Release Of Base Cations Research Articles

Base cations release in soils along the 127‐year Hailuogou glacial retreat chronosequence

AbstractAt the Hailuogou glacial retreat chronosequence, a mature forest has surprisingly fast developed in ∼120 yr, although the glacial debris is dominated by nutrient‐poor granite with a small contribution of carbonate minerals. In previous work, we hypothesized that the fast vegetation development is synchronized with initial fast carbonate weathering followed by slow silicate weathering. To test this hypothesis, we (a) characterized the composition of the glacial debris to elucidate the sources of base cations and (b) determined the base cation release kinetics from topsoils (0–10 cm) along the chronosequence with a weathering experiment at a constant pH value (pHstat). Besides granitic rocks, the glacial debris contained some meta‐sedimentary and meta‐volcanic calc‐silicate rocks, amphibolite, mica schist, and quartzite. Although the total Ca concentration of the glacial debris was only about double that of Mg, K, and Na, during the 1st day of the pHstat experiment, the released mass of Ca was >10 times higher than that of Mg and K, and even about 100 times higher than that of Na. The size of the fast‐reacting Ca‐carbonate pool decreased quickly in the first approximately 40 yr, after which a slow‐reacting Ca‐silicate pool matched the fast‐reacting pool with a size of 1.9 ± 0.6 g kg–1 Ca. In contrast, for Mg, K, and Na the slow‐reacting pool dominated from the beginning, suggesting that these elements mainly originated from silicate weathering. Our findings support the view that the well‐synchronized interplay between carbonate and silicate weathering facilitated the fast vegetation succession.

Net Geochemical Release of Base Cations From 25 Forested Watersheds in the Catskill Region of New York

Chemical weathering of minerals is the principal mechanism by which base cations (Ca2+, Mg2+, K+, and Na+) are released and acidity is neutralized in soils, bedrock, and drainage waters. Quantifying the release of base cations from watershed soils is therefore crucial for the calculation of “critical loads” of atmospheric acidity to forest ecosystems. We used a mass-balance approach to estimate the rate of release of base cations in 25 headwater catchments in the Catskill region of New York, an area historically subject to high inputs of acid deposition. In 2010–2013, total net base cation release via geochemical processes averaged 1,704 eq ha–1 yr–1 (range: 928–2,622). Calcium accounted for 58% of this total, averaging 498 mol ha–1 yr–1 (range: 209–815). Mass balance estimates of net geochemical release of base cations were most strongly driven by stream export and biomass uptake fluxes, with only minor contributions from precipitation. Documented rates of base cation depletion from soil exchange sites in the region were also small relative to the net geochemical release rates. We observed a significant influence of bedrock type on net base cation release rates (P = 0.002), and a weak but significant negative correlation with watershed elevation (r = −0.51). Relationships with other geographic factors such as aspect and watershed size were not significant. Net base cation release was 4.5 times higher than precipitation inputs of SO42– and NO3–, suggesting that sources of acidity internal to the watershed are now more important drivers of weathering than acid deposition. Our data suggest that release of base cations from most Catskill forest soils is sufficient to neutralize existing inputs of acidity.

Long Term Effects of Forest Liming on the Acid-Base Budget

In Rhineland-Palatinate (Germany), a high percentage of the forest area is located on poor soils with low buffering capacity. Extensive liming applications were performed to compensate for the negative consequences of acid deposition. In 1988, three experimental sites with untreated control plots and different liming treatments were established in coniferous stands to investigate the effectiveness of liming on acidification and its effect on forest ecosystems. Measuring deposition and seepage waters for 24 years allowed for calculating long-term acid-base budgets. The original approach was expanded by data from a detailed sampling of the forest stand and mineral weathering rates. Without liming, the acid load exceeded the buffer capacity by base cation release from silicate weathering during the whole observation period. As a result, there was a high release of aluminum. After liming seepage water output of organic anions, nitrate and sulfate increased in some cases, leading to a higher acid load. However, the carbonates of dolomitic limestone compensated for a higher acid load, resulting in less aluminum released compared to the control plots. Until sulfate output by seepage water declines and nitrogen emissions are reduced, liming and restricted biomass harvesting are required for forest stands on base poor soils to prevent further acidification, decline of nutrient stocks, and the destruction of clay minerals.

