Contribution of SO3 to the acid neutralizing capacity of Andosols exposed to strong volcanogenic acid and SO2 deposition

Soil response to acid and sulphur inputs is influenced largely by the soil's physico‐chemical properties. We studied the effects of such depositions in two types of Andosols exposed to volcanogenic emission (Masaya, Nicaragua), namely Eutric Andosols rich in allophanic constituents, and Vitric Andosols rich in volcanic glass. Small mineral reserves and large contents of secondary short‐range ordered minerals indicate a more advanced weathering of the Eutric than the Vitric Andosols. Strong correlations between soil specific surface and oxalate‐extractable Al, Si and Fe contents highlight the predominant contribution of short‐range ordered minerals to surface area. Both types of Andosols showed a decrease in pH upon acid input. Sulphur deposition increased the soil's S content to 5470 mg S kg^?1. However, the acid neutralizing capacity of the soil solid phase (ANC_s) was not significantly affected by the acid and S inputs. Non‐exchangeable (mineral reserve) and exchangeable cations and total contents of sulphur and phosphorus dictate most of the ANC_s variation. In the Vitric Andosols, mineral reserves contributed up to 97% to these four additive pools, whereas the exchangeable cations accounted for 1–4%. In the Eutric Andosols, the contribution of mineral reserves was less (71–92%), but the exchangeable cation content was greater (1–20%), whereas the contribution of sulphur and phosphorus was significant at 1–15% and 2–7%, respectively. The main process involved in H⁺ consumption is mineral weathering in Vitric Andosols and ion exchange in Eutric Andosols.     

One equation to analyse the pH of soil systems

Starting from the basic equations of chemical equilibrium, an analytical mathematical expression is derived that relates pH to base saturation, concentration of acid anions (SO₄^2?, NO₃^?, etc.) and other properties of the soil and soil solution. The equation is particularly valid in acid soils (low base saturation and relatively large, >100 μmol_c dm^?3, concentration of acid anions) in the range in which cation exchange is the buffering mechanism. Values of pH, alkalinity and degassed pH calculated with the aid of this equation compared well to values measured in three forest-floor horizons; calculated pH values also compared well to values measured on a number of acid soils. The equation is also used to derive analytical mathematical expressions for alkalinity, soil leaching sensitivity (a measure of the sensitivity of a soil solution to become dominated by A1³⁺), and other variables of interest in the context of acidification.     

模拟不同pH降雨和施氮对水耕铁渗人为土酸化的影响

室内模拟研究3个pH梯度降雨和3水平的施氮量对水耕铁渗人为土土壤酸化的影响。结果表明,不同pH降雨及施氮处理土壤的酸度累积量为4.73～15.57 mmol H+每柱,分别以pH 6.5降雨和不施氮处理、pH 2.5添加高氮量(N2)处理酸化速率为最低和最高,相同pH降雨处理下,致酸量随施氮量增加而上升;相同施氮下,不施氮处理土壤酸度累积随降雨pH降低而增加,但中施氮量(150 mg kg-1土)和高施氮量(300 mg kg-1土)下,pH 4.5处理土壤酸度累积量则小于pH 6.5处理;不同降雨及施氮处理NO3-淋溶致酸量为4.32～12.88 mmol每柱,NH+4淋溶消耗H+量为0.01～0.29 mmol每柱;正常酸沉降(pH 6.5)下,中施氮量和高施氮量处理致酸量都大于各梯度pH降雨的致酸量。以上结果表明,单施氮处理的致酸量大于单纯的酸沉降处理,而无论是降雨还是施氮,NO-3淋溶在加速土壤酸化进程中占主导作用。     

Modelling Acidification Effects on Coniferous Forest Soils

Two submodels for simulating the leaching of forest soils are described. SOILORG is used for O, E, and top B layers where Al(OH)₃ is absent and organic matter is the major base cation storage. SOILMIN cares for the rest of the profile where Al(OH)₃ control of Al is assumed and goethite provides most of the sulphate storage, clay mineral surfaces providing base cation storage. Results are presented from a test run for the period 1911 to 2030, based on data from a 260 cm deep soil profile in the SW of Sweden investigated 1990 and on a likely deposition scenario. Considering that the deposition of base cations exceeded the removal by stemwood in 1911 when the simulation started, the biologic acidification of the soil profile had reached a steady state before 1911 so that no additional acidification took place before 1930 and very little before 1950. After 1950 it was strongly enhanced by the increased acid deposition. In the mineral soil a considerable resistance against acidification is offered both by base cation exchange and sulphate adsorption, creating an acidification front which moved slowly down the B-horizon then accelerated, reaching the bottom of the profile in 1990. A deposition reduction by 2/3 during 1990–2010 will cause a partial recovery of pH, particularly in the deeper parts of the profile.     

