长期施用氮磷钾肥和石灰对红壤性水稻土酸性特征的影响

利用34年的长期定位施肥试验,研究不施肥(CK)、施氮磷钾肥(NPK)和氮磷钾化肥配施石灰(NPK+Ca O)对红壤性水稻土不同形态酸、土壤盐基离子及水稻植株阳离子吸收量的影响,探讨土壤交换性H+和Al3+占交换性酸的比例、土壤盐基离子、植株带出阳离子数量与土壤酸度的关系。结果表明,长期NPK处理早、晚稻土壤p H较CK处理分别降低0.2和0.3个单位,交换性酸提高2.3倍和4.2倍,水解性酸提高35.4%和40.0%;NPK+Ca O处理早、晚稻土壤p H较NPK处理分别提高0.5和0.7个单位,较CK处理分别提高0.3和0.4个单位,交换性酸、水解性酸均显著低于NPK和CK处理(p0.05)。土壤交换性H+、Al3+含量高低顺序均为NPK+Ca OCKNPK。土壤交换性盐基离子以交换性Ca2+所占比例最大(81.8%~89.3%),NPK+Ca O处理交换性Ca2+较CK和NPK处理分别提高40.1%和62.9%。交换性Ca2+、交换性盐基离子、盐基饱和度与土壤p H正相关,与交换性酸、水解性酸负相关,交换性Mg2+与交换性酸、水解性酸负相关,交换性Na+与水解性酸负相关。植株移出带走的钙、镁、钾、钠离子量及其总量对土壤p H、交换性酸和水解性酸有一定影响,但其相关性均不显著。研究表明长期施用化肥条件下通过配施石灰可有效缓解稻田土壤的酸化,促进酸性稻田土壤的生态修复与改良。     

Differential soil acidification caused by parent materials and land-use changes in the Pearl River Delta region

Soil acidification occurs widely across the world, which has been partly attributed to land-use change. However, measureable effect of land-use change as well as parent materials on soil acidification remains poorly understood. Here, a typical area with intensive land-use change in the Pearl River Delta of China was chosen for this study. Topsoil (0–20 cm) and subsoil (20–40 cm) samples (n = 169) under different land uses (paddy fields, vegetable lands and orchards) and parent materials (granite and alluvial sediment) were collected in 2020. Soil pH, exchangeable base cations, exchangeable acidity and pH buffering capacity were measured to evaluate the status of soil acidification. The change of soil pH over the last 15 years was evaluated via comparing with historical data (n = 329) in 2005. The results showed a higher exchangeable acidity and lower pH buffering capacity and exchangeable base cations of soils derived from granite compared with soils derived from alluvial sediment in 2020. In the last 15 years, significant soil acidification under different parent materials was observed under vegetable lands and orchards but not paddy fields. Faster pH decline was found under land-use change from paddy fields compared with the unchanged vegetable lands or orchards. Furthermore, stronger acidification under the same land-use change was observed for soils derived from granite compared with soils derived from alluvial sediment. These results indicate that land-use change induced soil acidification is dependent on parent materials. This study implies that cropping management such as suitable rotation operation may slow soil acidification, and measures including straw returning may ameliorate acidified soils.     

四环素类抗生素在土壤和堆肥中的吸附和降解

Two agricultural soils were collected from Dahu and Pinchen counties and swine manure compost (SMC) from Ping-tung County in Taiwan, China to investigate the sorption and dissipation of three tetracyclines (TCs), i.e., oxytetracycline (OTC), tetracycline (TC) and chlortetracycline (CTC), in compost, soils and soil/compost mixtures with different organic carbon (OC) contents. There were seven treatments in total. TCs were most strongly adsorbed to SMC in all treatments due to the high OC content. When SMC was present in the soils, the sorption of TCs was significantly enhanced, which might be attributed to the increased OC content and CEC. The adsorption of TCs showed non-linear adsorption isotherms and fitted well to the Freundlich model. After 49 d of incubation at 25 ℃ in soils and soil/compost mixtures in the dark, TCs elapsed in all substrates, with the time required for 50% degradation (DT₅₀) between 20 and 41 d, and the time for 90% degradation (DT₉₀) between 68 and 137 d. Soil amended with compost enhanced the stability of TCs and reduced their mobility. The dissipation of TCs in a soil environment was slow, indicating that these compounds might be persistent in soil.     

