Acidity neutralization mechanism in a forested watershed in Central Japan

The contributions of cation exchange and mineral weathering to the neutralization of acidity in the Jingahata watershed in central Japan were estimated through a laboratory weathering experiment and runoff chemistry measurements. The laboratory experiment was conducted in a stirred-flow reactor for a whole soil sample collected from the C horizon in the watershed. The concentration ratios of base cations (Ca²⁺, Mg²⁺, K⁺ and Na⁺) to Si (BC/Si) released during the steady-state stage of the laboratory experiment were in good agreement with the ratios of the net flux of base cations to the flux of Si in the streamwater (BC _{N ET}/Si _L).This result suggests that the acidity in the watershed is neutralized primarily by mineral weathering without causing a net loss of base cations from exchange sites. The alkalinity/acidity balance estimated for the watershed shows that the total weathering rate of base cations is approximately 3.26 keq ha^?1 yr^?1. Weathering of plagioclase (An₄₁) contributes 83% of the total weathering rate. The dominant acidity source is CO₂ released within the soil horizons, accounting for roughly 85% of the total acidity flux (3.20 keq ha^?1 yr^?1). This high internal production of acidity suppresses the relative importance of atmospheric acidity inputs (0.3 keq ha^?1 yr^?1).     

Proton Budget for a Japanese Cedar Forest Ecosystem

The proton budget for a Japanese cedar (Cryptomeria japonica) forest in Gunma Prefecture, Japan, was studied by estimating biogeochemical fluxes. The proton budgets were estimated for three individual compartments of the ecosystem: vegetation canopy, and the upper (O horizon + 0–10 cm) and lower (10–100 cm) soil layers. The dominant proton sources in the compartments were atmospheric deposition (1.2 kmol ha^?1 yr^?1), nitrification (5.1 kmol, ha^?1 yr^?1) and base-cation uptake by vegetation (8.0 kmol, ha^?1 yr^?1) respectively. These proton sources were neutralized almost completely within the individual compartments mainly by base-cation release from the canopy or the soil. The sum of internal proton sources was five times as large as that of external ones. Nitrogen input from the atmosphere was 2.2 kmol ha^?1 yr^?1, whereas its output from the lower soil layer was 3.9 kmol ha^?1 yr^?1, indicating that a net loss of nitrogen occurred in the ecosystem. However, this did not cause the acidification of soil leachates because of a sufficient release rate of base cations from the soil.     

Relative role of soil nutrients vs. carbon availability on soil carbon mineralization in grassland receiving long-term N addition

High nitrogen (N) input often induces soil carbon (C) limitation, eutrophication of macronutrients, deficiency of base cations, and accumulation of toxic micronutrients. These changes are perceived to be critical factors in regulating soil C mineralization. Previous studies primarily focused on the individual effects of C, macronutrients, exchangeable base cations, and micronutrients on soil C mineralization. However, the relative importance of those factors in regulating soil C mineralization, especially in N-enriched ecosystems, remains unclear. To disentangle the relative contributions of aforementioned factors, lime and/or glucose were added to soils that were collected from a field experiment with historical N addition (6 years) at seven rates (0–50 g N m⁻² year⁻¹) in a grassland ecosystem. Lime and glucose were added to improve the soil C and key nutrient conditions. The responses of soil C mineralization rate to changes in soil C and macronutrients (N and P), exchangeable base cations (K⁺, Na⁺ and Mg²⁺), and micronutrients (Fe²⁺, Mn²⁺, Cu²⁺ and Zn²⁺) were examined. We found that lime addition decreased soil micronutrients, while glucose addition improved the soil available P and exchangeable base cations, especially at high historical N addition rates. The soil C mineralization was weakly associated with changes in soil nutrients, including the availability of N, P, exchangeable base cations, and micronutrients, which were conventionally and previously considered as the vital drivers of soil C mineralization. However, soil C mineralization strongly increased with glucose-induced enhancement of C availability and the subsequent enhancement of microbial biomass under increasing N addition rates. Based on the Structural Equation Model, the standardized total effects of C, macronutrients (N and P), base cations and micronutrients on soil C mineralization were 0.86, − 0.29, 0.15 and − 0.08, respectively. Findings from this study demonstrated that the N-induced significant changes in soil nutrients (e.g., eutrophication of N and P, base cations deficiency and accumulation of toxic macronutrients) mediated soil C mineralization, with C availability being the most critical driver for C mineralization in N-enriched soil. This study provides insight into the mechanistic understanding of the relationship between N input and terrestrial C cycling.     