Catchment export of base cations: improved mineral dissolution kinetics influence the role of water transit time

Abstract. Soil mineral weathering is one of the major sources of base cations (BC), which play a dual role in forest ecosystems: they function as plant nutrients and buffer against the acidification of catchment runoff. On a long-term basis, soil weathering rates determine the highest sustainable forest productivity that does not cause acidification. It is believed that the hydrologic residence time plays a key role in determining the weathering rates at the landscape scale. The PROFILE weathering model has been used for almost 30 years to calculate weathering rates in the rooting zone of forest soils. However, the mineral dissolution equations in PROFILE are not adapted for the saturated zone, and employing these equations at the catchment scale results in a significant overprediction of base cation release rates to surface waters. In this study, we use a revised set of PROFILE equations which, among other features, include retardation due to silica concentrations. Relationships between the water transit time (WTT) and soil water concentrations were derived for each base cation, by simulating the soil water chemistry along a one-dimensional flow path, using the mineralogy from a glacial till soil. We show how the revised PROFILE equations are able to reproduce patterns in BC and silica concentrations as well as BC ratios (Ca2+/BC, Mg2+/BC and Na+/BC) that are observed in the soil water profiles and catchment runoff. In contrast to the original set of PROFILE equations, the revised set of equations could reproduce the fact that increasing WTT led to a decreasing Na+/BC ratio and increasing Ca2+/BC and Mg2+/BC ratios. Furthermore, the total release of base cations from a hillslope was calculated using a mixing model, where water with different WTTs was mixed according to an externally modeled WTT distribution. The revised set of equations gave a 50 % lower base cation release (0.23 eq m−2 yr−1) than the original PROFILE equations and are in better agreement with mass balance calculations of weathering rates. Thus, the results from this study demonstrate that the revised mineral dissolution equations for PROFILE are a major step forward in modeling weathering rates at the catchment scale.

The mechanism for inhibiting acidification of variable charge soils by adhered Pseudomonas fluorescens

Acidification in variable charge soils is on the rise due to increased acid deposition and use of nitrogenous fertilizers. The associated low pH and cation exchange capacity make the soils prone to depleted base cations and increased levels of Al3+. Consequently, Al toxicity to plants and soil infertility decrease crop yield. This study was designed to investigate the effect of Pseudomonas fluorescens on the acidification of two Ultisols. The simulated acidification experiment demonstrated that the pH of bacteria-treated soil was higher than that of control under similar conditions, suggesting that the adhered bacteria inhibited soil acidification. This observation was attributed to the association of organic anions (RCOO− or RO−) on bacteria with H+ to form neutral molecules (RCOOH or ROH) and reducing the activity of H+ in solution. The bacteria also inhibited the increase in soil soluble Al and exchangeable Al during soil acidification. The adhesion of bacteria on the soils increased soil effective cation exchange capacity (ECEC) and exchangeable base cations at each pH compared to control. The release of exchangeable base cations from bacteria-treated soil, and the decrease in soil ECEC and exchangeable base cations with decreasing pH confirmed that protonation of organic anions on adhered bacteria was mainly responsible for the inhibition of soil acidification. The change of zeta potential of the bacteria with pH and the ART-FTIR analysis at various pH provided more evidence for this mechanism. Therefore, the bacteria in variable charge soils played an important role in retarding soil acidification.