电动模拟土壤酸化及其交换性离子组成变化

土壤酸化及其环境效应研究是土壤环境领域的重要内容。自行设计了模拟土壤酸化的电动装置,该装置由直流电源、反应槽、石墨电极组成,并采用四种不同类型土壤,研究了电动模拟土壤酸化后土壤pH、交换性酸和交换性阳离子组成的变化。实验结果显示,经电动处理后土壤pH发生明显变化,土壤pH由阳极到阴极逐渐升高,pH变幅为水稻土燥红土红壤赤红壤,水稻土的pH变化比红壤更为明显;土壤交换性H+和Al~(3+)含量在阳极附近最高,交换性Al~(3+)占交换性酸总量达65%以上;交换性Ca~(2+)、Mg~(2+)、K~+和Na~+表现出离阳极越远,含量越大的规律,其中交换性Ca~(2+)和Mg~(2+)在模拟酸化后含量变化较大,而交换性K~+和Na~+的变化幅度相对较小。结果表明,电动处理可快速获得不同pH梯度的土壤样品,并模拟了土壤酸化过程中的阳离子迁移过程,是模拟土壤酸化及其效应研究的有效方法。     

Effects of fertilization practices on aluminum fractions and species in a wheat soil

Purpose

To better understand the effect of fertilizer practices on soil acidification and soil organic matter (SOM) stocks in a rice-wheat system, a field experiment was conducted to (i) investigate the influence of fertilizer practices on the Al forms in solid phases and the distribution of Al species in water extracts and (ii) explore the relationship between the Al forms, the quantity and composition of SOM, and soil acidity.

Materials and methods

Seven fertilizer treatments including CL (no fertilizer), NK, PK, NPK, N₂PK (PK and 125 % of N), NP₂K (NK and 125 % of P), and organic fertilizer (OF) were applied to induce various changes in pH and SOM composition (i.e., total C and N contents, C/N ratio, and SOM recalcitrant indices) in a rice-wheat system. After 6-year cultivation, different pools of Al forms (i.e., amorphous Al; organically bound Al of varying stability; exchangeable Al; water-soluble inorganic Al³⁺, Al-OH, Al-F, Al-SiO₃, and Al-SO₄; and organic Al monomers) were quantified and related with SOM composition and soil pH during the wheat phase.

Results and discussion

Fertilizer types significantly changed soil pH and SOM composition and which explained 84 % of the variance of Al forms using redundancy analysis. An interaction between soil pH and SOM quality on Al forms also existed but only accounted for a very small (6 %) portion of the variation. Compared to CL and chemical fertilizer, OF practice with relative low SOM stabilization is likely to favor the formation of amorphous Al in order to bind more SOM. The decrease in exchangeable acidity and water-extractable Al via hydroxyl-Al precipitation but not in the form of organo-aluminum complexes evidenced this phenomenon. In contrast, chemical fertilizer input increased exchangeable Al and water extract Al (especially Al³⁺), partly at the expense of organically bound Al. The destabilization of organic-aluminum complexes was a mechanism of pH buffering evidenced by the increased soluble Al-dissolved organic matter (DOM) as soil pH decreases. Further, the magnitude of this trend was much greater for elevated N input compared with P input.

Conclusions

Chemical fertilizer with relative high SOM stabilization favored the formation of exchangeable Al and soluble Al resulting in soil acidification, whereas OF with relative low SOM stabilization tended to transform exchangeable Al and soluble Al to amorphous Al, thereby alleviating soil acidification and enhancing C stocks in a rice-wheat system.

     

Distribution of Aluminum Fractionation in the Acidic Rhizosphere Soils of Masson Pine (Pinus massoniana Lamb)