Deposition and Leaching of Sulphate and Base Cations in a Mixed Boreal Forest in Eastern Finland

Monthly fluxes of sulphate (SO₄ ^2-) and base cations(Ca²⁺, Mg²⁺, K⁺) were studied from 1993 to 1996 as precipitation passed through forest vegetation and surfacesoil layers in an area receiving low and declining levels of atmospheric sulphate pollution. The canopy was dominated by mature Norway spruce (Picea abies Karsten) and the soilwas a podzol developed on glacial till material. The mean annual bulk deposition of SO₄ ^2- collected in the open was 136 mol_c ha^-1 and that of Ca²⁺, Mg²⁺ and K⁺ was 44, 11 and 25 mol_c ha^-1, respectively. The annual total throughfall deposition of SO₄ ^2- was 318 mol_c ha^-1 and that of Ca²⁺, Mg²⁺ and K⁺ was 151, 64 and 181 mol_cha^-1, respectively. Sulphate was the dominant anion accompanying the base cations leached from the canopy. More than half (58%) of the annual total throughfall deposition ofSO₄ ^2- was retained by the O-horizon and only 15% leached from below the B-horizon. The annual leaching of Ca²⁺, Mg²⁺ and K⁺ from below the B-horizon was14, 25 and 9% of the annual total throughfall deposition, respectively. The transport of base cations through the soil was predominantely countered by SO₄ ^2- anions.     

Soil disturbance and elemental dynamics in a Northern Hardwood forest soil,USA

Loss of soil nutrients due to disturbance may serve as an index of the homeostasis of biogeochemical cycling and ecosystem stability. Soil and the surrounding root system were disturbed during the installation of Soil Containment Systems (SCSs) in the hill slope at the Bear Brook Watershed in Maine (BBWM). The SCSs were constructed from high density PVC pipe (24 cm i.d. and 30 cm height) implanted at field. Leachate cations and anions, soil organic matter and exchangeable cations were analyzed. Leachate NO₃ ^? was higher by an order of magnitude compared to undisturbed soils from the same research site and other hardwood forest soils in the northeast U.S. The concentrations of cations in the leachate from SCSs were also higher and loss of NO₃ ^? was positively correlated with the loss of most cations. Calcium was the dominant cation representing 55% of the base cation composition of soil leachate. Monthly losses of Ca²⁺, Mg²⁺ and K⁺ were 1.8, 1.6 and 1.2% of total exchangeable pools, respectively. Disturbance of the BBWM soil ecosystem caused high rates of NO₃ ^? leaching which markedly changed the soil biogeochemistry. These results and other supporting data from watershed mass balances and experimental chemical additions suggest that BBWM may be N saturated.     

Measurement of ammonia exchange over grassland in the Hungarian Great Plain

The net dry flux of ammonia gas was measured between the atmosphere and a semi-natural grassland with low nitrogen input in Hungary, during the years of 2000 and 2001. A continuous flow denuder system was used to detect the ammonia concentrations at three levels (0.5, 1.0 and 2.0 m above the vegetation). Fluxes were calculated by the aerodynamic gradient method. According to the measurements, the net dry ammonia flux in the vegetation period is 0.37 kg N ha⁻¹ (emission) and −5.0 kg N ha⁻¹ (deposition) in the dormant season. For comparison the total atmospheric (dry + wet) input is −9.2 kg N ha⁻¹ year⁻¹ including all nitrogen forms and excluding ammonia. Net emission was observed only at daytime during the vegetation period when the canopy concentration exceeded the atmospheric ammonia concentration, due to an elevated stomatal compensation point. In all other times (night-time, outside the vegetation period) net deposition flux was observed. A sudden increase of N-input (application of 100 kg N ha⁻¹ fertiliser) resulted in a large enhancement in emission during daytime, which lasted for 2-week period after the application of fertiliser, when the accumulated N-loss (emission factor) of fertiliser was amounted to approximately 1.3%. During night-time week deposition was detected from the fertilised sector suggesting that ammonia is emitted mainly by the plant through stomata in daytime, rather than from the soil. Measured fluxes have been compared to the prediction of a single layer compensation point model. The agreement is good, but some challenges remain for the selection of the parameterisation for individual model parameters.     