Modelling long-term impacts of fertilization and liming on soil acidification at Rothamsted experimental station

Liming is widely used to reduce the impacts of soil acidification and optimize soil pH for agricultural production. Whether models can simulate the effect of liming on soil pH, and base saturation (BS), and thereby guide lime application, is still largely unknown. Long-term experimental data from a grassland (Park Grass, 1965–2012) and arable land (Sawyers Field, 1962–1972) at Rothamsted Research, UK, were thus used to assess the ability of the VSD+ model to simulate the effects of long-term fertilization and liming on soil acidification. The VSD+ model was capable of simulating observed soil pH and BS changes over time in the long-term liming experiments, except for a treatment in which sulphur (S) was added. Normalized Mean Absolute Errors (NMAE) and Normalized Root Mean Square Errors (NRMSE) of simulated and observed pH values, averaged over the observation periods varied between 0.02 and 0.08 (NMAE) and 0.01–0.05 (NRMSE). The acidity budget results for Park Grass suggest that nitrogen (N) transformations contributed most to acidity production, causing predominantly aluminium (Al) exchange in the topsoil (0–23 cm) followed by base cation (BC) release, but in the treatment with S addition, BC uptake had a nearly similar effect on acidity production. However, in Sawyers Field, the acidity budget suggested that BC uptake was the dominant cause of soil acidification, while the impacts of N transformations were limited. Liming was found to sufficiently replenish BC and decrease Al exchange in the topsoil layer. Overall, the VSD+ model can adequately reconstruct the impacts of fertilizer and liming applications on acid neutralizing processes and related soil pH and BC changes at the soil exchange complex.

Application of wood biochar in polluted soils stabilized the toxic metals and enhanced wheat (Triticum aestivum) growth and soil enzymatic activity

Biochar is a stable carbonaceous by-product of pyrolysis and can be used for toxic metals (TMs) retention in polluted soil. Wheat (Triticum aestivum) was grown in three polluted soils collected from Chenzhou (CZ), Tongguan (TG) and Fengxian (FX), China. Wood biochar (WBC) was applied at 0, 0.5, 1.0 and 2.0% to each pot filled with 2 kg polluted soil. The results showed that WBC was efficient to alter soil pH and electrical conductivity (EC). The changes in soil pH and EC had a direct relationship with the immobilization and phytostabilization of TMs in the three soils. The bioavailable TMs (Zn, Pb, Cd, and Cu) were reduced in the soil after WBC amendments due to ion exchange, precipitates of metal-carbonates and metal-phosphates, and chemisorption on WBC surface. The reduction in the bioavailable TMs content also resulted in the diminution in TMs shoot uptake in wheat. Similarly, the TMs uptake in wheat root were also reduced as a result of WBC application. The reduction in bioavailable TMs and the release of essential nutrients and base cations from the WBC also increased the wheat shoot and root dry biomasses production. The application of WBC in polluted soil also improved soil health and the urease and β-glucosidase enzymes were also enhanced. The results concluded that WBC was efficient to reduce the bioavailability of TMs and shoot and root uptake, improved wheat dry biomasses production and soil enzymatic activities in industrial and smelter/mines polluted soils.

Impacts of earthworm species on soil acidification, Al fractions, and base cation release in a subtropical soil from China.

