The solubility of aluminium in two Swedish acidified forest soils: An evaluation of lysimeter measurements using batch titration data

This paper presents aluminium (Al)-solubility data for two acid forest soils (Inceptisol and Spodosol), obtained in connection with lysimeter measurements (tension-cup and zero-tension lysimeters) and batch equilibrium experiments. The solubility of Al obtained in the batch experiments was used as a reference to test whether Al³⁺in soil solutions collected by the lysimeters was in equilibrium with secondary forms of solid-phase Al (Al(OH)₃or organically bound Al). The relation between pH and Al³⁺activity found for the zero-tension lysimeter solutions collected from the Inceptisol agreed well with that obtained in the batch experiment. This suggests that Al³⁺in the lysimeter solutions were in, or close to, equilibrium with the solid phase, whether this was organically bound Al (A horizon) or an Al(OH)₃phase (B horizon). For the tension-cup lysimeters, solutions obtained from the Inceptisol B and Spodosol Bs1 horizons were generally close to equilibrium with respect to secondary solid-phase Al (apparently Al(OH)₃; average ion activity product was 10^9.3and 10^8.8, respectively), whereas the Inceptisol A and Spodosol Bh solutions were not. The Al solubility in Inceptisol A and Spodosol Bh horizons was consistently higher than that obtained in the batch equilibrium experiment, indicating that the sampled solution partly originated from the underlying horizons. Thus, tension-cup lysimeters should be used with care in soils (or in parts of soil profiles) having steep solute concentration gradients because the soil volume from which the sample is drawn with this lysimeter type seems to be poorly defined.     

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.     

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.     

Soil Leachate Responses During 10 Years of Induced Whole-Watershed Acidification

Soil solution was collected from zero-tension lysimeters for 10 yr on two small central Appalachian watersheds in West Virginia, U.S.A. Ammonium sulfate fertilizer was applied to onecatchment 3 times per year during each year. The other watershedwas used as a reference to account for ambient baseline conditions. Ca and Mg concentrations collected below the A- andB-horizons of the treated watershed increased and then decreasedover time as a result of the treatment. By contrast, Ca and Mgconcentrations in the C-horizon continued to increase throughoutthe study period. The depletion in Ca and Mg that occurred inthe upper levels apparently occurred due to charge pairing andleaching of those base cations with NO₃ and SO₄. Theprogressively greater amounts of Ca and Mg carried through thesoil with these acid anions provided their continued increasingconcentrations in the C-horizon. NO₃ concentrations increased progressively with depth due to both the assimilationof NO₃ by vegetation and microorganisms in the upper soillayers and leaching of NO₃ into deeper soils by mesoporeflow. NO₃ became a more important ion over time with respectto pairing and leaching with base cations because its concentrations continued to increase in all soil layers, whereasSO₄ became retained in all soil layers after after severalyears of treatment, presumably induced by adsorption from increasing SO₃ concentrations.     

The effects of feeding byOniscus asellus (Isopoda) on nutrient cycling in an incubated hardwood forest soil

Summary Oniscus asellus produced changes in the nutrients leached from Oie and Oa horizons of a hardwood forest soil. Soil with isopods lost more K⁺ (54%) from the Oie horizon and more Ca²⁺ (25%), Mg²⁺ (40%), and water-extractable S (23%) from the Oa horizon than soil without isopods. In contrast, soils with isopods lost less Ca²⁺ (39076) from the Oie horizon and less dissolved C-bonded S (33%) from the Oa horizon than soil without isopods. In addition, the Oia and Oa horizons exhibited different nutrient dynamics. When isopods were present, the Oa horizon leachates accumulated more Na⁺ K⁺, Ca²⁺, Mg²⁺, NO₃ ^– , water-soluble SO₄ ^2–, and dissolved C-bonded S, and the Oie horizon retained more of these nutrients. The type of leaching solution also had a major effect on nutrients. Leaching with a simulated soil solution resulted in smaller nutrient losses for K⁺ and Mg²⁺ in both horizons and for Na⁺, Ca²⁺, and NO₃ ^– in the Oa horizon than leaching with distilled water.     

