Soil-solution chemistry in a low-elevation spruce-fir ecosystem,Howland, Maine

Soil solutions were collected monthly by tension and zero-tension lysimeters in a low-elevation red spruce stand in east-central Maine from May 1987 through December 1992. Soil solutions collected by Oa tension lysimeters had higher concentrations of most constituents than the Oa zero-tension lysimeters. In Oa horizon soil solutions growing season concentrations for SO₄, Ca, and Mg averaged 57, 43, and 30 μmol L^?1 in tension lysimeters, and 43, 28, and 19 μmol L^?1 in zero-tension lysimeters, respectively. Because tension lysimeters remove water held by the soil at tensions up to 10 kPa, solutions are assumed to have more time to react with the soil compared to freely draining solutions collected by zero-tension lysimeters. Solutions collected in the Bs horizon by both types of collectors were similar which was attributed to the frequency of time periods when the water table was above the Bs lysimeters. Concentrations of SO₄ and NO₃ at this site were lower than concentrations reported for most other eastern U.S. spruce-fir sites, but base cation concentrations fell in the same range. Aluminum concentrations in this study were also lower than reported for other sites in the eastern U.S. and Ca/Al ratios did not suggest inhibition of Ca uptake by roots. Concentrations of SO₄, Ca, K, and Cl decreased significantly in both the Oa and Bs horizons over the 56-month sampling period, which could reflect decreasing deposition rates for sulfur and base cations, climatic influences, or natural variation. A longer record of measured fluxes will be needed to adequately define temporal trends in solution chemistry and their causes.     

Speciation and mobilization of aluminium and cadmium in podzols and cambisols of S. Sweden

Processes governing the mobilization of Al and Cd in podzols and cambisols of S. Sweden having different tree layer vegetation (Picea abies, Fagus sylvatica, or Betula pendula) were investigated. Speciation of Al and Cd in soil solutions were performed by a column cation exchange procedure (cf. Driscoll, 1984) in combination with thermodynamic calculations. Podzols in spruce and beech stands were characterized by a high release of organic compounds from the O/Ah horizons, resulting in a high organic complexation of Al (c. 93%) in the soil solution from the E horizon (15 cm lysimeters). Organic complexes were mainly adsorbed/precipitated in the upper Bh horizon and the overall transport of Al at 50 cm depth was governed by a pH dependent dissolution of a solid-phase Al pool. In the cambisols, inorganic Al forms were predominant at both 15 and 50 cm depth, and Al solubility was closely related to solution pH. Secondary minerals like synthetic gibbsite, jurbanite, kaolinite or imogolite could generally not explain measured solution Al³⁺ activities. Results instead indicated that the relatively large organically bound solid-phase Al pools present in both soil types could do so. The column fractionation procedure could be used only qualitatively for Cd, but results strongly indicated that Cd-organo complexes contributed significantly to the overall mobilization of Cd in the podzol E horizons. In all other soil solutions, Cd²⁺ was the predominant species. Both solid-phase and solution chemistry suggests that ion exchange processes controlled the Cd²⁺ activities in these solutions. All reactive solidphase Cd was extractable by NH₄Cl and Cd²⁺ activities could in most cases effectively be modeled by the use of ion exchange equations. Solubilized Al³⁺ efficiently competed for exchange sites and played an important role for the Cd mobilization in these soils.     

The solubility characteristics of organic Al precipitates in allophanic Bs horizons could mimic those of Al hydroxides, and indicate the solubility of associated allophanes

It is shown that Al-humate and fulvate precipitates in Bs horizons of pH > 4.6 can be the source of the soluble aluminium which is rapidly released in equilibrium studies to give log₁₀{Al³⁺} + 3pH values near 9.4 at 8°C, so that it is not necessary to postulate an anomalously reactive but sparingly soluble Al(OH)₃ phase. These Al-organic precipitates will have reached equilibrium in the natural soil environment with the more slowly reacting hydroxy-aluminium precipitates present, including proto-imogolite allophane, but can release Al³⁺ much more rapidly than the inorganic precipitates in laboratory equilibrations and soil leaching episodes that yield lysimeter waters. Equilibrium concentrations of Al reported in a range of Bs horizons indicate that the allophanes present are less soluble than proto-imogolite sols prepared in the laboratory and matured for up to 2 years.     