Soil-exchangeable aluminum (Al) has toxic effects on living organisms in acidic soils. Earthworm presence and activity can alter soil pH, which has a significant influence on Al toxicity. However, the effects of earthworms on soil Al toxicity and fractions are still largely unknown. This laboratory study focused on the effects of three earthworm species (endogeics Pontoscolex corethrurus and Amynthas robustus, anecis Amynthas aspergillum) on soil acidification, Al fraction distribution, and base cation release. Three native earthworm species and a soil (latosolic red soil) collected from a botanical garden in South China were incubated under laboratory conditions. After 40days of incubation, six Al fractions in soil, namely exchangeable (AlEx), weakly organically bound (AlOrw), organically bound (AlOr), amorphous (AlAmo), Al occluded in crystalline iron oxides (AlOxi), and amorphous aluminosilicate and gibbsite (AlAag) fractions, were extracted using a sequential procedure. Soil pH; organic carbon; total nitrogen; total Al (AlTotal); exchangeable K, Na, Ca, Mg contents; and CEC were determined as well. Compared to control soil, pH values increased by 0.79, 0.41, and 0.57units in casts in the presence of P. corethrurus, A. robustus, and A. aspergillum, and 0.70, 0.32, and 0.50units in non-ingested soil, respectively. Compared to control soil, the 61.7%, 30.7%, and 36.1% of AlEx contents in casts and 68.5%, 25.9%, and 39.0% of AlEx in non-ingested soil significantly decreased with the addition of P. corethrurus, A. robustus, and A. aspergillum, respectively. Moreover, compared to control soil, the 78.7%, 37.7%, and 40.1% of exchangeable Ca2+ and 12.3%, 24.7%, and 26.8% of exchangeable Mg2+ contents in casts significantly increased with the presence of P. corethrurus, A. robustus, and A. aspergillum, respectively. Soil treated with P. corethrurus had higher soil pH values, exchangeable Ca2+ contents, and lower AlEx than those with A. robustus and A. aspergillum. Results of principal component analyses showed that P. corethrurus, A. robustus, and A. aspergillum casts and non-ingested soil differ for soil pH, Al fractions, and exchangeable base cations release. These results indicate that earthworms, especially P. corethrurus, can reduce soil Al toxicity, increase soil pH, and affect the release of exchangeable base cations.

Mechanisms for increasing soil resistance to acidification by long-term manure application

Soil pH buffering capacity (pHBC) plays a crucial role in determining soil acidification rates and the amount of lime required to ameliorate soil acidity. However, it remains poorly understood how soil organic matter affects soil pHBC. Here, Alfisol and Ultisol samples from long-term fertilization experiments (control, chemical N, P, and K (NPK), manure only (M), 1/2 NPK plus 1/2 M (1/2NPKM), and NPK plus M (NPKM)) were used to investigate the effects and underlying mechanisms of manure application on the pHBC and soil resistance to acidification through simulated acidification experiments. The results indicated that the application of manure increased pHBC and the resistance of soils to acidification in both the Alfisol and Ultisol. The pHBC of the Alfisol in the M and NPKM treatments was increased by 81 and 60% compared with the control, respectively. Similarly, the pHBC of the Ultisol in the NPKM treatment was 66% higher than that of the control. The extent of protons consumption by the Alfisol followed the order: M > NPKM > 1/2NPKM > NPK ≈ control during stimulated acidification, which was consistent with their pHBC. These results suggested that manure application increased the resistance of the Alfisol to acidification by increasing soil pHBC. The protonation of organic anions from the dissociation of weakly acidic functional groups on soil organic matter to form neutral molecules was the main mechanism responsible for the increase in pHBC and soil resistance to acidification induced by manure application. During this process, some exchangebale base cations were released from negatively charged sites on organic matter into soil solution. This mechanism was confirmed by the experimental observations: the release of base cations from soils increased, while soil exchangeable base cations and effective CEC decreased as soil pH decreased. The results are of fundamental significance for understanding the role of organic matter in retarding soil acidification through long-term manure application.

Spatial and temporal variations of base cation release from chemical weathering on a hillslope scale

Cation release rates to catchment runoff from chemical weathering were assessed using an integrated catchment model that included the soil's unsaturated, saturated and riparian zones. In-situ mineral dissolution rates were calculated in these zones as a function of pH, aluminum and dissolved organic carbon (DOC) concentrations along a hillslope in Northern Sweden where soil water was monitored over nine years. Three independent sets of mineral dissolution equations of varying complexity were used: PROFILE, Transition-State Theory (TST), and the Palandri & Kharaka database.Normalization of the rate-coefficients was necessary to compare the equations, as published rate-coefficients gave base cation release rates differing by several orders of magnitude. After normalizing the TST- and Palandri & Kharaka-rate coefficients to match the base cation release rates calculated from the PROFILE-equations, calculated Ca2+ and Mg2+ release rates are consistent with mass balance calculations, whereas those of Na+ and K+ are overestimated. Our calculations further indicate that a significant proportion of base cations are released from the organic soils in the near-stream zone, in part due to its finer texture. Of the three sets of rate equations, the base cation release rates calculated from the normalized TST-equations were more variable than those calculated using the other two sets of equations, both spatially and temporally, due to its higher sensitivity to pH. In contrast, the normalized Palandri & Kharaka-equations were more sensitive to variations in soil temperature.