Changes in the concentrations and speciation of aluminum in response to an experimental addition of ammonium sulfate to the bear Brook Watershed,Maine, USA

An understanding of the biogeochemistry of aluminum (Al) in acid-sensitive terrestrial and aquatic ecosystems is critical to assessments of the effects of acidic deposition. Bear Brook Watershed, Maine, USA includes paired watersheds, East Bear and West Bear. Starting in November 1989, experimental additions of ammonium sulfate ((NH₄)₂SO₄; 900 mol/ha-yr) have been made to West Bear Brook Watershed. Chemical analysis of soil and stream waters were conducted to evaluate the speciation of Al prior to (1987–89) and following (1989–92) the experimental treatments. Before the treatments, soilwater Al occurred largely as inorganic monomeric Al (Ali). Concentrations of organic monomeric Al (Alo), Ali and dissolved organic C (DOC) were high in soil solutions draining the E horizon, and decreased in the lower mineral soilwater (Bs horizon) and streamwater. Streamwater concentrations of monomeric Al (Alm) were largely in the form of Alo. After the (NH₄)₂SO₄ treatments were initiated in the West Bear Brook Watershed, concentrations of Alm increased in soilwater and streamwater, largely as Ali. These increases in Al accompanied decreases in pH and increases in concentrations of SO₄ ^2? and NO₃ ^? in drainage waters. Increases in stream concentrations of Al were particularly evident during high flow events. This pattern, coupled with the increases in concentrations of Ali in upper soilwaters in response to the (NH₄)₂SO₄ addition, suggests that episodic increases in Ali were due to inputs of water entering the stream from shallow hydrologic flowpaths.     

Aluminium chemistry and acidification processes in a shallow podzol on the Swedish westcoast

Processes pertinent to soil acidification with special emphasis on the solution chemistry of A1, were studied in three adjacent small catchments on the Swedish westcoast, with mixed coniferous forest and shallow podzols (average soil depth 50 cm). Soil solution from different depths, groundwater and stream-water were sampled. Separation of organic and inorganic Al species was done with an ion exchange technique. The concentration of organic A1 species was linearly correlated with the concentration of dissolved organic C (r,², varied from 0.38 to 0.69 with p, < 0.001). In the A horizon 83 to 97 % of the dissolved A1 consisted of organic species. The average concentration of total A1 varied from 3.3 to 9.8 μmole 1^?1, in soil leachates collected below the A₀, horizon, and from 29.3 to 47.0 pmole 1^?1, in leachates collected below the A₂, horizon. The organic Al species decreased in importance with increasing soil depth. Leachates collected below the B horizon had average total A1 concentrations ranging from 95.3 to 115 pmole 1^?1, with a contribution of organic species varying between 8 and 20% of the total concentration. Activity calculations indicated an equilibrium with A1(OH)SO₄, (pK _S = 17.23) in the lower part of the B horizon, while groundwater together with some of the leachates from the upper B horizon showed a better fit with A1₁₄(OH)₁₀SO₄ (pK₁ = 117.51). Streamwater was obviously influenced by the soil organic matter in the outflow areas in terms of A1- organic matter complexes and protolysis of dissolved organic acids. There was a net outflow of Al and sulphate from the lower part of the B horizon compared to input in throughfall precipitation. The relative concentration increase varied from 64.4 to 78.0 (A1) and from 1.52 to 1.92 (sulphate). The relative increase due to evapotranspiration was estimated to be 1.4. The corresponding concentration factors for Mg and Ca were from 2.06 to 2.38, and from 0.81 to 1.07, respectively, indicating a very low Ca weathering. Data were compared with other studies, both recent and older ones. The possible influence from present-day levels of H⁺ and sulphurous compounds in the atmospheric deposition is evaluated.     

Aluminium sulphate solubility in acid forest soils in Denmark

Ion leaching in 3 sandy spruce forest soils of different origin and pH was investigated in the laboratory. Zero-tension lysimeters containing undisturbed soil columns of varying soil depth were subjected to H₂SO₄ loadings for a period of 9 weeks. The analysis of the resulting leachate supports the hypothesis that Al-sulphate minerals may form in acidic soils when exposed to acid (H₂SO₄) deposition. In the B horizon of a glaciofluvial sandy soil (pH 4.2), both H⁺ and sulphate ions were retained to maintain 2pH + PSO₄ = 11.9 in the leachate solutions. This relation between H⁺ and sulphate activity may be due to an adsorption mechanism or a precipitation mechanism. The precipitation mechanism is favored by the good fit of leachate composition to the conditions for jurbanite [AlOHSO₄] formation from gibbsite [Al(OH)₃]. In the B horizon of a sandy till at pH 3.7, the Al in soil solution (0.5 mmol L^?1) was leached with sulphate. As the sulphate load was increased, some sulphate was retained. This may also be due to the dissolution and precipitation of an Al-sulphate mineral. The ion activity products of leachate solutions from the B horizon of this soil were close to the pK_s reported for jurbanite. The conditions for the possible existence and/or formation of Al-sulphate minerals in acidic soils are discussed.     

