech seedlings§

To assess the potential effects of Al toxicity on the roots of young European beech (Fagus sylvatica L.), seeds were sown in soil monoliths taken from the Ah and B horizons of forest soils with very low base saturation (BS) and placed in the greenhouse. The Ah horizons offered a larger supply of exchangeable cation nutrients than the B horizons. After 8 weeks of growth under optimal moisture conditions, the seedlings were further grown for 14 d under drought conditions. Root‐growth dynamics were observed in rhizoboxes containing soils from the Ah and B horizons. The concentrations of Al³⁺, base cations, and nitrate in the soil solution and element concentrations in the root tissue were compared with above‐ and belowground growth parameters and root physiological parameters. There was no strong evidence that seedling roots suffered from high soil‐solution Al³⁺ concentrations. Within the tested range of BS (1.2%–6.5%) our results indicated that root physiological parameters such as O₂ consumption decreased and callose concentration increased in soils with a BS < 3%. In contrast to the B horizons, seedlings in the Ah horizons had higher relative shoot‐growth rates, specific root lengths, and lengths and branching increments, but a lower root‐to‐shoot ratio and root‐branching frequency. In conclusion, these differences in growth patterns were most likely due to differences in nutrient availability and to the drought application and not attributable to differences in Al³⁺ concentrations in the soil solution.     

Forest soil chemical changes between 1949/50 and 1987

Soil profiles from the Alltcailleach Forest in north-east Scotland originally sampled in 1949/50 were resampled in 1987. Soil pH, exchangeable Ca, Mg, K and Na, extractable Al and cation exchange capacity were measured on the original stored and resampled soils. Chemical changes were characterized by decreases in pH, base cations, base saturation and cation exchange capacity. Extractable amounts of Al increased. Sequential leaching experiments showed a significant increase in the amount of extractable sulphate in mineral soil horizons. Changes in soil chemistry were interpreted to result from a combination of nutrient depletion caused by tree growth, natural pedogenic processes and atmospheric pollution effects.     

Soil chemical properties affecting NH4+ sorption in forest soils

Fourteen European forest soils from the boreal to the mediterranean climate on different parent materials were investigated with respect to their ability to store NH₄⁺ in exchangeable form, using sorption isotherms. Distribution coefficients for NH₄⁺ sorption per unit weight of soil were in the range of 0.02 to 0.77. NH₄⁺ sorption coefficients were usually highest in the forest floor of a given soil. NH₄⁺ sorption behaviour of mineral soil horizons was correlated to soil parameters that are determined during routine soil analysis. A combination of CEC and base saturation explained up to 95% of the variability Of NH₄⁺ sorption. In the forest floors, variability in NH₄⁺ sorption could not be explained quantitatively from independent soil parameters. The affinity of the sorption sites for NH₄⁺ was the most important factor for explanation of the variability in NH₄⁺ sorption in the forest floors but was of low importance in mineral soil horizons. As NH₄⁺ exchanges predominantly base cations, susceptibility of NH₄⁺ to transport through the soil profile increases with Iowbase saturation of a soil as well as with low CEC values.     

Soil acidification along a topographic gradient on Roundtop Mountain,Quebec, Canada

We examined the effects that different acidic loadings have had on soil chemistry along a toposequence on Roundtop Mountain. Due to fog interception by the forest canopy, the amount of time in the clouds is a major factor determining the amount and chemistry of precipitation reaching the soil and hence, acid precipitation loading is directly related to elevation. Soils on a transect from 520 to 850 m show a pattern of chemistry that corresponds to the loading of acidic deposition. Soil solutions collected at two elevations show different levels of both SO₄ and Cl, two of the anions in fog water as well as differences in concentrations of H ion and Al. Surface horizons of soils located at 850 m have pH in water as low as 3.7; in mineral horizons base saturation is extremely low (<5%) and Al saturation exceeds 95% in many cases. In contrast, lower on the mountain slope (below 650 m), pH is slightly higher (about 4.1) and base saturation rises to over 50% for the same soil horizons. There is a clear relationship between soil acidification and position on the mountain.     

