Base Cation Supply in Spruce and Beech Ecosystems of the Strengbach Catchment (Vosges Mountains, N-E France)

In spruce and beech stands, mineral budgets for a rotation period were calculated from measured element fluxes. The release of base cations by mineral weathering was calculated with the steady state soil chemistry model PROFILE. The calcium release rate by weathering of the mineral fine earth was extremely low. For the period of one rotation, mineral weathering cannot provide enough Ca to compensate timber harvesting and leaching. Forest sustainability depends strongly on the amounts of Ca gained from deposition and lost by biomass removal. Magnesium was supplied by atmospheric deposition and mineral weathering. Calculated weathering rates were close to present soil losses. However, as the model assumes that all dissolution reactions are congruent, the computed release rate of Mg from illite might be too high. Main inputs of K to the soil solutions were primarily attributed to canopy leaching and litterfall in upper horizons and to mineral weathering in deeper horizons. The cation budget of the beech stand was much more equilibrated than that of the spruce stand. Given possible changes in silviculture and deposition chemistry, the sustainability of the present stands is rather improbable with respect to their mineral supply.     

A preliminary review of weathering rates in relation to their method of calculation for acid sensitive soil parent materials

The release of base cations from chemical weathering is the fundamental process by which base cations lost through leaching or biological uptake are replenished. Soils with a high content of easily weatherable minerals will, in general, be readily able to neutralise incoming acidity and satisfy biological requirements through this supply of base cations from weathering. Conversely those soils with a low content of such minerals will be unable to buffer acid inputs or meet biological demands and will be vulnerable to acidification. It is evident therefore that an accurate estimate of the rate of chemical weathering is a prerequisite for any assessment of ecosystem sensitivity to acidification. The principal methods by which these calculations are made can be grouped into those based on element depletion in soil horizons calculated against a conservative element reference, catchment fluxes, laboratory studies and the use of mathematical models which utilise data from each of these sources. A review of the published data has been undertaken to determine if a systematic variation in weathering rates can be observed for a range of parent materials and/or methods used. Variations of 0.03–0.8 keq ha^?1yr^?1 for K⁺, 0.0–1.0 keq ha^?1yr^?1 for Na⁺, 0.01–1.39 keq ha^?1yr^?1 for Mg²⁺ and 0.0–5.8 keq ha^?1yr^?1 for Ca²⁺ were found. In general individual cation weathering rates determined from catchment fluxes, and also the model MAGIC, are dominated by Ca²⁺, with Mg²⁺ being the next most significant release rate. However it has not been possible to determine any other systematic variations due to the limited number of sites where weathering rate has been determined by more than one method.     

Weathering rates in catchments calculated by different methods and their relationship to acidic inputs

The sensitivity of catchments to acidification is often assessed by calculation of weathering rates for comparison of the rates of release of base cations with the measured acidic inputs. Methods of calculation of weathering rates include (1) long-term rates from elemental depletion in soil profiles; (2) current rates from input-output budgets; (3) strontium isotope ratios to modify current rates for calcium; (4) modelling using PROFILE or MAGIC; (5) laboratory experimental methods. Not all these methods can be applied in any one situation and when more than one method can be used, there are often discrepancies in the resulting figures. Comparison of long-term and current rates with acidic inputs are often consistent with the known acidification status of some Scottish catchments, but in others it is often difficult to establish a relationship. In some catchments where acidification only occurs under high-flow conditions, for example, long-term rates (12–24 meq m^?2a^?1) are an order of magnitude lower than current rates (185–340 meq m^?2a^?1). In seven Scottish catchments on four rock types, weathering rates calculated by PROFILE are of the same order of magnitude as long-term rates calculated for the same soil profiles. Current rates, on the other hand, are always higher than the long-term rates, sometimes by a factor as high as 22, and although this could indicate that release of base cations from these soils has increased in recent times, possibly due to anthropogenic inputs, the comparisons may not be valid.     

Estimation of Mineral Weathering Rates under Field Conditions Based on Base Cation Budget and Strontium Isotope Ratios

Base cation (BC) concentrations of rain, throughfall, percolation from leaf litter, and soil solution were periodically measured in two forests: Kannondai (red pine stand on volcanic soil) and Yasato (deciduous stands on granitic soil). Calculation of a BC budget gave the rate of BC release from soils; the BCs originated from mineral weathering and cation exchange. Weathering rates under field conditions were estimated from the Sr isotope ratios (⁸⁷Sr/⁸⁶Sr) of water and soil samples. Isotope ratios decreased in the order rain > throughfall > percolation > soil solution. Clay and silt had extremely high isotope ratios; this suggests that the sandy fraction, whose isotope ratio was smaller than that of the soil solution, was the main contributor to mineral weathering. Estimated BC weathering rates (kmol_c·ha^?1y^?1) were 1.16 for Ca and 0.57 for Mg at Kannondai, and 0.82 for Ca and 0.51 for Mg at Yasato. The unexpected high weathering rate of granitic soil in Yasao was due to the wide coverage of the original parent material by volcanic ash. The contribution of cation exchange derived by subtraction was a little smaller than the weathering rates and was similar to the values estimated from a dynamic model that we developed.     