Soil nutrient leaching in response to simulated acid rain treatment

Soil and soil solution nutrient concentrations were evaluated over a 30-mo period to determine the impact of simulated acidic precipitation (70:30 equivalent basis H₂SO₄: HNO₃) at pH values of 5.7, 4.5, 4.0, and 3.5 on forest. microcosms. Soil nutrient analysis indicated significantly lower concentrations of exchangeable Ca and Mg in the top 3.5 cm of the mineral soil after 30 mo of pH 3.5 treatment. Leachate collected from the pH 4.5, 4.0, and 3.5 treatments at the 25 cm depth (below the Å.: horizon) exhibited significant increases in Cl, NH₄, PO₄, K, and SO₄ concentrations compared to the pH 5.7 treatment. At the 50 cm depth (mid-profile) all leachate element concentrations except NH₄ increased significantly in response to treatment. At the 100 cm depth (profile bottom), no significant effects of treatment on leachate chemistry were observed. The elevated base cation concentration values found in the 50 cm soil solution samples support at least partially the described reduction in Ca and Mg in the surface soil horizon. The 100 cm concentration data indicate that cations mobilized out of the Å.: and upper B horizon in response to treatment were immobilized before reaching the bottom of the soil profile. Evaluation of nutrient flux out of the microcosm at the 100 cm depth did not indicate any statistically significant response to the treatment. Nitrate rather than SO₄ was found to be the dominant anion leaving the microcosm by an average factor of ～7 to 1.     

Chemical effects of pH 3 sulphuric acid on a soil profile

Cores of podzolic soil (monolith lysimeters) were treated for 4.8 yr with 1500 mm yr^?1 of either 0.5 mM H₂SO₄ at pH 3, equivalent to 24 g S m^?2 yr^?1 (acid treated) or distilled water (controls). The acid treatment was about 37 times greater than the average annual input of H₃O⁺ from rain at the site from which the monoliths were taken. Acid treatment acidified the litter (from pH(CaCl₂)3.4 to pH(CaCl₂)2.6) and the mineral soil to a depth of 80 cm (mean pH(CaCl₂) decrease of 0.2 unit). In the litter and upper A horizon, ion-exchange reactions provided the main neutralizing mechanism, resulting in a decrease in the reserves of extractable (in 2.5 % acetic acid) Ca, Mg, and Mn of about 70 to 80 %. Dissolution of solid phase Al from hydrous oxides provided most neutralization below this depth. Al3⁺ was the principal soluble Al species throughout the profile. In the litter and upper A horizon, some of the mobilized Al³⁺ was retained on cation exchange sites resulting in an increase in exchangeable Al. Deeper in the profile, where the exchange sites were effectively saturated with Al³⁺, no increase in exchangeable Al occurred, and Al³⁺ was, therefore, available for leaching. Some reversible adsorption of SO₄ ^2?, associated with hydrous Al oxides, occurred in the Bs and C horizons. The results are discussed in relation to possible effects of acid deposition over regions of Europe and N. America.     

Sulfur K-edge XANES spectroscopy reveals differences in sulfur speciation of bulk soils, humic acid, fulvic acid, and particle size separates