Soil organic matter stabilization in acidic forest soils is preferential and soil type-specific

Minerals with large specific surface areas promote the stabilization of soil organic matter (SOM). We analysed three acidic soils (dystric, skeletic Leptic Cambisol; dystric, laxic Leptic Cambisol; skeletic Leptic Entic Podzol) under Norway spruce (Picea abies) forest with different mineral compositions to determine the effects of soil type on carbon (C) stabilization in soil. The relationship between the amount and chemical composition of soil organic matter (SOM), clay content, oxalate‐extractable Fe and Al (Fe_o; Al_o), and dithionite‐extractable Fe (Fe_d) before and after treatment with 10% hydrofluoric acid (HF) in topsoil and subsoil horizons was analysed. Radiocarbon age, ¹³C CPMAS NMR spectra, lignin phenol content and neutral sugar content in the soils before and after HF‐treatment were determined and compared for bulk soil samples and particle size separates. Changes in the chemical composition of SOM after HF‐treatment were small for the A‐horizons. In contrast, for B‐horizons, HF‐soluble (mineral‐associated) and HF‐resistant (non‐mineral‐associated) SOM showed systematic differences in functional C groups. The non‐mineral associated SOM in the B‐horizons was significantly depleted in microbially‐derived sugars, and the contribution of O/N‐alkyl C to total organic C was less after HF‐treatment. The radiocarbon age of the mineral‐associated SOM was younger than that of the HF‐resistant SOM in subsoil horizons with small amounts of oxalate‐extractable Al and Fe. However, in horizons with large amounts of oxalate‐extractable Al and Fe the HF‐soluble SOM was considerably older than the HF‐resistant SOM. In acid subsoils a specific fraction of the organic C pool (O/N‐alkyl C; microbially‐derived sugars) is preferentially stabilized by association with Fe and Al minerals. Stabilization of SOM with the mineral matrix in soils with large amounts of oxalate‐extractable Al_o and Fe_o results in a particularly stable and relatively old C pool, which is potentially stable for thousands of years.     

An evaluation of cation exchange capacity measurements for soils in the tropics

Abstract

Comparisons of CEC and exchange acidity neasurements were made on a group of selected West African soils using three commonly used analytical procedures, namely, neutral‐acetate displacement, BaCl₂‐TEA leaching at pH 8, and unbuffered KCl extraction.

The three methods gave large differences in CEC values which followed the order of BaCl₂‐CEC>>NH₄OAc‐CEC> KCl‐CEC. Results of exchange acidity also followed the same order. The high exchange acidity values obtained by the BaCl₂‐TEA (pH 8) method were mainly due to changes in surface charge characteristics of Fe and Al oxides and hydrous oxides. The effective CEC method is recommended for routine soil analysis for highly weathered soils in the tropics.

Regression analysis of the base saturation values obtained from the three methods indicated the data followed a curvilinear relationship. The acetate method was more highly correlated with the effective CEC method than with the BaCl₂ method.     

Field and chemical Evaluation of volcanic ash deposition in some soils of Malaysia

A study was conducted to determine the extend of volcanic ash deposition and distribution in some soils of Malaysia. A total of 12 soil types of different geology and locations from Peninsular Malaysia and West Sarawak were collected and analysed for their physico‐chemical and dissolution analysis. All soils under study belonged to either the order of Inceptisols, Ultisols or Oxisol. They were acidic and had relatively low CEC and exchangeable bases. The Al saturation percent were higher in the Ultisols as compared to the Oxisols. Field and laboratory investigations, and the dissolution analysis comprising of the binary ratio, ferrihydrite percent and allophane content, suggested that the soils under study were highly weathered and non‐allophanic. The soils of West Sarawak, however, may contain a reasonable deposits of the volcanic ash materials, as shown by the higher pH_NaF values of near 9.4, but other laboratory analysis were still not conclusive of the result.     