土壤加速酸化的主要农业驱动因素研究进展

土壤酸化是土壤质量退化的一个重要方面,农业活动对其有极其重要的驱动作用。本文从土壤酸化加速的农业主驱因素:化肥、作物及有机物料等方面阐述它们对土壤酸化的影响。认为化肥尤其是生理酸性肥料和含硫肥料的不合理施用加速土壤酸化,而氮肥的致酸除受氮素形态影响外,硝化作用及硝化产物的淋溶是重要的致酸原因,同时豆科作物的固氮致酸作用也不容忽视。作物通过选择性吸收盐基阳离子,通过秸秆和子粒转移出生产系统后,导致土壤盐基量减少,土壤表面交换性酸增加;作物根系呼吸、根系分泌物及土壤溶液中重碳酸盐的淋溶也引起土壤酸化;而秸秆和畜禽粪便对土壤酸化的影响除受土壤本身性质影响外,秸秆中的灰化碱含量、畜禽粪便中的碳及氮和盐分去向对酸化也有重要的影响。     

Effects of experimental acidification and alkalinization on soil and growth and health of Acer saccharum Marsh.

Experimental application of eight acidifying, neutral, or alkalizer compounds (range: –16 to 16 kmol ha^–1 of acid‐neutralizing capacity [ANC]) was realized in two northern hardwood stands having significantly different soil base saturation (BS) (a “poor” and a “rich” site) to assess responses of soil physico‐chemical properties, and nutrition, growth, and health of sugar maple (Acer saccharum Marsh.) trees in the short (3 y) and longer term (10 y). The treatments influenced the main indicators of acidity in the forest floor (soil exchangeable‐Ca saturation [S_Ca], BS, exchangeable‐acidity saturation [S_H+Al], and the S_Ca/S_H+Al ratio) at both sites, their values increasing (decreasing for S_H+Al) along the ANC treatment gradient in both the short and longer term, except for pH. Base saturation of the upper 15 cm of the mineral B horizons of soils was influenced at the two sites 10 y after treatment application. Although ANC treatments affected nutrient concentrations of tree foliage in the short term, their effect was no longer detectable after 10 y at the two sites. Growth, however, was strongly related to ANC treatments after 10 y, but only at the poor site. From 1990 to 2000, the basal‐area growth rate of trees at the poor site was (mean ± SE) –0.62 ± 0.28 cm² y^–2 tree^–1 for the most negative ANC treatment to +0.90 ± 0.20 cm² y^–2 tree^–1 for the most positive ANC treatment. A climatic‐stress episode occurring in 1995/96 appeared to accentuate the growth decline of trees subjected to the most negative ANC treatment at the poor site. The experimental results support the hypothesis that atmospheric acid deposition load can cause forest soil base‐cation depletion, acidification, and predispose sugar maple to health and growth decline in the longer term in base‐cation‐poor soils, and that the phenomenon may be reversible by adding alkalizers.     

电渗析与酸淋洗模拟紫色土酸化的效果比较

为了比较电渗析与酸淋洗试验模拟紫色土酸化的效果,在重庆地区采集了不同pH(5.00和7.06)的2个紫色土,分别进行不同天数(1,2,5,7,10天)的电渗析和酸淋洗试验处理,并分析了试验处理前后土壤的酸度特征和交换性盐基成分含量变化。结果表明,在整个10天的淋溶处理过程中,2种紫色土的pH均无显著变化,说明紫色土具有一定的酸缓冲能力,短期的酸雨淋溶不能实现紫色土的严重酸化。而采用电渗析处理10天后,中性紫色土和酸性紫色土的pH分别降低3.4和1.1个单位。在整个电渗析处理过程中,土壤的交换性酸含量显著升高,盐基离子大量淋失。电渗析可以实现对紫色土的快速酸化处理。2种紫色土中,电渗析处理后中性紫色土的酸化程度大于酸性紫色土。这是由于中性紫色土的表面负电荷量更高,导致更多致酸离子吸附在土壤胶体表面,最终造成中性紫色土的酸化程度更加严重。因此,电渗析处理比酸雨淋溶处理对紫色土酸化效果更好,且可用于紫色土的酸化机理研究。进一步结合2种方法的技术可操作性,认为电渗析法是研究紫色土酸化问题的一种有效技术手段。     