Chemical and mineralogical weathering rates and processes in an upland granitic till catchment in Scotland

Weathering in an upland granitic till catchment receiving an intermediate level of acidic deposition has been studied by chemical and mineralogical analyses of soil profiles and chemical analysis of precipitation and streamwater. Long-term weathering rates for base cations calculated from analyses of soil profile horizons using Zr as an internal, immobile, index element are similar for alpine podzols and peaty podzols and are 2–3 meq.m^–2.a^–1 for Ca and Mg, and 10–11 meq.m^–2.a^–1 for K and Na. The high loss of Na is associated with the weathering of oligoclase, particularly in the coarse sand fraction. Loss of K is related to weathering of K-feldspar and micas. Current weathering rates for base cations calculated from input-output budgets are higher than long-term rates by factors of 12, 8 and 3 for Ca, Mg and Na, but lower by a factor of 7 for K probably due to biomass uptake. The higher current overall loss of base cations may be due to increased rates of weathering in recent times but this is not conclusive as there are large uncertainties inherent in both methods of estimation.     

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.     

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.     

Significance of DOM in the translocation of cations and acidity in acid forest soils

We estimated the contribution of dissolved organic matter (DOM) to cation leaching and the translocation of acidity in three acid forest soils. The analysis was based on monitored (2 years) concentrations of dissolved organic carbon (DOC) in the field, measured total acidities of DOM, and measured as well as predicted weighted mean dissociation constants of the organic acids. Although the forest floor solutions were strongly acidic (pH 3.47–4.10), a considerable proportion of the organic acids was dissociated and organic anions represented 22–40% of the total anions in the mineral soil input. The flux of DOM-associated exchangeable protons from the forest floor to the mineral soil ranged from 0.35 (Wülfersreuth) to 3.72 (Hohe Matzen) kmol ha^?1 yr^?1. In the subsoil, this organic acidity may be neutralized by microbial decomposition of the organic acids, but a part of the hydrogen ions may dissociate and contribute to acidification of the soil solution and to weathering processes. Due to the pronounced retention of DOM in the mineral subsoil horizons, the contribution of DOM to the output of cations and acidity from the soil is much lower than in the surface horizons but still significant.?     

Evaluation of elemental depletion weathering rate estimation methods on acid-sensitive soils of north-eastern Alberta, Canada

Immobile element-based weathering estimation methods assume that Zr (or Ti) is an immobile element, and that weathering rates of other elements can be estimated according to the enrichment of Zr in weathered horizons relative to an unweathered parent material. This approach was used to estimate base cation weathering rates for 33 soil profiles on acid-sensitive terrain in north-eastern Alberta. Zirconium generally showed enrichment within the rooting zone, but the deepest (subsoil) samples were not always associated with the lowest Zr concentrations. Weathering rates estimated with the Zr depletion and Pedological Mass Balance (PMB) methods were generally low (ranges: 0-51 and 0-58 mmol_c m^− 2 yr^− 1, respectively); however, low base cation oxide concentrations and heterogeneity within soil profiles complicated weathering rate calculations and net base cation gains were calculated for several (six) sites. Evaluation of the Zr depletion and PMB weathering estimates against those calculated with the process-oriented PROFILE model at a subset (n = 9) of the sites indicated the estimates were poorly related, with PROFILE rates typically being higher. The effects-based emissions management strategy for acid precursors in this region requires spatial coverage of soil properties (including weathering rates) across a large area, but the apparent limitations associated with the immobile element based methods in this region: identifying representative parent soils and deriving weathering rate estimates comparable to more robust methods are arguments against their candidacy for future use.     

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).     

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.     

Stoichiometry of base cations and silicon during weathering of a deep soil profile derived from granite