The effect of five years acid treatment on leaching,soil chemistry and weathering of a humo-ferric podzol

This paper describes the effect of treating a nutrient-poor forest soil in monolith lysimeters with H₂SO ₄, pH 3.0, for 4.75 yr. The lysimeters were instrumented with porous cup probes to distinguish processes occurring in each soil horizon. In the A horizon base cation exchange and sulphate absorption were the principal proton- consuming processes whereas lower down the profile Al³⁺ dissolution from hydrous oxides dominated. Acid treatment thus reduced the amount of amorphous Al in the lower horizons, but exchangeable Al was unaffected. Sulphate absorbtion was positively correlated with the distribution of Al hydrous oxides. High rates of nitrification reduced the differences between acid and control monoliths, but acid treatment significantly reduced soil pH down to 75 cm and reduced the levels of exchangeable base cations in the litter and A horizons. Acid treatment increased the leaching rates of base cations and Al. Consideration of the total base cation content shows that acid treatment increased the rate of weathering by 0.7–1.4 k eq ha^?1 yr^?1. The results should be useful in modelling more realistic rates of acid input to similar soils.     

Podzol development with time in sandy beach deposits in southern Norway

The coastal areas of SE Norway provide suitable conditions for studying soil development with time, because unweathered land surfaces have continuously been raised above sea level by glacio‐isostatic uplift since the termination of the last ice age. We investigated Podzol development in a chronosequence of six soils on sandy beach deposits with ages ranging from 2,300 to 9,650 y at the W coast of the Oslofjord. The climate in this area is rather mild with a mean annual temperature of 6°C and an annual precipitation of 975 mm (Sandefjord). The youngest soil showed no evidence of podzolization, while slight lightening of the A horizon of the second soil (3,800 years) indicated initial leaching of organic matter (OM). In the 4,300 y–old soil also Fe and humus accumulation in the B horizon were perceptible, but only the 6,600 y–old and older soils exhibited spodic horizons. Accumulation of OM in the A horizons reached a steady state in <2,300 y, while in the B horizons OM accumulated at increasing rates. pH dropped from 6.6 (H₂O)/5.9 (KCl) in the recent beach sand to 4.5 (H₂O)/3.8 (KCl) within approx. 4,500 y (pH_H2O)/2,500 y (pH_KCl) and stayed constant thereafter, which was attributed to sesquioxide buffering. Base saturation showed an exponential decrease with time. Progressive weathering was reflected by increasing Fe_d and Al_d contents, and proceeding podzolization by increasing amounts of pyrophophate‐ and oxalate‐soluble Fe and Al with soil age. These increases could be best described for most Fe and Al fractions by exponential models. Only the increasing amounts of Fe_p could be better described by a power function and those of Fe_o by a linear model.     

Aluminium release in relation to the determination of cation exchange capacity of some podzolized New Zealand soils

In upper mineral horizons, CEC by compulsive and isotopic exchange methods, using Ba²⁺ as the saturating cation, gave higher values than the effective CEC at natural soil pH, and much higher values than CEC determined with m NH₄OAc at pH 7. Cumulative Al release during leaching was considerably higher using Mg²⁺ and Ba²⁺ chlorides than K⁺ and NH₄⁺ chlorides, and gave a different shape extraction curve. Basal spacing of the dominant dioctahedral vermiculite in the soil clays contracted from 14.5Å to 10.0–10.9 Å when saturated with NH₄⁺ and K⁺, restricting release of interlayer Al. Lower horizons, containing a large proportion of Al-chlorite in the clay fraction, which did not contract with any of the cations, showed more normal exchange behaviour. On leaching, Al release was slightly greater with K⁺ and NH₄⁺, than with Mg²⁺ and Ba²⁺, chlorides. The implication of the results for CEC measurements is discussed.