Effects of nitrogen fertilization on the acidity and salinity of greenhouse soils.

A greenhouse pot experiment was conducted to study the effects of conventional nitrogen fertilization on soil acidity and salinity. Three N rates (urea; N0, 0 kg N ha(-1); N1, 600 kg N ha(-1); and N2, 1,200 kg N ha(-1)) were applied in five soils with different greenhouse cultivation years to evaluate soil acidification and salinization rate induced by nitrogen fertilizer in lettuce production. Both soil acidity and salinity increased significantly as N input increased after one season, with pH decrease ranging from 0.45 to 1.06 units and electrolytic conductivity increase from 0.24 to 0.68 mS cm(-1). An estimated 0.92 mol H(+) was produced for 1 mol (NO2 (-) + NO3 (-))-N accumulation in soil. The proton loading from nitrification was 14.3-27.3 and 12.1-58.2 kmol H(+) ha(-1) in the center of Shandong Province under N1 and N2 rate, respectively. However, the proton loading from the uptake of excess bases by lettuces was only 0.3-4.5 % of that from nitrification. Moreover, the release of protons induced the direct release of base cations and accelerated soil salinization. The increase of soil acidity and salinity was attributed to the nitrification of excess N fertilizer. Compared to the proton loading by lettuce, nitrification contributed more to soil acidification in greenhouse soils.

Chemical properties of decaying wood in an old-growth spruce forest and effects on soil chemistry

Live trees influence the nutrient status of the soil by the interception of substances from the atmosphere, the uptake of nutrients from the soil, and the deposition of litter. In an unmanaged old-growth spruce mountain forest on acidic soil, we analyzed how the death and decay of spruce trees affects the acidity and element concentrations of the soil, tree bark (or outermost stemwood) and stemflow. Key study objective was to examine whether the element release from decaying deadwood significantly increases the available soil nutrient stocks in the senescence phase of coniferous forests. Bark and stemflow chemistry responded to the death and decay of the trees with lowered acidity and reduced nutrient concentrations, which was attributed to the gradual loss of the intercepting canopy surface. Bark and stemflow concentrations of base cations (K, Ca, Mg) showed a transient peak in the course of wood decay. Published evidence suggests that the variability in bark and stemflow chemistry detected across the sequence of wood decay stages was sufficient to shape the epiphytic lichen and bryophyte communities. The death and decay of spruce trees also resulted in elevated base saturation near standing deadwood. Downed deadwood had a negligible effect on soil chemistry, among others due to slow decomposition in the studied cold mountain forest. Soil acidity was not significantly affected by deadwood. The release of base cations from standing deadwood to the soil suggests that sparing part of the trees in managed forests from logging could counteract nutrient depletion through timber harvesting.

Base cation fluxes and release by needle litter in three adjacent coniferous plantations

This study was carried out to evaluate base cation (K, Ca, Mg) fluxes and release by needle litter in three adjacent coniferous plantations (larch: Larix leptolepis; red pine: Pinus densiflora, rigitaeda pine: P. rigita × taeda) planted in the same year (1963) in the Sambong Exhibition Forests, Korea. Needle litter was collected monthly from July 2006 to June 2008 and litter decomposition rates were measured from December 2006 to June 2008. The concentrations and fluxes of K and Mg were significantly higher (P < 0.05) in the larch than in both pine plantations. The differences in K and Mg fluxes in needle litter were attributed to low nutrient concentrations of pine needle litter compared with larch needle litter, while the highest fluxes of Ca in the red pine plantation were due to high concentration and inputs of needle litter compared with other two coniferous plantations. Potassium and Mg concentrations (mg g−1) and remaining (mg bag−1) from needle litter during the decomposition processes were higher in the larch than in both pine plantations, while Ca concentration and remaining were significantly lower in the rigiteada than in the larch or red pine plantations. These results demonstrate that base cation cycling processes can be varied considerably after plantation establishment by the characteristics of needle litter fluxes and nutrient release among tree species types.