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

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

Apparent Cation – Exchange Equilibria and Aluminium Solubility in Solutions Obtained from Two Acidic Forest Soils by Centrifuge Drainage Method and Suction Lysimeters

Apparent cation–exchange equilibria and solubility of aluminium were analysed in two acidic forest soils: a Cambisol and a Cambic Podzol. Soil solution was obtained by a centrifuge drainage method from fresh soil samples and with suction lysimeters. The total positive charge of the measured cations as well as the concentrations of the cations were generally much larger in the centrifugates than in the lysimeter solutions, which implies that total charge of soil solution is larger in small pores than in large pores. Hydrogen ion in particular was concentrated in some of the centrifugates, the ratio centrifugate:lysimeter solution being over 10. The total positive charge of the measured cationsdecreased with increasing depth with both methods. Theapparent cation–exchange coefficients K _H-Ca, K _Al-Ca, and K _K-Ca had different values in the methods, and the variation in the cation exchange coefficients was larger in the lysimeter method than in the centrifuging method. The coefficient K _Mg-Ca had similar values in both methods. The results imply that mobile solution could not have cation–exchange equilibria with bulk exchangeable cations in the soils, although solution in small pores seemed to have equilibria. Solubility of Al did not follow the solubility of an Al(OH)₃ phase in the centrifugates, and the centrifugates with a H⁺ activity larger than 60 μmol were undersaturated with respect to the gibbsite. Solubility of Al was between gibbsite and amorphousAl(OH)₃ in the lysimeter solutions. Differencesbetween the centrifugates and the lysimeter solutionsin the ion concentrations and in the apparent chemicalequilibria were similar for both soils studied.     

Fractionation of dissolved organic carbon in soil water: Effects of extraction and storage methods

Abstract

We measured the concentration and composition (sensu Leenheer, 1981) of dissolved organic carbon (DOC) in lysimeter solutions from the forest floor of a spruce stand in Maine and in laboratory extracts of organic (Oa horizon) and mineral soils collected from various forests in Maine, New Hampshire, and Vermont. All soils were acid Spodosols developed from glacial till. The effects of different storage, extraction and filtration methods were compared. Extracts from Oa horizons stored fresh at 3°C contained a larger fraction of hydrophobic neutrals than lysimeter forest floor solutions (31 and 4% of DOC in stored and lysimeter solutions, respectively), whereas extracts from Oa horizons which had been extracted, incubated at 10–15°C, and extracted again had DOC compositions similar to that in lysimeter solutions. Mechanical vacuum and batch extractions of Oa horizons yielded DOC similar in concentration and composition if the extracts were filtered through glass fiber filters. Nylon membrane filters, however, removed more hydrophobic acids from batch extracts. Dissolved organic carbon extracted from frozen, air‐dry, and oven‐dry Oa and Bh horizons was relatively rich in hydrophilic bases and neutrals and was similar to that released after chloroform fumigation, indicating that common soil‐storage methods disrupt microbial biomass.     

Comparison of soil water chemistry and sample size requirements for pan vs tension lysimeters

A study was conducted to compare soil leachate chemistry and determine sample size requirements for tension vs pan (zero-tension) lysimeters. Analyses were performed on an annual and seasonal basis for one year of data collected at Pea Vine Hill, a forested site in southwestern Pennsylvania. On an annual basis, SO₄ ^?2, Ca⁺², Mg⁺², Mn⁺², K⁺ and specific conductance were significantly higher in tension lysimeter samples but no chemical species were significantly higher in pan lysimeters. Seasonal comparisons indicated chemical differences between lysimeter types were variable with more significant deviations present during wet periods. Nearly all significant seasonal differences were comprised of higher concentrations in tension compared to pan lysimeters. Disparities in leachate chemistry between lysimeter types were ascribed to different sources of water collected by the instruments especially during wet periods. Sample size requirements were calculated for two biweekly periods for each lysimeter type at three confidence levels. Based upon calculated sample demands, pan lysimeter soil leachate chemistry could be characterized with fewer samples than tension lysimeters. Less than .30 samples were generally necessary for pan B-horizon lysimeters at the 70% confidence level. Sample requirements were usually unreasonable at higher confidence levels.     