X-ray absorption near edge structure (XANES) spectra at the sulfur (S) K-edge (E=2472 eV) were compared for bulk soil material, humic and fulvic acid fractions, and different particle size separates from Ah horizons of two arable Luvisols, from an O and a Bs horizon of a Podzol under Norway spruce forest, and from an H horizon of a Histosol (peat bog). In the bulk soil samples, the contribution of reduced organic S (organic mono- and disulfides) to total sulfur increased from 27% to 52%, and the contribution of ester sulfate and SO₄²⁻-S decreased from 39% to 14% of total S in the following order: arable Luvisols Ah—forested Podzol O—Histosol H. This sequence reflects the increasing organic carbon content and the decreasing O₂ availability in that order. Neither sulfonate nor inorganic sulfide was detected in any of the bulk soil samples. For all samples except the Podzol Bs, the XANES spectra of the bulk soils differed considerably from the spectra of the humic and acid fractions of the respective soils, with the latter containing less reduced S (16-44% of total S) and more oxidized S (sulfone S: 19-35%; ester sulfate S: 14-38% of total S). Also the S speciation of most particle size fractions extracted from the Ah horizon of the Viehhausen Luvisol and the Bs horizon of the Podzol was different from that of the bulk soil. For both soils, the contribution of oxidized S species to total S increased and the contribution of sulfoxides and organic mono- and disulfides decreased with decreasing particle size. Thus, sulfur K-edge XANES spectra of alkaline soil extracts, including humic and fulvic acids or of particle size separates are not representative for the S speciation of the original soil sample they are derived from. The differences can be attributed to (i) artificial changes of the sulfur speciation during alkaline extraction (conversion of reduced S into oxidized S, loss of SO₄²⁻ during purification of the extracts by dialysis) or particle size separation (carry-over of water-soluble S, such as SO₄²⁻), but also to (ii) preferential enrichment of oxidized S in hydrophilic water-soluble soil organic matter (ester sulfate) and in the clay fraction of soils (ester sulfate, adsorbed SO₄²⁻).     

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.     

Bioavailability of DOC in leachates, soil matrix solutions and soil water extracts from beech forest floors

The biodegradability of dissolved organic carbon (DOC) in different fractions from the forest floor was studied. Soil leachate (SL, the soil solution in macropores which is freely drained from forest floor after rainfall), the soil matrix solution (SMS, the soil solution in meso-/micropores of the soil matrix), and soil water extracts (SWE) from two different beech forest floors were compared. Zero-tension and tension lysimeters were used to collect SL and SMS, respectively. Loss of DOC (during 21 days) and respiration of CO₂-C (during 7 days) were used as conventional measures of the availability of DOC. Bacterial production, measured using the leucine incorporation technique, and bacterial growth efficiency were also estimated. All methods were used to study differences in biodegradability between plots with and without ground flora (Deschampsia flexuosa or Anemone nemorosa) and different type of forest floor (with an organic (O) horizon or a mull (A) horizon). There were no differences in bioavailability of DOC from soil solutions extracted from plots with and without ground flora. The bioavailability of DOC in the different collected soil solutions varied, however. DOC in SWE was the most available, with a mean of 39% of DOC-loss in 21 days, and 18% of DOC being respired in 7 days. DOC in soil matrix solution was the least available of the soil solutions (7% respired), significantly less than DOC in soil leachate (11% respired). The methods measuring biodegradation of DOC, DOC-loss and CO₂-C respiration gave similar results and were comparable to bacterial production and bacterial growth efficiency, with the exception of SWE from the O-horizon at the D. flexuosa site, which had low bacterial production and bacterial growth efficiency, indicating a limitation of the bacterial growth. This study is one of the first to use bacterial production and bacterial growth efficiency for measuring bioavailability in terrestrial environments, giving an extra dimension for the process of biodegradation of DOC.     

Leaching of metals from a spruce forest soil as influenced by experimental acidification

Acidified (H₂SO₄+HNO₃, 3:1) throughfall waters (pH 3.16 and 3.40 as volume weighted means or control (untreated throughfall water, pH 3.72) were applied for 3.5 yr by an automatic irrigation device to lysimeters containing podzolized spruce forest soils of 0–5, 0–15 and 0–35 cm soil depth. The total volume of the leachates was measured together with their pH and total content of DOC, Na, K, Ca, Mg, Fe, Mn, Al, Cu, Zn, Cd and Pb and the initial amounts of metals and H in the soil. The main part of H⁺ added with the throughfall waters was retained within the soil. Concentrations and fluxes of Mg, Ca, Mn, Zn and Cd in the soil were significantly increased by addition of acidified throughfall waters; K was less affected. As a consequence of lowered flux of DOC in the A horizon as acid input increased, Fe, Al, Cu, and Pb fluxes also decreased. The mobility of these metals in the A horizon was shown to be regulated mainly by the formation of watersoluble organic compounds rather than directly by pH variations. Compared to the control, the additional annual loss of Mg from the soil profile in the most acid treatment was c. 10% of the currently exchangeable amount.     