Soil characteristics in teak plantations and natural forests in Ashanti Region,Ghana

Abstract

The goal of this study to was compare soils of natural forests converted to teak (Tectona grandis Linn. F) plantations (21.3±5.1 years) in the Offinso and Juaso Forest Districts in the Ashanti region, Ghana. Sites selected for this study were in the moist semi‐deciduous forest zone and had nearly identical physiographic characteristics. In each of three natural forest stands and three teak plantations, 16 soil pits were examined and soil samples from the 0–20 (major rooting zone) and 20–40 cm depths were analyzed for selected chemical and physical properties. In the 0–20 cm depths bulk density significantly increased (1.17 to 1.30 g cm^‐3), but soil organic matter (OM) content (13 to 11%), total nitrogen (0.3 to 0.2 %), available phosphorus (4.2 to 1.2 mg kg^‐1), and exchangeable potassium (0.4 to 0.3 cmol(+)kg^‐1), calcium (17.0 to 12.4 cmol(+)kg^‐1), and magnesium (3.8 to 3.2 cmol(+)kg^‐1) significantly decreased in soils where natural forests were replaced with teak plantations. Similar results also were found for the 20–40 cm soil depths. The higher nutrient contents in soils under the natural forest may have been due to more litter contributions from understorey vegetation observed there. In the teak plantations nutrient leaching losses may have accelerated due to increased mineralization and the inability of teak to use the increase in available nutrient.     

recent lake acidification and recovery trends in southern quebec,canada

A total of 51 lakes in southern Quebec, Canada, were sampled between 1985 and 1993 to study changes in water chemistry following reductions in SO₂ emissions (main precursor of acid precipitation). Time series analysis of precipitation chemistry revealed significant reductions in concentrations and deposition of SO₄ ^2- from 1981 to 1992 in southern Quebec as well as reductions in concentrations and deposition of base cations (Ca²⁺, Mg²⁺), NO₃ ^- and H⁺ in the western section of the study area. Reductions in atmospheric inputs of SO₄ ^2- have resulted in decreased lakewater SO₄ ^2- concentrations in the majority of the lakes in our study, although only a small fraction (9 of 37 lakes used in the temporal analysis) have improved significantly in terms of acidity status (pH, acid neutralizing capacity – ANC). The main response of the lakes to decreased SO₄ ^2- is a decrease in base cations (Ca²⁺+Mg²⁺), which was observed in 17 of 37 lakes. Seventeen lakes also showed significant increases in dissolved organic carbon (DOC) over the period of study. The resulting increases in organic acidity as well as the decrease in base cations could both play a role in delaying the recovery of our lakes.     

Effects of Weak Acids on Canopy Leaching and Uptake Processes in a Coniferous-Deciduous Mixed Evergreen Forest in Central-South China

The effects of Weak acids (WA) on the canopy leaching and uptake processes are evaluated by comparing the leached base cations or the absorbed protons while including and excluding WA, e.g. the WA-included method and the WA-excluded method. The seasonal WA throughfall flux is even larger than twice the bulk precipitation flux except summer, which not only partly agrees with the conclusion that the total deposition of WA equals twice the bulk or dry deposition flux in European Intensive Monitoring plots (level II), but also indicates the significant canopy leaching of WA in Shaoshan forest. The seasonal canopy leaching of base cations in association with WA accounts for 6–30% of the total base cations in throughfall, with an annual mean of 23%, which is slightly higher than the 15% at the Speulder forest in The Netherlands. The canopy exchange capacity of H⁺ to NH₄ ⁺ is closed to 6.0 while neglecting the WA exchange, which probably supports the assumption that the exchange capacity of H⁺ is six times that of NH₄ ⁺. Simultaneously, we suggest that the WA is competitive to a certain extent with protons to leach base cations of plant tissues during the canopy exchange processes.     