Impacts of simulated acid rain on recalcitrance of two different soils

Laboratory experiments were conducted to estimate the impacts of simulated acid rain (SAR) on recalcitrance in a Plinthudult and a Paleudalfs soil in south China, which were a variable and a permanent charge soil, respectively. Simulated acid rains were prepared at pH 2.0, 3.5, 5.0, and 6.0, by additions of different volumes of H2SO4 plus HNO3 at a ratio of 6 to 1. The leaching period was designed to represent 5 years of local annual rainfall (1,200 mm) with a 33 % surface runoff loss. Both soils underwent both acidification stages of (1) cation exchange and (2) mineral weathering at SAR pH 2.0, whereas only cation exchange occurred above SAR pH 3.5, i.e., weathering did not commence. The cation exchange stage was more easily changed into that of mineral weathering in the Plinthudult than in the Paleudalfs soil, and there were some K(+) and Mg(2+) ions released on the stages of mineral weathering in the Paleudalfs soil. During the leaching, the release of exchangeable base cations followed the order Ca(2+) >K(+) >Mg(2+) >Na(+) for the Plinthudult and Ca(2+) >Mg(2+) >Na(+) >K(+) for the Paleudalfs soil. The SARs above pH 3.5 did not decrease soil pH or pH buffering capacity, while the SAR at pH 2.0 decreased soil pH and the buffering capacity significantly. We conclude that acid rain, which always has a pH from 3.5 to 5.6, only makes a small contribution to the acidification of agricultural soils of south China in the short term of 5 years. Also, Paleudalfs soils are more resistant to acid rain than Plinthudult soils. The different abilities to prevent leaching by acid rain depend upon the parent materials, types of clay minerals, and soil development degrees.

Experimental acidification of two biogeochemically-distinct neotropical streams: Buffering mechanisms and macroinvertebrate drift

Research into the buffering mechanisms and ecological consequences of acidification in tropical streams is lacking. We have documented seasonal and episodic acidification events in streams draining La Selva Biological Station, Costa Rica. Across this forested landscape, the severity in seasonal and episodic acidification events varies due to interbasin groundwater flow (IGF). Streams that receive IGF have higher concentrations of solutes and more stable pH (~6) than streams that do not receive IGF (pH ~5). To examine the buffering capacity and vulnerability of macroinvertebrates to short-term acidification events, we added hydrochloric acid to acidify a low-solute, poorly buffered (without IGF) and a high-solute, well buffered stream (with IGF). We hypothesized that: 1) protonation of bicarbonate (HCO3−) would neutralize most of the acid added in the high-solute stream, while base cation release from the sediments would be the most important buffering mechanism in the low-solute stream; 2) pH declines would mobilize inorganic aluminum (Ali) from sediments in both streams; and 3) pH declines would increase macroinvertebrate drift in both streams. We found that the high-solute stream neutralized 745μeq/L (96% of the acid added), while the solute poor stream only neutralized 27.4μeq/L (40%). Protonation of HCO3− was an important buffering mechanism in both streams. Base cation, Fe2+, and Ali release from sediments and protonation of organic acids also provided buffering in the low-solute stream. We measured low concentrations of Ali release in both streams (2-9μeq/L) in response to acidification, but the low-solute stream released double the amount Ali per 100μeq of acid added than the high solute stream. Macroinvertebrate drift increased in both streams in response to acidification and was dominated by Ephemeroptera and Chironomidae. Our results elucidate the different buffering mechanisms in tropical streams and suggest that low-solute poorly buffered streams might be particularly vulnerable to episodic acidification.