The modified Tessier’s sequential extraction procedure and rhizobox cultivation were employed to investigate the distribution of aluminum (Al) fractions in the acidic rhizosphere soil of Masson pine (Pinus massoniana lamb) seedlings. The results showed that the Al in soils was fractionated into five operationally defined fractions. Three sets of soil samples used in the rhizoboxes were collected from the three forest sites in the southeast of China: Sichuan, Zhejian, and Jiangsu. At the end of 100-day cultivation, the rhizosphere Al fractions for the original or bulk soils were in the order of residual > iron-manganese (Fe-Mn) oxides > organic > carbonate > exchangeable. However, in rhizosphere soil, the Al fraction follows the order of residual > organic > Fe-Mn oxides > carbonate > exchangeable. On average, the rhizosphere experienced significant increase in organically bound Al and slight decrease in exchangeable Al contents, but had decreases in contents for the other three Al fractions compared to the nonrhizosphere. The correlation analysis indicated that the Al contents accumulated in roots were significantly and positively correlated with exchangeable Al contents in the rhizosphere, and also characterized by the major portion of organically bound Al, which exhibited a bioavailable transformation of Al fractions. Results indicated that decreases in both redox potential and soil pH, as well as increase in dissolved organic carbon (DOC), were observed in the rhizosphere. Exchangeable Al and organic Al fractions were dependent mainly on soil pH (hydrogen ion concentration) and DOC, accordingly. Decreasing rhizosphere pH from 5.93 to 3.42 accelerated the secretion of organic carbon. These data are helpful for understanding the mobility and bioavailability of Al fractions in the acidic rhizosphere soils of Masson pine.     

茶园土壤pH变化对土壤中铝特性的影响

土壤中铝的毒性强弱取决于铝的形态。为了解茶园土壤中铝的特性,以江苏省7个长期定位观测茶园为研究对象,采用化学连续提取法测定不同条件下土样中不同形态的铝含量,研究茶园土壤pH升高或降低过程中铝的形态转化及其影响因素。结果表明,茶园土壤在酸化过程中活性铝溶出明显增强,不同形态的铝含量有明显差异,依次为腐殖酸铝(Alh)铝的水合化物和氢氧化物(Aloh)交换态铝(Alex)有机态铝(Alo)水溶态铝(Alw)无机吸附态铝(Alino);土壤pH、有机质和酸容量是影响铝形态的重要因素;茶园土壤酸化过程中铝的水合化物和氢氧化物、无机吸附态铝以及水溶态铝会转化为交换态铝。土壤pH升高,交换态铝转化成羟基铝;有机结合态铝会影响其他铝形态的转化,腐殖酸铝在土壤pH升高时转化为铝的水合化物和氢氧化物。     

Effect of cultivation time on soil heavy metal accumulation and bioavailability in Phyllostachys praecox stands

Phyllostachys praecox is a bamboo species cultivated for edible shoots under intensive management. However, the potential pollution risk of heavy metals in bamboo soils is not clear under the intensive management for a long term. The objective of this study was to evaluate the effect of cultivation time on soil heavy metal accumulation and bioavailability in bamboo stands subjected to intensive management. Soil samples were collected from a chronosequence of bamboo stands which had been cultivated for 0, 1, 2, 4, 8, and 10 years in Lin''an, Zhejiang Province of China. Eight heavy metals (Cu, Zn, Pb, Ni, Cr, Cd, As, and Hg) present in the soil were selected, and their potential pollution risk was evaluated by chemical speciation analysis. Possible heavy metal sources were explored using multivariate and cluster analysis. Our results showed that Zn, Cu, Hg, and Cd contents in the soil increased with the cultivation time, while Ni, Cr, Pb, and As levels were similar among all stands. Furthermore, the bioavailabilities of all analyzed heavy metals increased with the cultivation time. Multivariate and cluster analysis showed that sources of Ni, Cr, Pb, and As were likely lithogenic in origin, whereas input of Zn, Cu, Hg, and Cd was mainly due to cultivation practices. Current bamboo management strategies raised the potential risks of heavy metal pollution in bamboo shoots in the long term. Soil acidification in P. praecox stands induced by intensive cultivation should be controlled since it stimulated and improved the bioavailability of heavy metals. Appropriate management strategies should thus be adopted to ensure safe and sustainable production of bamboo shoots.     