Natural and anthropogenic components of soil acidification

The following 8 theses are theoretically founded and experimentally quantified. 1. Rocks contain only bases and no acid precursors. Therefore, with the exception of sulfide containing rocks, soils cannot acidify as a result of atmospheric rock weathering. 2. A consumption of protons in rocks and soils results in a decrease of their acid neutralizing capacity (ANC) and can result in the buildup of a base neutralizing capacity (BNC). Strong soil acidification leads to the formation of stronger acids from weaker acids in the solid phase; this may be connected with a decrease in the BNC. 3. Weak acids (carbonic acid) lead in geological times to the depletion of bases without a larger accumulation of labile cation acids. Strong acids (HNO₃, organic acids, H₂SO₄) can lead within a few decades to soil acidification, i.e. to leaching of nutrient cations and the accumulation of labile cation acids. 4. The acid input caused by the natural emission of SO₂ and NO_x can be buffered by silicate weathering even in soils low in silicates. 5. The cause of soil impoverishment and soil acidification is a decoupling of the ion cycle in the ecosystem. 6. Acid deposition in forest ecosystems which persists over decades leads to soil acidification. 7. Formation and deposition of strong acids with conservative anions (SO₄, NO₃) shifts soil chemistry into the Al or Al/Fe buffer range up to great soil depth. In such soils eluvial conditions prevail throughout the solum and even in upper part of the C horizon: in connection with the decomposition of clay minerals, Al and eventually Fe are being eluviated. The present soil classification does not include this soil forming process. 8. In the long run, soil acidification by acid deposition results in the retraction of the root system of acid tolerant tree species from the mineral soil, and in water acidification.     

Inorganic sulphate extraction from SO2-impacted Andosols

Sulphate sorption on to the surface of short‐range ordered minerals and precipitation of Al‐hydroxy sulphate contribute to the acid neutralizing capacity of soils. The correct measurement of total inorganic sulphate is thus essential in soils that are accumulating SO₄^2– anions. We extracted SO₄^2– by various solutions, namely 0.005 m Ca(NO₃)₂, 0.016 m KH₂PO₄, 0.5 m NH₄F and 0.2 m acidic NH₄‐oxalate (pH 3), from Vitric and Eutric Andosols exposed to prolonged deposition of acid and SO₂ from an active volcano (Masaya, Nicaragua). We attributed sulphate extractable by KH₂PO₄ (20–3030 mg kg^?1) to anion‐exchangeable SO₄^2–, which was much smaller than NH₄F‐ and oxalate‐extractable SO₄^2– (400–9680 and 410–10 480 mg kg^?1, respectively). Our results suggest the occurrence of a sparingly soluble Al‐hydroxy‐mineral phase extractable by both NH₄F and oxalate. The formation of Al‐hydroxy minerals would result from the combination of enhanced weathering caused by strong acid loading and simultaneous occurrence of large SO₄^2– concentrations in soil solution. Oxalate extracted slightly more inorganic SO₄^2– than did NH₄F, this additional amount of SO₄^2– correlating strongly with oxalate‐extractable Si and Fe contents. Preferential occlusion of SO₄^2– by short‐range ordered minerals, especially ferrihydrite, explains this behaviour. If we exclude the contribution of occluded sulphate then oxalate and NH₄F mobilize similar amounts of SO₄^2– and are believed to mobilize all of the inorganic SO₄^2– pool.     

Soil acidification and the importance of liming agricultural soils with particular reference to the United Kingdom

Soil acidification is caused by a number of factors including acidic precipitation and the deposition from the atmosphere of acidifying gases or particles, such as sulphur dioxide, ammonia and nitric acid. The most important causes of soil acidification on agricultural land, however, are the application of ammonium‐based fertilizers and urea, elemental S fertilizer and the growth of legumes. Acidification causes the loss of base cations, an increase in aluminium saturation and a decline in crop yields; severe acidification can cause nonreversible clay mineral dissolution and a reduction in cation exchange capacity, accompanied by structural deterioration. Soil acidity is ameliorated by applying lime or other acid‐neutralizing materials. ‘Liming’ also reduces N₂O emissions, but this is more than offset by CO₂ emissions from the lime as it neutralizes acidity. Because crop plants vary in their tolerance to acidity and plant nutrients have different optimal pH ranges, target soil pH values in the UK are set at 6.5 (5.8 in peaty soils) for cropped land and 6.0 (5.3 in peaty soils) for grassland. Agricultural lime products can be sold as ‘EC Fertiliser Liming Materials’ but, although vital for soil quality and agricultural production, liming tends to be strongly influenced by the economics of farming. Consequently, much less lime is being applied in the UK than required, and many arable and grassland soils are below optimum pH.     