Analysis of Proton Generation and Consumption of Forest Surface Soils in Hokkaido, Northern Japan

We determined proton budgets of surface soils in a deciduous forest (Df) and a coniferous forest (Cf) of Volcanogenous Regosols in Tomakomai, Hokkaido of northern Japan. The total H⁺ source was 12.9 and 11.6 kmol_c ha^?1 y^?1 at Df and Cf respectively, and the external H⁺ was 1% at Df and 2% at Cf. The primary H⁺ sources were vegetation uptake of base cations and nitrification, while the major H⁺ sinks were release of base cations and NO₃ ⁺ uptake by vegetation. Leaching incubation experiments using A horizon soils including Df and Cf with NH₄ ⁺ solutions (5.3, 15.9 mg N L^?1) showed that H⁺ from nitrification was generally higher in the Df soil than Cf soil, and nitrification of Tomakomai Df soil was the highest in both treatments. Results of multiple regression analyses suggested that pH_kCl and exchangeable Ca²⁺ contributed to the H⁺ generation via nitrification. Leaching experiments with dilute HCl (pH 3.3) revealed that cation release (mainly Ca²⁺) occurred, and the proportion of release by decrease of exchangeable cations was higher than that by mineral weathering. Mineral weathering in the Tomakomai soil was higher than the other soils.     

Forest canopy transformation of atmospheric deposition

Solute fluxes to the ground in open plots and under the forest canopy of different species were investigated in a number of long-term ecosystem studies in West Germany. From the canopy flux balance, rates of interception deposition and canopy/deposition interactions were assessed. Chemically, both open precipitation and throughfall are dilute solutions of H₂SO₄ and HNO₃ and their salts. For the sites investigated, mean pH in bulk precipitation ranged from 4.1 to 4.6, and in throughfall from 3.4 to 4.7. The increase in acidity after canopy passage at most sites indicates considerable interception deposition of strong acids to the forest stands, exceeding the rate of H+ buffering in the canopy. Evidence for buffering processes can be directly deduced from the fact that on sites with high soil alkalinity and high foliage base status, throughfall pH is usually higher than precipitation pH. Furthermore, the same idea can be concluded from changes in solution composition after canopy passage: the H⁺/SO _inf4 ^sup2? ratio is decreasing at most sites, while alkali earth cations from exchange processes occur in throughfall (Ca²⁺/SO _inf4 ^sup2? ratio increases). Solution composition and element flux data are presented for each of the sites, and the regional, orographical and site specific (species composition, ecosystem state) differentiations are discussed. A method for the assessment of total deposition and of canopy interactions such as H⁺-buffering and cation leaching is described, and results of calculations are shown. From these calculations it is concluded that forest ecosystems in Germany receive mean H⁺ loads of ca. 1 to 4 keq H⁺ · ha^?1 · a^?1 from atmospheric deposition. Acidity deposition rates seem to be related to a few key factors such as regional characteristics and ecosystem characteristics.     