Assessment of Uncertainty in Long-Term Mass Balances for Acidification Assessments: A MAGIC Model Exercise

Long-term (1860-2010) catchment mass balance calculations rely on models and assumptions which are sources of uncertainty in acidification assessments. In this article, we report on an application of MAGIC to model acidification at the four Swedish IM forested catchments that have been subject to differing degrees of acidification stress. Uncertainties in the modeled mass balances were mainly associated with the deposition scenario and assumptions about sulfate adsorption and soil mass. Estimated base cation (BC) release rates (weathering) varied in a relatively narrow range of 47-62 or 42-47 meq m(-2) year(-1), depending on assumptions made about soil cation exchange capacity and base saturation. By varying aluminum solubility or introducing a dynamic weathering feedback that allowed BC release to increase at more acidic pHs, a systematic effect on predicted changes in acid neutralizing capacity (ΔANC ca. 10-41 μeq l(-1)) and pH (ca. ΔpH = 0.1-0.6) at all sites was observed. More robust projections of future changes in pH and ANC are dependent on reducing uncertainties in BC release rates, the timing, and extent of natural acidification through BC uptake by plants, temporal changes in soil element pools, and fluxes of Al between compartments.

Impact of nitrogenous fertiliser-induced proton release on cultivated soils with contrasting carbonate contents: A column experiment

An experimental study was carried out in order to evaluate the impact of nitrogen fertiliser-induced acidification in carbonated soils. Undisturbed soil columns containing different carbonate content were sampled in the field. Fertiliser spreading was simulated by NH 4Cl addition on top of the soil column. Soil solution composition (mainly nitrate and base cations) was studied at the soil column’s base. Nitrification occurred to a different extent depending on soil type. Higher nitrification rates were observed in calcareous soils. In all the soil types, strong correlations between leached base cation and nitrate concentrations were observed. Regression coefficients between base cations, nitrate and chloride were used to determine the dominant processes occurring following NH 4Cl spreading. In non-carbonated soils, nitrogen nitrification induced base cation leaching and soil acidification. In carbonated soils, no change of soil pH was observed. However, fertilisers induced a huge cation leaching. Carbonate mineral weathering led to the release of base cations, which replenished the soil exchangeable complex. Carbonated mineral weathering buffered acidification. Since direct weathering might have occurred without atmospheric CO 2 consumption, the use of nitrogen fertiliser on carbonated soil induces a change in the cation and carbon budgets. When the results of these experiments are extrapolated on a global scale to the surface of fertilised areas lying on carbonate, carbonated reactions with N fertilisers would imply an additional flux of 5.7 × 10 12 mol yr −1 of Ca + Mg. The modifications of weathering reactions in cultivated catchments and the ability of nitrogen fertilisers to significantly modify the CO 2 budget should be included in carbon global cycle assessment.

Phosphorus and base cation accumulation and release patterns in decomposing Scots pine, Norway spruce and silver birch stumps

Tree stumps are integral constituents of managed forest ecosystems, but their role in nutrient cycling is poorly understood. We studied phosphorus (P), potassium (K), calcium (Ca) and magnesium (Mg) dynamics in decomposing Scots pine (Pinus sylvestris), Norway spruce (Picea abies), and silver birch (Betula pendula) stumps in southern Finland in a chronosequence of 0-, 5-, 10-, 20-, 30- and 40-year-old clear-cut areas. Along with the decomposition of pine and spruce stumps, the amount of P in stumps increased, but K and Ca were released, and the amount of Mg initially decreased and then increased. All nutrients, except K, accumulated in birch stumps during the first ten years, but were released thereafter. After 40 years of decomposition, pine and spruce stumps contained 180% and 202% of their initial amounts of P, respectively. In addition, the amounts of Mg were larger than the initial amounts in 40-year decomposed pine (126%) and spruce (202%) stumps. In contrast, birch stumps lost 64% and 75%, respectively, of their initial amounts of P and Mg over a 40-year period. The stumps of all the species were found to release K and Ca. Pine, spruce and birch stumps lost 48%, 64% and 87% of their initial amount of K, and 49%, 35% and 42% of their initial amount of Ca, respectively, during the 40-year period. The results indicate that decomposing stumps of the major tree species in Fennoscandian forests are long-term nutrient pools and they serve as P sinks, thus potentially reducing P leaching after clear-cutting.