有机肥替代化学氮肥提升红壤抗酸化能力

【目的】长期过量施用化学氮肥加剧了红壤区农田土壤酸化,严重制约着该区域农业的可持续发展。施用石灰和有机肥是防治红壤酸化的主要措施,我们研究了有机无机肥配合提高红壤抗酸化能力的作用与机理。【方法】本研究基于2009年在湖南祁阳中国农业科学院红壤站开展的有机肥替代化学氮肥长期定位试验,其中4个处理分别为单施化肥(由于酸化严重,于2018年底添加石灰改良)、有机肥替代化肥氮20%、40%和60%,供试有机肥为猪粪。采集2018和2020年的土壤样品,分析各施肥处理红壤pH、交换性酸铝、阳离子交换量、有机质、酸缓冲能力等指标的变化及相互关系。【结果】至2018年,单施化肥处理较试验之初土壤pH降低了0.48个单位,交换性酸、铝分别增加了2.74和1.06 cmol/kg;添加石灰改良后,土壤pH升高了0.58个单位,交换性酸、铝分别降低了2.62和1.45 cmol/kg。有机肥替代化肥氮40%和60%处理均可有效防治红壤酸化,其中以替代60%处理效果最佳;至2020年60%有机替代处理土壤pH较初始值提高了0.78个单位,交换性酸和交换性铝分别降低了1.10和1.25 cmol/kg。有机肥...     

Response of Soil and Plant to Boron-Doped Aluminum Hydroxide

The aims of this work are to test whether boron (B) may alleviate soil acidification and aluminum (Al) phytotoxicity to rape (Brassica napus L.) in acidic soil. The Al hydroxide that reacted with borax was called ad-B-Al hydroxide. Point of zero charge (PZC) of Al hydroxide (pH 4.86) was greater than that of ad-B-Al hydroxide (pH 4.68). Compared with the control, ad-B-Al hydroxide raised the soil pH significantly by 0.10 pH units. Rape was planted in the control soil, the soil treated with Al hydroxide, and the soil treated with ad-B-Al hydroxide. It was found that the B content of the soil and rape seedlings grown on the soil treated with ad-B-Al hydroxide was greater than the others. Biomass production of rape seedlings grown in the soil treated with ad-B-Al hydroxide was significantly increased compared to that in the others. These demonstrated that ad-B-Al hydroxide can be an important source of B for plants and alleviate acidity of acidic soils because it can decrease exchangeable acid and Al toxicity in soil significantly.     

集约经营下南方竹园土壤酸化特征与缓冲容量研究

高强度集约经营下竹园土壤质量退化是制约竹笋持续丰产高效的主要障碍因素。通过研究集约经营雷竹林典型土壤剖面的酸度特征、养分变化以及土壤酸碱缓冲容量,以期探明集约经营下雷竹林衰退的可能因素。结果表明,雷竹种植后,表层土壤呈现明显的酸化现象,表土的最低pHH2O值达到了3.75;表土的有机质和速效磷含量明显提高,表土(0~20 cm)速效磷含量最高可达350 mg kg-1;竹林土壤铝的形态分析表明,有机配合态铝在表土中的含量较高,并随剖面深度的降低而降低;土壤交换态铝含量与pHH2O和pHKCl呈极显著负相关,有机配合态铝含量与有机质和速效磷含量呈极显著正相关;竹园土壤的酸碱缓冲容量在8.58~14.31 mmol kg-1之间,有机质含量是影响竹园土壤缓冲容量的主要因素。     

长期定位施肥对亚热带丘陵地区红壤旱地质量的影响Ⅰ.酸度

研究了中国科学院红壤生态实验站长期定位施肥试验5种不同施肥处理对土壤pH、土壤交换性氢、铝的影响,及其与土壤有机质之间的相关性。结果表明,长期不同施肥处理均提高了土壤pH,降低了土壤交换性氢和交换性铝含量,改良了红壤的酸性。施用有机肥(M)、有机肥+菌剂(BM)、有机肥+菌剂+微量元素(BMT)显著优于施用化肥(F)和化肥+微量元素(TF)的处理。添加微量元素和有效菌剂后土壤交换性氢、铝含量略有提高。土壤有机质与土壤pH呈显著正相关,与土壤交换性氢含量的相关性不显著,而与土壤交换性铝含量呈显著负相关。随着土壤有机质含量的增加,土壤交换性氢占土壤交换性酸度比例越大。长期施用有机肥、提高土壤有机质含量是改良红壤酸度和减轻铝毒较好的农艺措施。     

Increases in pH and soluble salts influence the effect that additions of organic residues have on concentrations of exchangeable and soil solution aluminium