Canopy leaching of cations in Central European forest ecosystems – a regional assessment

The leaching of Ca, Mg, and K from canopies is a major pathway of these cations into forest soils. Our aim was to quantify rates of canopy leaching and to identify driving factors at the regional scale using annual fluxes of bulk precipitation and throughfall from 37 coniferous and deciduous forests of North and Central Europe. Total deposition of Ca, Mg, K, and H⁺ was estimated with Na as an index cation. The median canopy leaching increased in the order: Mg (0.11 kmol_c ha^–1 a^–1) < Ca (0.31 kmol_c ha^–1 a^–1) < K (0.39 kmol_c ha^–1 a^–1). Canopy leaching of Ca and K was positively correlated with the calculated total H⁺ deposition and H⁺ buffered in the canopy, whereas canopy leaching of Mg was not. With contrasting effects, fluxes of SO₄‐S and NH₄‐N in throughfall explained to 64 % (P<0.001) of the Ca canopy leaching. Fluxes of NH₄‐N and Ca were negatively correlated, suggesting that buffering of H⁺ by NH₃ deposition reduced canopy leaching of Ca. Amount of bulk precipitation and SO₄‐S in throughfall were identified as much weaker driving factors for canopy leaching of K (r²=0.28, P<0.01). Our results show that Ca is the dominant cation in buffering the H⁺ input in the canopy. At the regional and annual scale, canopy leaching of Mg appears to be unaffected by H⁺ deposition and H⁺ buffering in the canopy.     

Mechanism of reduction of exchangeable aluminum by gypsum application in acid andosols

Mechanism of reduction of exchangeable aluminum in acid Andosols treated with gypsum was studied by using cation exchange resin methods to determine the amount of polymerized aluminum. Two types of acid Andosols were used as test soils: Kitakami light colored Andosol (fine, mixed, mesic, Andic Dystrochrept) and Kawatabi thick high humic Andosol (medial, mesic mixed Alic Pachic Melanudand). Polymerization of aluminum in the soil solution of both Kitakami and Kawatabi Andosols treated with gypsum was suggested based on an analysis using cation exchange resin methods, whereas that in monomer aluminum solution was not detected. Accumulation of polymerized aluminum in both Kitakami and Kawatabi Andosols was determined by using cation exchange resin, and the amounts of polymer aluminum trapped by the resin and the ratio of polymer aluminum to monomer aluminum were increased with the incubation time. The values of CEC which decreased in the Kitakami Andosol after gypsum treatment were almost equivalent to the amounts of cation exchange sites occupied by polymer aluminum ions which were calculated based on the decrease of the values of Y _l. We conclude that the mechanism of reduction of exchangeable aluminum in strongly acid Andosols treated with gypsum is as follows: firstly, exchangeable aluminum adsorbed on the cation exchange sites of soils may be released into the soil solution due to the increase in the ion strength caused by gypsum application, and then monomer aluminum in soil solution may be polymerized in the presence of soil colloidal materials. Consequently, the polymer aluminum formed in the soil solution may be selectively and irreversibly fixed on the cation exchange sites of 2 : 1 clay minerals.     

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.     

酸雨对黄土磷的淋溶效应

采用室内土柱模拟淋溶试验,分析了陕西省杨凌区3种土壤在5个酸雨梯度的侵蚀作用下,土壤磷的释放和迁移规律.结果表明,酸雨会使土壤受到一定程度的酸化,而土壤的酸化程度与酸雨的pH值、土壤的类型、土壤的pH值、阳离子交换量、有机质含量有关.土壤对酸雨的缓冲能力由大到小的顺序为:腐殖质层＞母质层＞黏化层.随着酸雨累积淋溶量的增加,土壤磷的释放总量呈增加趋势,但淋失率会下降.酸雨的pH值为5时土壤磷的累积淋失量最大,土壤磷的累积淋失量和淋失率顺序为:腐殖质层＞黏化层＞母质层.酸雨对腐殖质层的磷具有最强侵蚀效应.母质层和黏化层的酸化主要发生在土壤表层,而腐殖质层酸化主要发生在土壤底层,酸雨侵蚀后腐殖质层酸化最严重.长期的酸雨侵蚀会导致土壤磷流失,造成土壤养分贫瘠化.     