Evaluation of the stoichiometry of base cations (BCs, including K⁺, Na⁺, Ca²⁺, and Mg²⁺) and silicon (Si) (BCs:Si) during soil mineral weathering is essential to accurately quantify soil acidification rates. The aim of this study was to explore the differences and influencing factors of BCs:Si values of different soil genetic horizons in a deep soil profile derived from granite with different extents of mineral weathering. Soil type was typic acidi-udic Argosol. Soil samples were collected from Guangzhou, China, which is located in a subtropical region. To ensure that the BCs and Si originated from the mineral weathering process, soil exchangeable BCs were washed with an elution treatment. The BCs:Si values during weathering were obtained through a simulated acid rain leaching experiment using the batch method. Results showed that soil physical, chemical, and mineralogical properties varied from the surface horizon to saprolite in the soil profile. The BCs:Si values of soil genetic horizons during weathering were 0.3-3.7. The BCs:Si value was 1.7 in the surface horizon (A), 1.1-3.7 in the argillic horizon (Bt), and 0.3-0.4 in the cambic (Bw) and transition (BC) horizons, as well as in horizon C (saprolite). The general pattern of BCs:Si values in the different horizons was as follows: Bt > A > Bw, BC, and C. Although BCs:Si values were influenced by weathering intensity, they did not correlate with the chemical index of alteration (CIA). The release amounts of Si and BCs are the joined impact of soil mineral composition and physical and chemical properties. A comprehensive analysis showed that the BCs:Si values of the soil derived from granite in this study were a combined result of the following factors: soil clay, feldspar, kaolinite, organic matter, pH, and CIA. The main controlling factors of BCs:Si in soils of different parent material types require extensive research. The wide variance of BCs:Si values in the deep soil profile indicated that H⁺ consumed by soil mineral weathering was very dissimilar in the soils with different weathering intensities derived from the same parent material. Therefore, the estimation of the soil acidification rate based on H⁺ biogeochemistry should consider the specific BCs:Si value.     

Effects of Acid Deposition on Forest Soils in Northernmost Russia: Modelled and Field Data

In addition to strong natural stresses forest ecosystems in the Kola Subarctic, Russia, receive high loads of sulphur and heavy metals from the nickel smelter. To estimate soil response to acid deposition we compared the soil field data along a pollution gradient and simulated time effects. Multivariate technique was applied to investigate spatial distribution of soil field data. Time response of soils to acid deposition was evaluated with the SMART model. According to field observations there is no evidence for strong soil acidification effects close to the smelter. Concentrations of exchangeable Ca and base saturation increase, while acidity decrease in lower soil mineral horizons towards the pollution source. However, some features seem to reflect the early stages of the started acidification. Most soil profiles have low pH values. Despite increasing of exchangeable Ca and Mg towards the smelter in lower mineral horizons due to geological inheritance, they do not reveal the same trends in the upper ones. Concentration of exchangeable K in organic horizons decreases towards the smelter, thus confirming the starting acidification. As result, exchangeable base cations are depleted in the considerable part of shallow soil profiles. According to model simulation the present acid load does not effect considerably on forest soils in background areas, however, dramatic shift in soil chemistry near the smelter is expected within several decades. Due to low pool of exchangeable base cations and low weathering rate continued acid deposition can lead to increased soil acidification and nutrient imbalance.     

Effects of Atmospheric Sea-Salt Deposition on Soils and Freshwaters in Northeast Scotland

The majority of Scottish upland soils are particularly sensitive to acid deposition because of their low weathering rates. The compositions of the exchangeable base cations of such soils in the United Kingdom are dominated by sea salt inputs rather than by mineral weathering inputs of base cations. Catchments with low mineral weathering rates are also those particularly susceptible to freshwater acidification. Therefore, catchments exhibiting a high sea salt effect should also exhibit the most acid waters under base flow and storm flow conditions. A field evaluation study based on 61 catchments in NE Scotland has shown that this is indeed the case. River water pH under both base flow and high flow conditions is correlated stronhly with the relative contribution of Na+ to the sum of Ca2+, Mg2+ and Na+. From these results, an attempt is being made to produce a quantitative signature of weathering for the soils within the catchment upstream of the sampling point. Representative soil samples from the LFH, AE, B and C horizons and on 4 different parent materials have been obtained from the surrounding catchments to validate the above results for associated soil solutions. Sampling took place on upland moorland podzols under Calluna vulgaris. Tension lysimeters were used to sample the soil solutions so that their chemistry could be compared with that of the relevant river water.     

Modelling geochemistry and Lake pH since glaciation at Lake Gårdsjön

The soil acidification model SAFE was modified to calculate historical changes in geochemistry and runoff since the last glaciation ended at the Lake Gårdsjön F1 catchment 12 000 B.P. Changes in runoff pH and ANC, soil weathering rate, soil mineralogy, soil texture and base saturation was also calculated. The changes in mineralogy compared favorable to data. Modeled historic weathering rates were slightly higher than data suggest, while present weathering rate was somewhat to low, 37 mmol_c m^?2 yr^?1. The weathering rate was very high immediately after the last glaciation, and decreased as the smaller particles were consumed by weathering. The calculated runoff pH follows the pattern of the paleo-inferred pH. SAFE suggests a natural depletion of base cations in the C-layer.     