Atmospheric deposition to grassland canopies: Lysimeter budgets discriminating between interception deposition,mineral weathering and mineralization

Lysimeter experiments were used to determine atmospheric input to grassland canopies. The combined effect of interception deposition + mineral weathering + mineralization was calculated from input/output budgets. Four types of lysimeters were used, either filled with very pure quartz sand or chalk grassland soil, and either without vegetation or planted with Brachypodium pinnatum (L.) Beauv., Combination of budgets for these four types of lysimeters yielded separate estimates of interception deposition and mineral weathering + mineralization. Ratios between total deposition and bulk deposition were 1.74 and 1.93 for N and S, respectively. Sources and sinks of H⁺ for lysimeters with chalk grassland soil and planted with Brachypodium (abbrev. CP-lysimeters) were about 10 times larger than for lysimeters without plants and filled with quartz sand. The contribution of atmospheric input to total H⁺-sources was 80% for bare lysimeters filled with quartz sand, and only 12% for CP-lysimeters. Bulk deposition and total atmospheric deposition of N was 1.25 and 2.18 kmol ha^?1 yr^?1, respectively, whereas N mineralization of chalk grassland soil yielded 1.62 kmol ha^?1 yr^?1, ‘Acid rain’ has only a minor influence on H⁺-transformations within a chalk grassland ecosystem, but N cycling is seriously affected by atmospheric input.     

Annual Element Budget of Soil in Snow-Dominated Forested Ecosystem

Seasonal fluctuation of concentration and flux of major inorganic ions in throughfall, stem flow, snowpack and soil solution was investigated at a natural cool temperature mixed forest in Hokkaido, northern Japan, in order to clarify the effect of snowmelt on the solute dynamics in the forest soil in snow-dominated region. Na⁺, Ca²⁺, Mg²⁺, Cl^? and SO₄ ^2? concentrations in soil solution showed a large fluctuation in the snowmelt period. The percentage of output of these elements from soil during the snowmelt period in the annual output was as follows. Mg²⁺: 51%, Na⁺ and Cl^?: 59 and 60%, SO₄ ^2?: 65%, Ca²⁺: 77%. Our results indicated that the snowmelt event was very important to quantify the annual elemental budgets in this region. Although the leaching of base cation from the soil was larger than that of inputs and accumulation into the vegetation, annual decreasing rate of acid neutralization capacity (ANC_(s)) from the soil was mostly affected by the base cation accumulation into the vegetation, related that the base cations weathering accompanied with bicarbonate was slow due to the acidic and weathered soil in the studied site. It is suggested that the weakly acidic soil which has low ANC_(s) in snow-dominated region will be relatively sensitive to the future increase of acidic deposition.     

Chemical Composition of Precipitation, Throughfall and Soil Solutions at Two Forested Sites in Guangzhou, South China

Rain water at two forested sites in Guangzhou (south China) show high concentrations of SO₄ ^2?, NO₃ ^? and Ca²⁺ and display a remarkable seasonal variation, with acid rain being more important during the spring and summer than during the autumn and winter. The amount of acid rain represents about 95% of total precipitation. The sources of pollutants from which acid rain developed includes both locally derived and long-middle distance transferred atmosphere pollutants. The seasonal variation in precipitation chemistry was largely related to the increasing neutralizing capacity of base cations in rainwater in winter. Soil acidification is highlighted by high H⁺ and Al³⁺ concentrations in soil solutions. The variation in elemental concentration in soil solution was related to nitrification (H⁺, NH₄ ⁺ and NO₃ ^?) and cation exchange reaction (H⁺, Al³⁺) in soil. The negative effect of soil acidification is partly dampened by substantial deposition of base cations (Ca²⁺, Mg²⁺ and K⁺) in this area.     

Mapping of Base Cation Deposition in South Korea

Deposition of non-seasalt base cations (Ca²⁺ + Mg²⁺+ K⁺) in South Korea was mapped for 1994 to 1997 on a 11 × 14 km grid using the so-called inferential modeling technique. It is found that the annual mean wet deposition of non-seasalt base cations is about 290 eq ha^-1 yr^-1 with a maximum of 470 eq ha^-1 yr^-1 and a minimum of 120 eq ha^-1 yr^-1 while the annual mean dry deposition is about 130 eq ha^-1 yr^-1 with a maximum of 240 eq ha^-1 yr^-1 and a minimum 70 eq ha^-1 yr^-1. Theannual mean total deposition of non-seasalt Ca²⁺ + Mg²⁺ + K⁺ is found to be about 420 eq ha^-1 yr^-1 with the predominant range of 400 eq ha^-1 yr^-1 to 550 eq ha^-1 yr^-1 thatoccupies more than 45% of total deposition of non-seasalt base cations and dry deposition constitutes on average30% of the total base cation deposition. About 30% of the annualtotal deposition of sulfur is found counteracted by depositionof non-seasalt base cations over South Korea.     