Effect of soil pH on cation and anion solubility

Abstract

The effect of soil pH on the exchangeability and solubility of soil cations (Ca, Mg, Na, K, and NH₄‐N) and anions (NO₃‐N, Cl, and P) was investigated for 80 soils, spanning a wide range in physical and chemical properties and taxonomic groups. This information is needed from environmental and agronomic standpoints to estimate the effect of changes in soil pH on leachability and plant availability of soil nutrients. Soils were incubated with varying amounts of acid (H₂SO₄) and base (CaCO₃) for up to 30 days. Although acid and base amendments had no consistent effect on cation exchangeability (as determined by neutral NH₄OAc), amounts of water‐soluble Ca, Mg, Na, K, NH₄‐N, and P decreased, while NO₃‐N and Cl increased with an increase in soil pH. The increase in cation solubility was attributed to an increase in the negative charge of the soil surface associated with the base addition. The change in surface electrostatic potential had the opposite effect on amounts of NO₃‐N and Cl in solution, with increases in N mineralization with increasing soil pH also contributing to the greater amount of NO₃‐N in solution. The decrease in P solubility was attributed to changes in the solubility of Fe‐, A1‐, and Ca‐P complexes. The logarithm of the amount of water‐soluble cation or anion was a linear function of soil pH. The slope of this relationship was closely related (R² = = 0.90 ‐ 0.96) to clay content, initial soil pH, and size of the cation or anion pool maintaining solution concentration. Although the degree in soil pH buffering increased with length of incubation, no effect of time on the relationship between cation or anion solubility and pH was observed except for NO₃‐N, due to N mineralization. A change in soil pH brought about by acid rain, fertilizer, and lime inputs, thus, affects cation and anion solubility. The impact of these changes on cation and anion leachability and plant availability may be assessed using the regression equations developed.     

Mobilization of Cd upon acidification of agricultural soils: column study and field modelling

The potential effect of acidification of contaminated sandy soils on Cd transport in the unsaturated zone was assessed. Forty‐eight soil profiles were sampled at five depths in a polluted field that was set aside in 1992. The Cd concentration in the top 30 cm of this field was, on average, 10 mg kg⁻¹. A column experiment was carried out with one of the topsoil samples. Homogeneously packed columns were leached with 0.001 m CaCl₂, adjusted to pH 3 or pH 5.7, at a pore water velocity of 6 cm day⁻¹. The Cd and proton transport was predicted with coupled transport equations. The Cd transport was modelled by assuming local equilibrium and by using sorption parameters derived from batch experiments, while acidification was modelled with a kinetic approach, on the assumption that proton buffering was due to cation exchange and mineral weathering. Organic matter was the main contributor to the cation exchange capacity of these soils. Observed and predicted pH and Cd profiles in the columns agreed well. With the same model, the proton and Cd transport at field scale was calculated for each of the 48 profiles sampled (‘grid model’). It was predicted that the field‐averaged Cd concentration in the seepage water will increase from 6 μg litre⁻¹ at present to 200 μg litre⁻¹ over 260 years, which greatly exceeds the maximum permissible concentration (MPC) in groundwater of 5 μg litre⁻¹. Predictions of Cd transport using field‐averaged soil properties yielded a later breakthrough time and a larger peak Cd concentration than predicted with the grid model, which illustrates the impact of spatial variability on solute transport. Continuation of liming practices is a possible solution to prevent breakthrough of Cd at concentrations far in excess of the MPC.     

Characterization of Andosols in Yakushima Island

We examined soils derived from volcanic ash of Kikai-Akahoya tephra on Yakushima Island, Japan, and classified them according to the Unified Soil Classification System of Japan, 2nd Approximation (USCSJ 2nd) and the World Reference Base for Soil Resources (WRB). Five pedons with horizons showing high (>20%) volcanic glass content were investigated. Soils developed under evergreen broad-leaved forests had high acid oxalate-extractable aluminum (Alo) and acid oxalate-extractable silicon (Sio) concentrations, and low acid oxalate-extractable iron (Fe)/dithionite-citrate-extractable Fe ratio. This indicates a warmer climate and less severe leaching conditions compared with soils developed under coniferous forests dominated by Cryptomeria japonica and grasslands dominated by Pseudosasa owatarii. All soils contained considerable amount of hydroxyl-Al-interlayered 2:1 clay minerals. The surface horizons of the pedons developed under the cool-temperate C. japonica forests contained smectite as a result of podzolization. However, the surface horizon of the pedon developed under cool-temperate P. owatarii grasslands did not contain smectite. All pedons belonged to the Kuroboku soils great group (USCSJ 2nd) and Andosols (WRB). Pedons in mountainous areas did not contain horizons with more than 6?g?kg^?1 of Sio and hence were classified as non-allophanic Andosols. In mountainous areas, it was observed that allophane formation was inhibited by Al leaching due to intense rainfall (>10,000?mm year^?1); Al consumption due to the formation of the Al-humus complex; and Al incorporation into the interlayers of vermiculite. The low soil water pH [pH(H₂O)] and leaching of silicon (Si) in mountainous areas would support these anti-allophanic effects.     