Direct and indirect effects of increasing dissolved organic carbon levels on pH in lakes recovering from acidification

In this study, we examine the impact of increasing concentrations of dissolved organic carbon (DOC) on the recovery from acidification for 66 lakes in Southern Sweden. The lakes are small, weakly buffered, and have all been affected by acidifying deposition. A majority of the lakes (∼75%) showed an increase in DOC concentrations between 1990 and 2008. The method used in this study was to model pH in 2008 from DOC, acid neutralizing capacity, pCO2 (partial carbon dioxide pressure), and Al speciation, using both the DOC observed in 2008 and the “unelevated” DOC of 1990. Furthermore, we consider the indirect effects of increasing DOC on acidity, i.e., the ancillary effects from DOC on pCO2, Al transport and speciation, and release of base cations (BCs). Our results indicate that the DOC increase in the latest decades has retarded the recovery from acidification by 0.13 pH units (median for all lakes) and by more than 1 unit for individual lakes. The effects of elevated pCO2 and BC concentrations accompanying the DOC increase compensated for each other for the average lake, whereas the effects of higher Al transport on pH were minor. The estimate of the amount of BCs released with the organic anions is however uncertain, and further studies on this topic are needed.

Carbon dioxide emissions of soils under pure and mixed stands of beech and spruce, affected by decomposing foliage litter mixtures

Soil respiration is the largest terrestrial source of CO 2 to the atmosphere. In forests, roughly half of the soil respiration is autotrophic (mainly root respiration) while the remainder is heterotrophic, originating from decomposition of soil organic matter. Decomposition is an important process for cycling of nutrients in forest ecosystems. Hence, tree species induced changes may have a great impact on atmospheric CO 2 concentrations. Since studies on the combined effects of beech–spruce mixtures are very rare, we firstly measured CO 2 emission rates in three adjacent stands of pure spruce ( Picea abies), mixed spruce–beech and pure beech ( Fagus sylvatica) on three base-rich sites (Flysch) and three base-poor sites (Molasse; yielding a total of 18 stands) during two summer periods using the closed chamber method. CO 2 emissions were higher on the well-aerated sandy soils on Molasse than on the clayey soils on Flysch, characterized by frequent water logging. Mean CO 2 effluxes increased from spruce (41) over the mixed (55) to the beech (59) stands on Molasse, while tree species effects were lower on Flysch (30–35, mixed > beech = spruce; all data in mg CO 2–C m −2 h −1). Secondly, we studied decomposition after fourfold litter manipulations at the 6 mixed species stands: the O i – and O e horizons were removed and replaced by additions of beech –, spruce – and mixed litter of the adjacent pure stands of known chemical quality and one zero addition (blank) in open rings (20 cm inner diameter), which were covered with meshes to exclude fresh litter fall. Mass loss within two years amounted to 61–68% on Flysch and 36–44% on Molasse, indicating non-additive mixed species effects (mixed litter showed highest mass loss). However, base cation release showed a linear response, increasing from the spruce – over the mixed – to the beech litter. The differences in N release (immobilization) resulted in a characteristic converging trend in C/N ratios for all litter compositions on both bedrocks during decomposition. In the summers 2006 and 2007 we measured CO 2 efflux from these manipulated areas (a closed chamber fits exactly over such a ring) as field indicator of the microbial activity. Net fluxes (subtracting the so-called blank values) are considered an indicator of litter induced changes only and increased on both bedrocks from the spruce – over the mixed – to the beech litter. According to these measurements, decomposing litter contributed between 22–32% (Flysch) and 11–28% (Molasse) to total soil respiration, strengthening its role within the global carbon cycle.