Seasonal Dynamics of Biogeochemical Proton and Base Cation Fluxes in a White Birch Forest in Hokkaido, Japan

Biogeochemical proton and base cation fluxes in a 30-year old white birch forest composed of Dystric Cambisols in northern Hokkaido, Japan were estimated using data on atmospheric deposition (AD), throughfall (TF), stemflow (SF), and discharge from soils (DS) and plant uptake (UP) from early June to November 1999. In the monitoring period, proton flux was 0.20kmol_cha^?1 for AD, 0.07 for TF+SF, and 0.03 for DS, indicating that atmospheric acid input was neutralized through plant and soil. Base cation flux was 1.29 for AD, 1.23 for TF+SF, and 0.99 for DS and plant base cation uptake was 2.14, indicating that the soil was the major source of base cation for plant. However, these seasonal fluxes showed various trends. Cumulative base cation flux in TF+SF showed constant increase trend during the whole period, which was similar to AD. Proton flux in AD jumped once just after a heavy rain of 255mm for 8 days at the end of July. Trends for the proton and base cation fluxes in TF plus SF were similar to that of AD. Although proton and base cation fluxes of DS were not found until middle July because of vegetation uptake and no flow, both fluxes increased suddenly after the heavy rain in July. After August, the base cation and proton fluxes in the DS increased continuously, due to the lack of plant uptake and intermittent rainfall. In this study, it is clear that plant activity and water flow are very important driving force for seasonal dynamics of biogeochemical cycling.     

Nutrient Element Contents and Cation Exchange Capacity in Fine Fractions of Southeastern Nigerian Soils in Relation to Their Stability

Abstract

Soils collected from 15 locations from SE Nigeria at the 0‐ to 20‐cm depth were studied for the nutrient elements of fine fractions and their role in the stability of the soils. The objective was to understand the role of these elements in the stability of the aggregates. The fine fractions were clay and silt, and elements measured in the fine fractions were exchangeable sodium (Na⁺), potassium (K⁺), calcium (Ca²⁺), magnesium (Mg²⁺), exchangeable acidity (EA), cation exchange capacity (CEC), and available phosphorus (P). The aggregate stability was measured at the microlevel with clay dispersible indices and water‐stable aggregate (WSA) <0.25 mm, and at macrolevel with other WSA indices and mean‐weight diameter (MWD). Soils varied from loamy sand to sandy clay. There were more exchangeable cations, CEC, EA, and available P in clay than in the silt fraction. Whereas EA values ranged from 2.8 to 10.4 cmol kg^?1, they were between 1.6 and 9.2 cmol kg^?1 in silt. The CEC in the clay fraction was from 7.4 to 70 cmol kg^?1 and between 4.0 and 32.8 cmol kg^?1 in the silt fraction. The WDC were from 50 to 310 g kg^?1 while the average dispersion ratio (DR) was generally higher than the corresponding clay‐dispersion ratio (CDR), and the MWD ranged from 0.45 to 2.68 mm. Soils with WSA skewed mostly to higher WSA (>2–1.00 mm) had a higher MWD. Exchangeable Ca²⁺ in clay correlated significantly with CDR and WSA sizes 1.0–0.5 mm and 0.5–0.25 mm (r=0.45,* 0.51,* and 0.60*), respectively, but negatively correlated with clay flocculation index (CFI) (r=?0.45*). Also, available P in clay correlated respectively with CDR and CFI (r=0.45*, ?0.45*), whereas K⁺ in silt correlated significantly with WDSi (r=0.64*), CFI (r=0.62*), and CDR (r=?0.65*). Principal component analysis revealed that elemental contents in the silt fraction can play very significant roles in the microaggregate stability.     