It has been suggested that additions of organic residues to acid soils can ameliorate Al toxicity. For this reason the effects of additions of four organic residues to an acid soil on pH and exchangeable and soil solution Al were investigated. The residues were grass, household compost, filter cake (a waste product from sugar mills) and poultry manure, and they were added at rates equivalent to 10 and 20 t ha^?1. Additions of residues increased soil pH measured in KCl (pH_(KCl)) and decreased exchangeable Al³⁺ in the order poultry manure > filter cake > household compost > grass. The mechanism responsible for the increase in pH differed for the different residues. Poultry manure treatment resulted in lower soil pH measured in water (pH_(water)) and larger concentrations of total (Al_T) and monomeric (Al_mono) Al in soil solution than did filter cake. This was attributed to a soluble salt effect, originating from the large cation content of poultry manure, displacing exchangeable Al³⁺ and H⁺ back into soil solution. The considerably larger concentrations of soluble C in soil solution originating from the poultry manure may also have maintained greater concentrations of Al in soluble complexed form. There was a significant negative correlation (r = ?0.94) between pH_(KCl) and exchangeable Al. Concentrations of Al_T and Al_mono in soil solution were not closely related with pH or exchangeable Al. The results suggest that although additions of organic residues can increase soil pH and decrease Al solubility, increases in soluble salt and soluble C concentrations in soil solution can substantially modify these effects.     

EFFECT OF SOIL pH AND ORGANIC MATTER ON LABILE ALUMINIUM IN SOILS UNDER PERMANENT GRASS

The rates of extraction of Na, K, Mg, Ca, and Al with 1M NH₄ NO₃ from the mineral-and organic-rich layers of some Park Grass (Rothamsted) soils were measured at the pH of the soil. Below pH 3.7 exchangeable Al, derived from the kinetics curve, increases with decreasing soil pH and is less in the organic-rich layer. The sum of the basic exchangeable cations, ∑(Na + K + Mg + Ca), increases with increasing soil pH and is more in the organic-rich layer. The extraction of exchangeable Al obeys first order kinetics, the rate constant being similar for all the soils (mean value 36 ± 7 × 10^?6|s^?1), which implies that exchangeable Al is released from surfaces with similar properties for the adsorption of Al, and that the rate is not affected by soil pH and organic matter. The rate of extraction of non-exchangeable Al is the same in the mineral-and organic-rich layers of each soil, and is maximal at about pH 3.7, decreasing sharply at more and less acid pH values.     

Effects of nitrogen fertilizer on the acidification of two typical acid soils in South China

Purpose

A laboratory incubation under constant temperature and humidity was conducted to estimate the impacts of nitrogen (N) fertilizers on the acidification of two acid soils (Plinthudult and Paleudalfs) in south China.

Materials and methods

The experiment had three treatments, i.e., control (CK), addition of urea (U), and addition of ammonium sulfate (AS). We measured soil pH, nitrate (NO₃ ^?), ammonium (NH₄ ⁺), exchangeable hydrogen ion (H⁺), and aluminum ion (Al³⁺) concentrations at various intervals during the 90 days of incubation. Soil buffering capacity (pHBC) was also measured at the end of the experiment.

Results and discussion

The application of N fertilizers resulted in soil acidification. The U treatment caused greater acidification of the Plinthudult soil than the AS treatment, while there were no differences between U and AS treatments on the acidification of the Paleudalfs. At the end of the trial, the pHBC of Plinthudult in AS treatment was greater than that in CK and U treatments, which may be due to the buffering system of NH₄ ⁺ and NH₄OH. However, the pHBC of Paleudalfs was unchanged between treatments. The dynamics of exchangeable H⁺ and Al³⁺ corresponded to that of soil pH. Correlation analysis showed that both soil exchangeable H⁺ and soil exchangeable Al³⁺ were significantly related to soil pH.

Conclusions

Application of urea and ammonium sulfate caused acidification in both soils and increased soil exchangeable Al³⁺ and H⁺ concentrations in the Paleudalfs. The application of urea increased exchangeable Al³⁺, and ammonium sulfate increased pHBC in the Plinthudult.     