Dynamics of aqueous aluminum species in a podzol affected by experimental MgSO4 and (NH4)2SO4 treatments

Chemistry of aqueous Al in a podzol on a Norway spruce (Picea abies [L.] Karst.) site in the Black Forest (SW Germany) and changes induced by experimental applications of MgSO₄ were studied. Soil solution taken from the O, E and BC horizons were analyzed for the fractions ‘labile monomeric Al’, ‘non-labile monomeric Al’, and ‘acid-reactive Al’. The activities of ‘inorganic monomeric Al’ species and the saturation indices (SI) of the soil solution with respect to Al-bearing minerals were calculated using the equilibrium speciation model WATEQF. On the untreated plot, soil leachates are characterized by Al_tot concentrations of 0.1 mg L^?1 (mineral soil). In the O horizon, the fractions ‘acidsoluble Al’ and ‘non-labile monomeric Al’ (mainly organically complexed Al) together comprise 80% of Al_tot. In the leachates from the mineral soil Al³⁺ prevails, being 50% of Al_tot. Al-F-complexes make up 5 to 10% in all horizons. MgSO₄ and (NH₄)₂SO₄ treatments resulted in an intense Al mobilization up to 50 mg L^?1. In this situation, 60% of Al_tot is covered by Al³⁺ and 40% by non-phytotoxic Al-SO₄-complexes. After rainfall events, mobilized Al is quickly translocated into the subsoil, with water flow through macropores then appearing to be an important mechanism. In both treatments, soil solution chemistry was favorable for the precipitation of the Al(OH)SO₄-type minerals alunite and jurbanite. However, a control of Al solubility by this process is not likely due to kinetic restraints. Application of MgSO₄ was followed by an increase of the Mg/Al molar ratio in the soil solution, whereas the Ca/Al ratio decreased. After treatment with (NH₄)₂SO₄ both the Ca/Al and the Mg/Al ratios deteriorated.     

Movement of aluminium as an inorganic complex in some podzolised soils,New Zealand

Chemical and mineralogical data are presented for three Spodosols (podzols) and a related Inceptisol (yellow-brown loam). Allophane with an Al/Si atomic ratio close to two is identified in the B horizons of all four soils, and minor amounts of imogolite are present in association with allophane in all but one soil where small-particle gibbsite occurs. Parent materials for these soils are essentially non-vitric. Allophane (Al/Si = 2) has been estimated quantitatively in all soils using oxalate-extractable Si (Si₀) and is selected clay fractions using both Si₀ and infrared spectroscopy. Maximum concentrations of allophane (Al/Si = 2) range from 5% to 18% of fine earth (< 2 mm) fractions and all occur in B horizons. Fe₀ values are low relative to Al₀ values except for the upper horizons of the Inceptisol. Al₀ values peak in B horizons and the ratio pyrophosphate-extractable Al to Al₀ decreases from about 1 in A and upper B horizons to 0.1–0.4 in lower B horizons.An interpretation of the data is consistent with recent proposals that the movement of Al in podzolisation is due primarily to the formation of inorganic complexes with Si. Chemical criteria for spodic horizons should be consistent with the total illuviation of Al and Fe (and perhaps Si), rather than just the organic-bound fraction of Al and Fe in these horizons as indicated by amounts in extractants such as pyrophosphate.     

Comparison of chemical composition of soil solutions collected by zero-tension plate lysimeters with those from ceramic-cup lysimeters in a forest soil