Effect of simulated sulfuric acid rain on the chemistry of a sulfate-adsorbing forest soil

Simulated H₂SO₄ rain (pH 3.0, 3.5, 4.0) or control rain (pH 5.6) was applied for 3.5 yr to large lysimeter boxes containing a sulfate-adsorbing forest soil and either red alder (Alnus rubra Bong) or sugar maple (Acer saccharum Marsh.) seedlings. After removal of the plants and the litter layer, soil samples were obtained at 15-cm intervals to a total depth of 90 cm. Elevated SO₄ concentrations caused by the simulated H₂SO₄ rain were most pronounced for the top 15 cm, but extended down to 45 cm (maple) or 75 cm (alder). There were no effects on SO₄ concentrations at a depth of 75 to 90 em. This confirmed the existence of a sulfate front between 20 cm and 100 cm, as postulated earlier on the basis of extracted soil solutions. Decreases in Mg and Ca concentrations, base saturation, and soil pH were limited to the uppermost 15 cm and, in most cases, to the pH 3.0 treatment. Concentrations of Mg and Ca for the pH 3.0 treatments were greater than control at a depth of 15 to 30 cm, indicating transport of these cations from the soil surface. Concentrations of Na and K, and cation exchange capacity, were not affected by simulated H₂SO₄ rain. Elevated concentrations of NO₃ and extractable Zn throughout the alder systems indicated (1) either increased rates of symbiotic N-fixation or decreased rates of N immobilization; and (2) mobilization of Zn by all acid rain treatments.     

Variability and relationships between Pb,Cu, and Zn concentrations in soil solutions and forest floor leachates at heavily polluted sites

Seasonal variability of Cu, Pb, and Zn concentrations in litter leachates and soil solutions was examined in an afforested zone surrounding a copper smelter in SW Poland. Litter leachates (with zero‐tension lysimeters) and soil solutions (with MacroRhizon suction‐cup samplers, installed at a depth of 25–30 cm) were collected monthly at three sites differing in contamination levels in the years 2009 and 2010 (total Cu: 2380, 439, and 200 mg kg^–1, respectively). Concentrations of Cu in the litter leachate were correlated with dissolved organic C (DOC), whereas Zn and Pb were mainly related to leachate pH. Metal concentrations in the soil solution were weakly influenced by their total content in soils and the monthly fluctuations reached 300, 600, and 700% for Cu, Pb, and Zn, respectively. Metal concentrations in soil solutions (Cu 110–460 μg L^–1; Zn 20–1190 μg L^–1; Pb 0.5–36 μg L^–1) were correlated with their contents in the litter leachates. Chemical speciation, using Visual Minteq 3.0, proved organically‐complexed forms even though the correlations between metal concentrations and soil solution pH and DOC were statistically insignificant. The flux of organically‐complexed metals from contaminated forest floors is believed to be a direct and crucial factor affecting the actual heavy metal concentrations and their forms in the soil solutions of the upper mineral soil horizons.     

Effects of reduced atmospheric deposition on soil solution chemistry and elemental contents of spruce needles in NE—Bavaria,Germany

The decrease in anthropogenic deposition, namely SO₄^2— and SO₂, in European forest ecosystems during the last 20 years has raised questions concerning the recovery of forest ecosystems. The aim of this study was to evaluate if the long term data of element concentrations at the Fichtelgebirge (NE‐Bavaria, Germany) monitoring site indicates a relationship between the nutrient content of needles and the state of soil solution acidity. The soil at the site is very acidic and has relatively small pools of exchangeable Ca and Mg. The trees show medium to severe nutrient deficiency symptoms such as needle loss and needle yellowing. The Ca and Mg concentrations in throughfall decreased significantly during the last 12 years parallel to the significant decline in the throughfall of H⁺ and SO₄^2— concentrations. Soil solution concentrations of SO₄^2—, Ca and Mg generally decreased while the pH value remained stable. Aluminum concentrations decreased slightly, but only at a depth of 90 cm. Simultaneously a decrease in the molar Ca/Al and Mg/Al ratios in the soil solution was observed. Ca and Mg contents in the spruce needles decreased, emphasizing the relevance of soil solution changes for tree nutrition. The reasons for the delay in ecosystem recovery are due to a combination of the following two factors: (1) the continued high concentrations of NO₃^— and SO₄^2— in the soil solution leading to high Al concentrations and low pH values and, (2) the decreased rates of Ca and Mg deposition cause a correlated decrease in the concentration of Ca and Mg in the soil solution, since little Ca and Mg is present in the soil's exchangeable cation pools. It is our conclusion that detrimental soil conditions with respect to Mg and Ca nutrition as well as to Al stress are not easily reversed by the decreasing deposition of H⁺ and SO₄^2—. Thus, forest management is still confronted with the necessity of frequent liming to counteract the nutrient depletion in soils and subsequent nutrient deficiencies in trees.     