Long Term Changes of Base Cation Pools in Soil and Biomass in a Beech and a Spruce Forest of Southern Sweden

During the past 60 years there has been a considerable decline in pH in mineral soil beneath spruce and beech stands at Tönnersjöheden Experimental Forest in south-west Sweden. In this report an attempt is made to estimate the corresponding declines in base cation pools. The exchangeable storage of Na, K, Ca and Mg in soil, down to 70 cm depth, is calculated to have decreased by 57–60 per cent for beech and by 56–74 per cent for the spruce stands during the period 1927–1984. The calculated cation depletions are compared with estimated nutrient uptake in biomass, base cation release by weathering and leaching losses due to percolation of strong mineral acids and organic anions during the period. The biological acidification may explain about 50–60 per cent of the total losses of base cations from soil, the cation accumulation in biomass then explain 41–43 per cent units for beech and 34–45 per cent units for spruce. The estimated losses of base cations due to acid rain correspond to an amount of cations similar to that accumulated in the spruce biomass during one generation.     

Prolonged leaching of mineral forest soils with dilute HCl solutions: the solubility of Al and soil organic matter

Long-term acidification has been shown to result in a considerable decrease in the amount of organically bound soil Al and in a gradual decrease in the solubility of Al. We examined the solubility of soil organic matter (SOM) and Al in four acid mineral soils (one Arenosol Ah, two Podzol Bh, and one Podzol Bs) as they were leached sequentially using a solution containing 0.001 m HCl and 0.01 m KCl. The acid leaching resulted in relative decreases in Al that were 2–6 times greater than for organic C. The organic C and Al dissolved by the acid leaching originated mainly in the pyrophosphate-extractable fraction of the elements. Protonation seems to be a major mechanism in stabilizing the residual SOM, as indicated by small changes in effective cation exchange capacity with the degree of acid leaching. In the samples of Podzol Bh and Arenosol Ah soils the solubility of Al (defined as log₁₀{Al³⁺} + 1.5pH) in equilibrium suspensions (0.01 m KCl) was closely related to the ratio of pyrophosphate-extractable Al to pyrophosphate-extractable organic C. The Podzol Bs sample probably contained a small amount of a surface-reactive Al(OH)₃ phase, which rapidly became depleted by the acid leaching.     

Performance assessment of nanoparticulate lime to accelerate the downward movement of calcium in acid soil

Calcium in conventional lime (CL) moves downward extremely slowly into the soil in the short term. To monitor the effects of using nanoparticulate lime (NL) in low affordable doses and in large doses on accelerating the downward movement of Ca in a simulated plough layer profile (0–25 cm), we ran a column leaching experiment with an acid soil with NL applied into the top 5 cm. The experiment evaluated a reference treatment (0 NL), three low doses of NL (8, 40 and 80 kg ha^?1 = 0.02×, 0.1×, and 0.2× the NL needed to raise soil pH to 6.0 in the top 5 cm: NLR_pH‐6), and two large doses (400 and 800 kg ha^?1 = 1× and 2× NLR_pH‐6). Over the short term (70 days), NL accelerated the downward movement of Ca, likely by mass flow of nanoparticles down soil micro‐ and macropores. Applying NL to the top 5 cm at 40 and 80 kg ha^?1 was effective at increasing the downward movement of Ca and the neutralization of soil acidity (in terms of pH) to 20 cm depth, as well as rectifying Al toxicity (in terms of exchangeable Al) to ≤ the critical limit to 10 cm. NL at 80 kg ha^?1 was most economically justified in terms of rectifying Al toxicity throughout the profile. Therefore, NL may introduce new and alternative application strategy that allowing lower rates of lime to be used and thereby offset economic constraints posed by high application rates.