We analysed the chemistry of solutions collected from soil by zero-tension plate lysimeters and cup lysimeters connected to a constant suction (600 hPa) under Douglas fir in the Beaujolais mountains (France). The chemistry of zero-tension lysimeters' (ZTL) and tension lysimeters' (TL) solutions differed enormously: TL solutions were most concentrated in Si, NH₄-N, NO_3--N, Cl^?, Mg²⁺ and A1³⁺ and TOC, whereas Ca²⁺ and K⁺ concentrations were greater in ZTL solutions. Organic matter (OM) greatly influenced the solution chemistry in both ZTL and TL. The chemistry of ZTL solutions was affected mainly by OM mineralization in the forest floor and upper soil horizon, and that of TL solution seemed to be related to destabilization of humified compounds under the new vegetation. Nitrification was important: residual nitrification led to excess protons neutralized in weathering or ion exchange reactions, mobilized cations, mainly A1³⁺. Selectivity coefficients calculated both for ZTL and TL solutions formalized the differences between the two types of solutions. Nevertheless, these coefficients remained most often within the same order of magnitude indicating relations between them. Solutions from the two devices provided different information and should not be used for the same objectives. Solutions from ZTL are suited for ecosystem input-output budgets, whereas TL solutions are more useful when equilibrium between the solution and solid phase or when plant nutrition are considered.     

SOLUBILITY OF ALUMINIUM IN SOILS OF THE HUMID TROPICS

Soil samples obtained from genetic horizons of an upland and acid sulphate soil of Sierra Leone, were equilibrated with 0.01 M CaCI using a 1:2 soil to solution ratio. Al³⁺ activity was estimated from total Al measured in the equilibrium extract, by accounting for hydrolysis and the formation of other complex species. The Al³⁺ activity was pH-dependent, but the Al(OH)³ ion product was I'airly constant throughout the upland soil profile; Al³⁺ activity was near that expected for equilibrium with kaolinite and quartz. In the acid sulphate soil alunite appeared to control the activity of Al³⁺.     

Comparison of soil solution chemistry assessment using zero-tension lysimeters or centrifugation

The composition of soil solutions obtained from the field varies with the method of extraction. Variations in sampling methods and the difficulties in extracting representative samples from soils in space and time, can explain divergent results. In this study we compared soil solutions from a forest soil in northern Sweden obtained by a centrifuge drainage technique and by zero-tension monolith lysimeters. Zero-tension lysimeters were destructively sampled, and centrifuge solutions from this soil were compared with that from soil outside. In our study we found three major differences in the solute composition between the centrifugate and the lysimeter leachate: (i) larger concentrations of most solutes in the mor layer centrifugate than in the mor layer leachate, (ii) accumulation of nitrate in the lysimeters, and (iii) larger concentrations of base cations in the zero-tension lysimeters below 0.3 m depth. Water contents within the lysimeters were up to 3.5 times greater than under natural conditions and the water yields from the lysimeters indicate that water residence time ranged from < 1 to >5 years. This study shows that differences in results from the two methods are due to inherent differences in the methods themselves and not just to the collection of different soil waters. The hydrological anomaly and disturbance induced by the zero-tension lysimeters affects the solute chemistry and thus the applicability of the results to field conditions.     

pH and solubility of aluminium in acidic forest soils: a consequence of reactions between organic acidity and aluminium alkalinity

Data from two Podzol O and E horizons, sampled in 1-cm layers at 13 points within 2 m × 2 m plots, were used to test the hypothesis that the composition of hydrogen ions (H) and aluminium (Al) adsorbed to the solid-phase soil organic matter (SOM) determines pH and Al solubility in organic-rich acidic forest soils. Organically adsorbed Al was extracted sequentially with 0.5 m CuCl₂ and organically adsorbed H was determined as the difference between total acidity titrated to pH 8.2 and Al extracted in 0.5 m CuCl₂. The quotient between fractions of SOM sites binding Al and H (N_Al/N_H) is shown to determine the variation in pH and Al solubility. It is furthermore shown that models in which pH and Al solubility are linked via a pH-dependent solubility of an Al hydroxide and in which cation exchange between Al³⁺ and Ca²⁺, rather than cation exchange between Al³⁺ and H⁺, is the main pH-buffering process cannot be used to simulate pH or Al solubility in O and E horizons. The fraction of SOM sites adsorbing Al increased by depth in the lower O and throughout the E horizon at the same magnitude as sites adsorbing H decreased. The fraction of sites binding the cations Ca²⁺ + Mg²⁺ + K⁺ + Na⁺ remained constant. It is suggested that a net reaction between Al silicates (proton acceptors) and protonated functional groups in SOM (proton donors) is the long-term chemical process determining the composition of organically adsorbed H and Al in the lower part of the O and in the E horizon of Podzols. Thus, in the long term, pH and Al solubility are determined by the interaction between organic acidity and Al alkalinity.     