Measurements of atmospheric deposition and internal circulation of base cations to a forested catchment area

The dry deposition of base cations to a Norway spruce stand was estimated by multiplying the ratio of the ion deposition to the sodium deposition on a surrogate surface with the dry deposition of sodium on the forest stand. The method can in principle only be applied to species that are present only in particles, but the method gives reasonable results when tested on ions that are also dry deposited in other forms (SO ₄ ^2– . NO ₃ ^– and NH ₄ ⁺ ). The atmospheric input and especially the dry deposition of base cations is an important replacement for the loss of base cations from the soil by run-off. The calculated internal circulation of K⁺ and Ca²⁺ showed maxima synchronously with rainfall maxima and constitute 71% and 53%, respectively, of the net throughfall deposition. The internal circulation of Ca²⁺ was almost equal to the SO₂ uptake.     

Proton Budgets of Forest Ecosystems on Volcanogenous Regosols in Hokkaido,Northern Japan

The proton budgets of deciduous and coniferous forest ecosystems on volcanogenous regosols in Hokkaido, northern Japan, were studied by measuring the biogeochemical fluxes (atmospheric deposition, canopy leaching, vegetation uptake and leaching from soil) at each site during a three year period. The proton budgets were developed for individual compartments of the ecosystem: vegetation canopy, organic and mineral soil layers. At both sites, atmospheric S deposition was the dominant proton source in the vegetation canopy. In organic horizons, dissociation of weak acids (bicarbonate and/or organic acids) and vegetation uptake of base cations were the dominant proton sources, and the net mineralization of base cations was the dominant proton sink. Atmospheric acid deposition was almost neutralized in the forest canopy and organic horizon. At both sites, weathering and/or ion exchange of base cations and protonation of weak acids (mainly bicarbonate) were the dominant proton sinks in the mineral soil. In both organic and mineral soil, internal proton sources (mainly vegetation uptake of base cations and dissociation of weak acids) exceeded external proton sources, indicating that acid deposition was not the main driving force of soil acidification in the studied forest ecosystems.     

Soil sulphur speciation in two glacier forefield soil chronosequences assessed by S K‐edge XANES spectroscopy

In regions with little atmospheric input of sulphur (S) and S‐poor parent material, the bio‐availability of S, which is dependent on its speciation, may limit ecosystem production and succession. In our study, soil S speciation in two glacier forefield soil chronosequences (Hailuogou Glacier, Gongga Shan, China; Damma Glacier, Swiss Alps) was investigated for the first time. Different S species were quantified by synchrotron‐based X‐ray absorption near‐edge structure (XANES) spectroscopy at the S K‐edge. Both chronosequences show similar patterns and pedogenetic trends of their topsoil S status. Topsoil concentrations of total S were correlated with the concentrations of organic carbon and pedogenic Fe/Al oxyhydroxides. Both moraine materials contained inorganic sulphides, which in the topsoil were oxidized within 30 (Hailuogou) or 75 years (Damma) of soil development after deglaciation. About 50% of total S in the fresh moraine material at Hailuogou and 75% of that in the 15 year‐old soil at Damma was organically‐bound. During initial soil development, the contribution of organic S to total S increased at the expense of inorganic sulphide and sulphate, resulting in organic S percentages > 90% of total topsoil S after 30 (Hailuogou) and 75 (Damma) years of pedogenesis. Organic S compounds with electronic oxidation states of the S atom > + 1.5 (sulphoxides, sulphones, sulphonates and ester sulphates) dominated the organic S pool in all soils. Hence, microbial degradation of non‐sulphide organic S (sulphonates and ester sulphates) is probably important to mitigate S scarcity caused by limited availability of SO₄^2?‐S in these soils. Changes in topsoil S speciation during initial stages of pedogenesis and ecosystem succession in glacier forefields under a cool, humid climate appear to be governed by combined effects of mineral weathering (oxidation of inorganic sulphides and formation of S‐adsorbing sesquioxides), accumulation and microbial turnover of soil organic matter and the type of vegetation succession.