Equilibria of weak acids and organic Al complexes explain activity of H+ and Al3+ in a salt extract of exchangeable cations

Two sequential extractions with unbuffered 0.1 m BaCl₂ were done to study the release of salt-exchangeable H⁺ and Al from mineral horizons of five Podzols and a Cambisol. Released Al was found to have a charge close to 3+ in all horizons and in both extractions. This finding was supported by the near-equality of the titrated exchangeable acidity (EA_T) and the sum of exchangeable acids (EA = H_e + 3Al_e, calculated from the pH and Al concentration of the extract). The ratio between EA of the second and the first extraction was over 0.50 in the Bs2 and C horizons and smaller in the other horizons. H⁺ was assumed to be in equilibrium with weak acid groups, and the modified Henderson–Hasselbach equation, pK_HH = pH ? n log (α/(1 ? α)), was used to explain pH of the extract. The degree of dissociation (α) was calculated as the ratio between effective and potential cation exchange capacity. Value of the empirical constant n was found to be near unity in most horizons. When the monoprotic acid dissociation was assumed in all horizons, pK_HH had the same value in both extractions. For Al³⁺, two equilibrium models were evaluated, describing (i) complexation reactions of Al³⁺ with soil organic matter, and (ii) equilibrium with Al(OH)₃. Apparent equilibrium constants were written as (i) pK_o = xpH ? pAl³⁺, and (ii) log Q_gibbs= log Al³⁺ ? 3log H^+. The two extractions gave an average reaction stoichiometry x close to 2 in all horizons. Results suggest that an equilibrium with organic Al complexes can be used to express dissolved Al³⁺, aluminium being apparently bound to bidentate sites. The value of log Q_gibbs was below the solubility of gibbsite (log K_gibbs = 8.04) in many horizons. In addition, log Q_gibbs of the second extraction was greater than that of the first extraction in all horizons except the C horizon. This indicates that equilibrium with Al(OH)₃ cannot explain dissolved Al³⁺ in the soils. We propose that the models of pK_HH and pK_o can be used to simulate exchangeable H⁺ and Al³⁺ in soil acidification models.     

LONG-TERM CHANGES IN FOREST SOIL ACIDITY IN PENNSYLVANIA,U.S.A.

Forest soil acidification has been reported to cause reduced forest productivity and decline of some tree species. Soil acidification may cause increased bioavailability of Al and Mn, which are potentially phytotoxic. In an attempt to measure whether or not Pennsylvania forest soils have become more acidic, soil samples were collected at 11 undisturbed forested sites in Pennsylvania in 1993. Limited soil chemistry data obtained through 4 previous studies conducted between 1957 and 1979 were available for each site. Soil pH and concentrations of exchangeable Ca and Mg were measured; results were compared to those obtained in earlier studies. Soil exchangeable Al concentrations were determined for 6 sites for which previous data were available. Chemical analysis methods were evaluated to ensure that methods used in 1993 were comparable to those of the original investigators. Mean pH and exchangeable Mg declined most consistently over the study period in the O horizon and the uppermost A horizon. Mean exchangeable AI decreased in the O horizon and increased in the A horizon. Given the high sulfate and nitrate deposition loads in Pennsylvania, it seems likely that the observed changes are at least in part a consequence of acidic deposition.     

南方茶园土壤酸化特征及交换性酸在水稳性团聚体中的分布

通过采集浙江省杭州西湖龙井茶园土壤,研究茶园土壤剖面的酸度特征、养分变化以及交换性酸在水稳性团聚体中的分布特征,以了解南方茶园土壤的酸化过程。结果表明:茶园表层土壤(0-20cm)酸化严重,最低的pHH2O值达到4.0,并且有明显的深层化趋势;表土的有机质和速效磷含量较高,速效磷含量最高可达138.2mg/kg;表土团聚体分级表明茶园土壤有良好的团聚体结构,具有良好的水稳性;除了交换性H+在0.5～0.25mm和0.25～0.106mm水稳性团聚体之间没有明显差别外,交换性酸总量、交换性H+和交换性Al 3+含量均随着水稳性团聚体粒径的减小而降低;水稳性大团聚体中交换性Al 3+相对交换性H+占有明显的优势,而在0.106～0.05mm水稳性微团聚体中交换性H+占有明显的优势。交换性酸总量、交换性H+和交换性铝主要分布于>2mm和2～0.5mm水稳性团聚体中,同时在不同粒级团聚体中的分布随粒径的减小而降低。     

Acidity,nutrient stocks,and organic‐matter content in soils of a temperate deciduous forest with different abundance of European beech (Fagus sylvatica L.)