Comparison of soil solution chemistry in zero tension and ceramic-cup tension lysimeters

The chemistry of soil solutions collected from plastic 0-tension and ceramic-cup tension lysimeters was compared. Except for NO^?₃ there was no systematic difference in the chemistry of major cations, anions, pH or Al speciation of the solutions collected by the two types of lysimeter. although there were some differences at both 25 and 75 cm depths, on such occasions the difference at the other depth was either in the apposite direction or non-significant. The concentration of NO^?₃ was significantly lower in the 0-tension lysi meters and, although the mechanism is not clearly understood, this may be due to uptake by micro-organisms feeding on fine organic matter particles in these solutions. The choice of lysimeter can be based on the objectives and constraints of the research project, rather than on the fact that the soil solution is more representative with one type of lysimeter than another.     

Aluminium chemistry in two contrasted acid forest soils and headwater streams impacted by acid deposition,Vosges mountains,N.E. France

Al chemistry was studied in two acidic watersheds, one with a podzol, the other with an acid brown soil, in the Vosges mountains (N.E. France), by analysing both leaching and centrifugation soil solutions and spring waters over 3 yr. In the podzol, Al was mobilized in the eluvial horizons under the predominant influence of organic acidity, then leached down the profile as organic and F-bound Al. Strong undersaturation with respect to proto-imogolite and imogolite showed that the proto-imogolite theory of podzolization could not apply. Al was transferred from the soil to spring water mostly as Al³⁺ and Al-F. Al³⁺, as well as additional minor species (AlOH²⁺, AlSO₄ ⁺), originated from the redissolution of the top of the spodic horizons under the influence of both soil solution acidity and the occurrence of mobile anions derived from atmospheric deposition. Conversely, in the acid brown soil, Al mobilization was regulated by nitrate and occurred mainly as Al³⁺. Most of Al was retained in the deep soil and only traces of monomeric Al reached spring water. In the podzol eluvial horizons, soil solutions were undersaturated with respect to all relevant mineral phases and their chemical composition agree with the concept of a mobilization of Al from the solid soil organic Al and a control of Al³⁺ activity by complexation reaction with the solid and soluble soil organic matter and F. In the acid brown soil, soil solutions were found to be in equilibrium with natural alunite, and the formation of this mineral, if confirmed, would account for the occurrence of 'open' vermiculites instead of the expected hydroxy-Al interlayered vermiculites. Al solubility control in surface water of both watersheds remains unclear. The Al-F species in both watersheds and the likely control of Al solubility by alunite in the acid brown soil emphasize the influence of acid deposition on Al chemistry in acid watersheds.     

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.     

Factors controlling Al-activity in soil solutions in an acid forest soil of the German Solling area

The forests of the German Solling area are heavily impacted by acidic deposition. Analysis of soil solutions derived from suction lysimeters in the field reveal strong vertical gradients of Al-activity in the soil solution and increasing activity with soil depth. Temporal pattern of Al- activity in soil solutions under field conditions cannot easily be predicted by equilibrium models using Al(OH)₃ dissolution. Percolating disturbed soil samples under laboratory conditions with artificial acid soil solutions undersaturated to Al(OH)₃ solids resulted in high rates of Al release in the 30–40 cm layer and revealed Al(OH)₃ as a possible Al-activity controlling solid. The laboratory findings are not in coincidence with field observations. This discrepancy with respect to the regulation of Al activity in the 30–40 cm layer is attributed to the effect of soil structure and the interaction of macropores and micropores under field conditions. Al activity of the soil solution in the 0–10 cm layer seems to be regulated by exchange reactions with organic substances.     

Soil tests for aluminum toxicity in the presence of organic matter: Laboratory development and assessment

Abstract

Al toxicity in plants is related to the activity of Al³⁺ and Al‐hydroxy monomers in the soil solution, whereas Al complexed with ligands such as fluoride (F), sulphate (SO₄ ^2‐), and oxalate is not toxic. Estimation of toxic Al relies on measurement of “labile”; Al after short contact times with colorimetric reagents or cation‐exchange resins. However, shifts in equilibrium may result in non‐toxic forms of Al reacting with the complexing agent or resin.