Impacts of termites on selected soil physicochemical characteristics in the highlands of Southwest Ethiopia

Termites are reported to improve soil physicochemical properties thereby enhance soil fertility of their mound and foraging areas. Empirical study pertaining to these effects is missing in Southwest Ethiopia. For this study, soil samples affected by termite activities were collected at 1 m interval within 0–3 m distance from the base of six termite mounds on gently sloping and sloping land and analyzed for physicochemical parameters. The result of the analysis depicted that soil bulk density (1.38–1.15 g cm^?3) and moisture content (21.1–9.9%) decreased with increased distance from the mound base. While clay content decreased with increased distance from the mound base from72.0% to 45.5%, sand and silt contents increased from 8.0% to 21.3% and 19.3% to 28.5%, respectively. PH (6.23), organic carbon (3.85%), total nitrogen (0.4%), cation exchange capacity CEC (30.43 cmol kg^?1), exchangeable Ca (13.73 cmol kg^?1), Mg (3.15 cmol kg^?1), and PBS (56.8%) were higher on termite mounds. While, electrical conductivity (0.03 dS m^?1–0.06 dS m^?1), exchangeable K (0.52–0.93 cmol kg^?1) and Na (0.02–0.03 cmol kg^?1) showed increasing trend with the distance from the mound base. Our results indicated that termite mounds are important sinks of organic matter and mineral nutrients, and hence contribute to the enhancement of soil fertility. Thus, for subsistent farmers the uses of termite mounds as a fertilizer present an opportunity to improve agricultural production.     

Are ion exchange processes important in controlling the cation chemistry of soil- and runoff waters ?

Soil- and stream water elemental concentrations from a subcatchment in the Lake Gårdsjön area have been used to evaluate the importance of ion exchange processes on the transport of cations to aquatic ecosystems. The importance of cation exchange processes in the upper organic and upper B soil horizons was demonstrated using lysimeter water data from a recharge area and soil water flow simulated with SOIL model during winter rain events with high sea-salt concentration. The importance of the hydrological conditions, such as water flow and water pathway, silicate weathering and the ion exchange of Al with H⁺ on the streambed materials in controlling cation concentrations in soil and stream waters are also discussed. With the SAFE model, the contribution of cations from ion exchange by depletion of base cations from the exchange matrixes compared to from weathering was also assessed. SAFE calculations indicate that the release rate of base cation by ion exchange to runoff water has decreased since 1945 and is very low, approx. 0.1 keq/ha per year, at present time as a result of soil acidification due to S and N inputs.     

Pedotransfer function to predict density of forest soils in Switzerland

Soil density is an important soil property, but respective measurements are usually scarce. With data from 559 mineral soil horizons (134 sites) we developed a linear regression pedotransfer function (PTF) for the density of forest soils (sieved to ≤ 2 mm). The field estimate of density was the most important covariate. RMSE of 0.205 Mg m^?3 and R² of 0.67, calculated on independent data (131 horizons), were better than the statistics obtained by published, recalibrated PTF (RMSE 0.271–0.324 Mg m^?3; R² 0.28–0.42).     

Water flow paths in soil control element exports in an Andean tropical montane forest

We tested the hypothesis that concentrations of chemical constituents in stream water can be explained by the depth of water flow through soil. Therefore, we measured the concentrations of total organic carbon (TOC), NO₃‐N, NH₄‐N, dissolved organic nitrogen (DON), P, S, K, Ca, Mg, Na, Al and Mn in rainfall, throughfall, stemflow, litter leachate, mineral soil solution and stream water of three 8–13 ha catchments on steep slopes (1900–2200 m above sea level) of the south Ecuadorian Andes, from April 1998 to April 2003. Peak C (14–22 mg litre^?1), N (0.6–0.9 mg litre^?1), K (0.5–0.7 mg litre^?1), Ca (0.6–1.0 mg litre^?1), Mg (0.3–0.5 mg litre^?1), Al (110–390 μg litre^?1) and Mn (3.9–8.4 μg litre^?1) concentrations in stream water were associated with lateral flow (fast near‐surface flow in saturated topsoil) while the greatest P (0.1–0.3 mg litre^?1), S (0.3–0.7 mg litre^?1) and Na (3.0–6.0 mg litre^?1) concentrations occurred during low baseflow conditions. All elements had greater concentrations in the organic layer than in the mineral soil, but only C, N, K, Ca, Mg, Al and Mn were flushed out during lateral‐flow conditions. Phosphorus, S and Na, in contrast, were mainly released by weathering and (re‐)oxidation of sulphides in the subsoil. Baseflow accounted for 32% to 61% of P export, while > 50% of S was exported during intermediate flow conditions (i.e. lateral flow at the depth of several tens of cm in the mineral soil). Near‐surface water flow through C‐ and nutrient‐rich topsoil during rainstorms was the major export pathway for C, N, Al and Mn (contributing > 50% to the total export of these elements). Near‐surface flow also accounted for one‐third of total base metal export. Our results demonstrate that near‐surface flow related to storm events markedly affects the cycling of many nutrients in steep tropical montane forests.