The production and composition of leaf litter, soil acidity, exchangeable nutrients, and the amount and distribution of soil organic matter were analyzed in a broad‐leaved mixed forest on loess over limestone in Central Germany. The study aimed at determining the current variability of surface‐soil acidification and nutrient status, and at identifying and evaluating the main factors that contributed to the variability of these soil properties along a gradient of decreasing predominance of European beech (Fagus sylvatica L.) and increasing tree‐species diversity. Analyses were carried out in (1) mature monospecific stands with a predominance of beech (DL 1), (2) mature stands dominated by three deciduous‐tree species (DL 2: beech, ash [Fraxinus excelsior L.], lime [Tilia cordata Mill. and/or T. platyphyllos Scop.]), and (3) mature stands dominated by five deciduous‐tree species (DL 3: beech, ash, lime, hornbeam [Carpinus betulus L.], maple [Acer pseudoplatanus L. and/or A. platanoides L.]). The production of leaf litter was similar in all stands (3.2 to 3.9 Mg dry matter ha^–1 y^–1) but the total quantity of Ca and Mg deposited on the soil surface by leaf litter increased with increasing tree‐species diversity and decreasing abundance of beech (47 to 88 kg Ca ha^–1 y^–1; 3.8 to 7.9 kg Mg ha^–1 y^–1). The soil pH_(H2O) and base saturation (BS) measured at three soil depths down to 30 cm (0–10 cm, 10–20 cm, 20–30 cm) were lower in stands dominated by beech (pH = 4.2 to 4.4, BS = 15% to 20%) than in mixed stands (pH = 5.1 to 6.5, BS = 80% to 100%). The quantities of exchangeable Al and Mn increased with decreasing pH and were highest beneath beech. Total stocks of exchangeable Ca (0–30 cm) were 12 to 15 times larger in mixed stands (6660 to 9650 kg ha^–1) than in beech stands (620 kg ha^–1). Similar results were found for stocks of exchangeable Mg that were 4 to 13 times larger in mixed stands (270 to 864 kg ha^–1) than in beech stands (66 kg ha^–1). Subsoil clay content and differences in litter composition were identified as important factors that contributed to the observed variability of soil acidification and stocks of exchangeable Ca and Mg. Organic‐C accumulation in the humus layer was highest in beech stands (0.81 kg m^–2) and lowest in stands with the highest level of tree‐species diversity and the lowest abundance of beech (0.27 kg m^–2). The results suggest that redistribution of nutrients via leaf litter has a high potential to increase BS in these loess‐derived surface soils that are underlain by limestone. Species‐related differences of the intensity of soil–tree cation cycling can thus influence the rate of soil acidification and the stocks and distribution of nutrients.     

Acidification of Solid and Solution Phases at Greater Depths (> 150 cm) at Solling Spruce Site

The acidification of the soil and percolation water at soildepths from 150 to 500 cm was studied at the Solling spruce sitefrom 1991 to 1996. NH₄Cl exchangeable cations of the fineearth and bedrock fractions were obtained from different depthsand the soil solution composition was monitored at 150, 200,300, 400 and 500 cm depths using seven suction lysimeters at each depth.In the seepage water collected from 150 and 200 cm depth, pHvalues decreased in the period 1991 to 1996, but no significantchanges were observed in solutions collected below 200 cm depth.Element budgets of Al and M_b (Na, K, Mg, Ca) cationsindicated that buffering by exchange of Al with M_b cationsoccurred mainly in surface 200 cm soil depth. High variabilities in concentrations of SO₄ (at 150 cm) andM_a (Al, Mn, H, Fe) cations (at 300 and 500 cm) wereobserved. High variabilities in M_a cations could beassigned to one of the lysimeters at each depththat extracted low pH solutions. The amount of exchangeablecations in the fine earth and the bedrock fractions indicatedthat the acidification front (exchangeable M_b cations < 80equivalent percent) had occurred to soil depth of more than 360cm, but the extent of acidification that might have occurred inthe preindustrial period is not known. In both fine earth andbedrock fractions, depthwise changes of exchangeable M_a andM_b cations were quite similar, suggesting that rockfractions have contributed to proton buffering not only bysilicate weathering but also by cation exchange.