A series of laboratory experiments tested the degree to which labile Al is related to Al³⁺ in simplified media and compared methods of estimating labile Al in the presence of organic ligands and in soils. Cation‐exchange resins extracted more than the theoretical concentration of Al³⁺ from solutions containing a range of concentrations of OH^‐ and SO₄ ^2‐. More Al was extracted in 15 s by 8‐hydroxy‐quinoline than by Chelex‐100 from solutions of Al‐humate at pH 4. In sands which had been spiked with Al and organic matter, the estimation of labile Al varied with both the method of measurement and type of extract. The cations present in commonly used soil‐extracting chloride solutions can decrease the proportion of organically complexed Al.     

Solution chemistry in acid forest soils: Are the BC : Al ratios as critical as expected in Switzerland?

The molar ratio of base nutrient cations to total dissolved aluminum (BC : Al_tot) in the soil solution was measured at six forest sites in Switzerland in acid mineral soils to determine whether the ratio measured in the field was lower than the critical value of 1, as predicted by the mapping of exceedances of critical loads of acidity. The soil chemistry was then related to the soil solution composition to characterize the typical effective base saturation (BS) and BC : Al ratio in soil leading to critical BC : Al_tot in the soil solution. The median BC : Al_tot ratio in the soil solution never reached the critical value in the root zone at any sites for the whole observation period (1999–2002), suggesting that the BC : Al_tot ratios measured in the field might be higher than those modeled for the determination of critical loads of acidity. The gibbsite model usually applied for the calculation of critical loads was a poor predictor of the Al³⁺ activity at the study sites. A curvilinear pH‐pAl³⁺ relationship was found over the whole range of pH (3.8–6.5). Above a pH of 5.5, the slope of the pH‐pAl³⁺ relation was close to 3, suggesting equilibrium with Al(OH)₃. It decreased to values smaller than 1.3 below a pH of 5.5, indicating complexation reactions with soil organic matter. The BS and the BC : Al ratios in the soils were significantly correlated to the BC : Al_tot ratios in the soil solution. The soil solutions with the lowest BC : Al_tot ratios (≤ 2) were typically found in mineral soils with a BS below 10 % and a BC : Al ratio in the soil lower than 0.2. In acid pseudogleyed horizons overlying a calcareous substrate, the soil solution chemistry was strongly influenced by the composition of the underlying soil layers. The soil solutions at 80 cm had pH values and BC : Al_tot ratios much higher than expected. This situation should be taken into account for the calculations of critical loads of acidity.     

Aluminum compounds in soil solutions and their migration in podzolic soils on two-layered deposits

The fractional composition of aluminum compounds was studied in soil solutions obtained using vacuum lysimeters from loamy podzolic soils on two-layered deposits. The concentration of aluminum was estimated in brooks and a river draining the area with a predominance of these soils. In soil solutions, the concentration of aluminum was experimentally determined in the following compounds: (1) organic and inorganic monomers, (2) stable complexes with HAs and FAs together with polymers, and (3) the most stable complexes with HAs and FAs together with fine-crystalline and colloidal compounds. The total Al concentration in soil solutions from forest litter was 0.111–0.175 mmol/l and decreased with depth to 0.05 mmol/l and lower in solutions from the IIBD horizons. More than 90% of the Al in the solutions was bound into complexes with organic ligands. Some amount of Al in solution could occur in aluminosilicate sols. The translocation of Al complexes from the litter through the AE horizon to the podzolic horizon was accompanied by an increase in the ratio between the Al concentration in fraction 2 and the C concentration in the solution. The concentrations of Al_tot in the surface waters varied in the range from 0.015 to 0.030 mmol/l. Most of the Al came to the surface waters from the litter and AE horizons and partially from the podzolic horizon due to the lateral runoff along the waterproof IIBD horizon. Approximate calculations showed that the recent annual removal of Al from the AE and E horizons with the lateral runoff was 7 to 560 mg (3–21 mmol) from 1 m².