Soil Solution Chemical Response to Two Decades of Experimental Acidification at the Bear Brook Watershed in Maine

We examined long-term changes in soil solution chemistry associated with experimental, whole watershed-acidification at the Bear Brook Watershed in Maine (BBWM). At BBWM, the West Bear (WB) watershed has been treated with bimonthly additions of ((NH₄)₂ SO₄) since 1989. The adjacent East Bear (EB) watershed serves as a biogeochemical reference. Soil solution chemistry in the EB watershed was relatively stable from 1989?C2007, with the exception of declining SO₄?CS concentrations associated with a progressive decline in SO₄?CS deposition during this period. Soil solution chemistry in WB reflected a progressive change in acid-neutralization mechanisms from base cation buffering to Al buffering associated with treatment during this period. Total dissolved Al concentrations progressively increased over time and were ~4× higher in 2007 than in 1989. Treatment of WB was also associated with long-term increases in soil solution H⁺, SO₄?CS, and NO₃?CN, whereas soil solution dissolved organic carbon (DOC) was unresponsive to treatment. For solutes such as Ca, H⁺, and SO₄?CS, changes in stream chemistry were generally parallel to changes in soil solution chemistry, indicating a close coupling of terrestrial and aquatic processes that regulate the chemistry of solutions in this first-order stream watershed. For other solutes such as Al and DOC, solute concentrations were higher in soil solutions compared with streams, suggesting that sorption and transformation processes along hydrologic flow-paths were important in regulating the chemistry of solutions and the transport of these solutes.     

Nutrient balance in Scots pine (Pinus sylvestris L.) forest 1. Design of experiments

The main objectives of the project described in the present and four following papers are:

1. To study tree growth and nutrient status of forest soil as influenced by atmospheric depositions of S and N.
2. To study the influence of plant growth, litter decomposition and atmospheric depositions on soil acidity.
3. To study the influence of atmospheric deposition on the release of N₂O from soil.

One field plot experiment in a Scots pine forest and one lysimeter experiment were established in 1990 on weakly podzolized soils (Cambic arenosol). The experiment was established in a young Scots pine forest. N, Mg and P were applied in a factorial design. The experiment includes 12 treatments and three blocks. Soil was collected in a long-term field experiment with acid rain and filled into lysimeters (bucket type) by horizon. Under each horizon tension lysimeters were installed. The lysimeters were under a roof to avoid input of natural precipitation. S was applied as sulphuric acid diluted to pH levels of 5.5, 4.0, 3.5 and 3.0 and applied in a quantity of 1000 mm ”rain” yr^?1. Nitrogen (NH₄NO₃) was applied in three quantities: 0, 30 and 90 kg N ha^?1 yr^?1. Seedlings of Scots pine were planted in the lysimeters. Lysimeters with no trees were also established. The experiment includes four replicates.     

Effects of the addition of forest floor extracts on soil carbon dioxide efflux

Composition and effects of additions of fibric (Oi) and hemic/sapric (Oe + Oa) layer extracts collected from a 20-year-old stand of radiata pine (Pinus radiata) on soil carbon dioxide (CO₂) evolution were investigated in a 94-day aerobic incubation. The ¹³C nuclear magnetic resonance spectroscopy indicated that Oi layer extract contained greater concentrations of alkyl C while Oe + Oa layer extract was rich in carboxyl C. Extracts from Oi and Oe + Oa layers were added to a forest soil at two different polyphenol concentrations (43 and 85 μg g⁻¹ soil) along with tannic acid (TA) and glucose solutions to evaluate effects on soil CO₂ efflux. CO₂ evolution was greater in amended soils than control (deionized water) indicating that water-soluble organic carbon (WSOC) was readily available to microbial degradation. However, addition of WSOC extracted from both Oi and Oe + Oa layers containing 85 μg polyphenols g⁻¹ soil severely inhibited microbial activity. Soils amended with extracts containing lower concentrations of polyphenols (43 μg polyphenols g⁻¹ soil), TA solutions, and glucose solutions released 2 to 22 times more CO₂-C than added WSOC, indicating a strong positive priming effect. The differences in CO₂ evolution rates were attributed to chemical composition of the forest floor extracts.