Fluoro‐mobilization of metals in a Slovak forest soil affected by the emissions of an aluminum smelter

Depositions originating from a central Slovak Al smelter may increase metal solubility in adjacent soils because they contain F (mainly HF). The reason for fluoro‐mobilization of metals may be the formation of soluble fluoro‐metal complexes or the mobilization of organic matter and subsequent formation of organo‐metal complexes. The objectives of our work were (1) to assess the extent of metal mobilization by fluoride in a Slovak Lithic Eutrochrept affected by the emissions of an Al smelter and (2) to model the dissolved metal species with the help of a chemical equilibrium model (MINEQL+). The O (Moder), A, and B horizons were equilibrated with solutions at F concentrations of 0, 0.9, 2.7, and 9.0 mmol l^—1. In the extracts, the concentrations of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Zn, dissolved organic carbon (DOC), free and complexed F, and the pH and electrical conductivity (EC) were determined. The heavy metal concentrations in the O horizon (Cd: 0.99, Cr: 18.0, Cu: 44, Ni: 26, Pb: 110, and Zn: 84 mg kg^—1) were 2.5 to 9 times larger than those in the A and B horizons. The concentrations of H₂O‐soluble F decreased from the O (261 mg kg^—1) to the A (103 mg kg^—1) and B horizon (92 mg kg^—1). In batch experiments increasing addition of F increased the equilibrium concentrations of Al, Cr, Cu, Fe, Ni, Pb, and DOC in all samples, of Cd in the A, and of K in the B horizon. At the same time the concentrations of complexed F and pH increased whereas EC decreased. Chemical equilibrium modelling indicated that the mobilizing effect of F resulted from the formation of fluoro‐Al complexes and organo‐complexes of all other metals.     

Dissolved organic carbon and nitrogen in precipitation,throughfall, soil solution,and stream water of the tropical highlands in northern Thailand

Dissolved organic matter (DOM) is important for the cycling and transport of carbon (C) and nitrogen (N) in soil. In temperate forest soils, dissolved organic N (DON) partly escapes mineralization and is mobile, promoting loss of N via leaching. Little information is available comparing DOC and DON dynamics under tropical conditions. Here, mineralization is more rapid, and the demand of the vegetation for nutrients is larger, thus, leaching of DON could be small. We studied concentrations of DOC and DON during the rainy seasons 1998–2001 in precipitation, canopy throughfall, pore water in the mineral soil at 5, 15, 30, and 80 cm depth, and stream water under different land‐use systems representative of the highlands of northern Thailand. In addition, we determined the distribution of organic C (OC) and N (ON) between two operationally defined fractions of DOM. Samples were collected in small water catchments including a cultivated cabbage field, a pine plantation, a secondary forest, and a primary forest. The mean concentrations of DOC and DON in bulk precipitation were 1.7 ± 0.2 and 0.2 ± 0.1 mg L^–1, respectively, dominated by the hydrophilic fraction. The throughfall of the three forest sites became enriched up to three times in DOC in the hydrophobic fraction, but not in DON. Maximum concentrations of DOC and DON (7.9–13.9 mg C L^–1 and 0.9–1.2 mg N L^–1, respectively) were found in samples from lysimeters at 5 cm soil depth. Hydrophobic OC and hydrophilic ON compounds were released from the O layer and the upper mineral soil. Concentrations of OC and ON in mineral‐soil solutions under the cabbage cultivation were elevated when compared with those under the forests. Similar to most temperate soils, the concentrations in the soil solution decreased with soil depth. The reduction of OC with depth was mainly due to the decrease of hydrophobic compounds. The changes in OC indicated the release of hydrophobic compounds poor in N in the forest canopy and the organic layers. These substances were removed from solution during passage through the mineral soil. In contrast, organic N related more to labile microbial‐derived hydrophilic compounds. At least at the cabbage‐cultivation site, mineralization seemed to contribute largely to the decrease of DOC and DON with depth, possibly because of increased microbial activity stimulated by the inorganic‐N fertilization. Similar concentrations and compositions of OC and ON in subsoils and streams draining the forested catchments suggest soil control on stream DOM. The contribution of DON to total dissolved N in those streams ranged between 50% and 73%, underscoring the importance of DOM for the leaching of nutrients from forested areas. In summary, OC and ON showed differences in their dynamics in forest as well as in agricultural ecosystems. This was mainly due to the differing distribution of OC and ON between the more immobile hydrophobic and the more easily degradable hydrophilic fraction.     

Variation in the sensitivity of DOC release between different organic soils following H2SO4 and sea‐salt additions

Long‐term monitoring data from eastern North America and Europe indicate a link between increased dissolved organic carbon (DOC) concentrations in surface waters over the last two decades and decreased atmospheric pollutant and marine sulphur (S) deposition. The hypothesis is that decreased acidity and ionic strength associated with declining S deposition has increased the solubility of DOC. However, the sign and magnitude of DOC trends have varied between sites, and in some cases at sites where S deposition has declined, no significant increase in DOC has been observed, creating uncertainty about the causal mechanisms driving the observed trends. In this paper, we demonstrate chemical regulation of DOC release from organic soils in batch experiments caused by changes in acidity and conductivity (measured as a proxy for ionic strength) associated with controlled SO₄^2? additions. DOC release from the top 10 cm of the O‐horizon of organo‐mineral soils and peats decreased by 21–60% in response to additions of 0–437 µeq SO₄^2? l^?1 sulphuric acid (H₂SO₄) and neutral sea‐salt solutions (containing Na⁺, Mg²⁺, Cl^?, SO₄^2?) over a 20‐hour extraction period. A significant decrease in the proportion of the acid‐sensitive coloured aromatic humic acids (measured by specific ultra‐violet absorbance (SUVA) at 254 nm) was also found with increasing acidity (P < 0.05) in most, but not all, soils, confirming that DOC quality, as well as quantity, changed with SO₄^2? additions. DOC release appeared to be more sensitive to increased acidity than to increased conductivity. By comparing the change in DOC release with bulk soil properties, we found that DOC release from the O‐horizon of organo‐mineral soils and semi‐confined peats, which contained greater exchangeable aluminium (Al) and had lower base saturation (BS), were more sensitive to SO₄^2? additions than DOC release from blanket peats with low concentrations of exchangeable Al and greater BS. Therefore, variation in soil type and acid/base status between sites may partly explain the difference in the magnitude of DOC changes seen at different sites where declines in S deposition have been similar.     

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.     

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.     

Microbial decomposition of leached or extracted dissolved organic carbon and nitrogen from pasture soils

Microbial decomposition of extracted and leached dissolved organic carbon (DOC) and nitrogen (DON) was demonstrated from three pasture soils in laboratory incubation studies. DOC concentration in water extracts ranged between 29 and 148 mg C L^?1 and DON concentration ranged between 2 and 63 mg N L^?1. Between 17 and 61 % of the DOC in the water extracts were respired as CO₂ by microbes by day 36. DON concentrations in the extracts declined more rapidly than DOC. Within the first 21 days of incubation, the concentration of DON was near zero without any significant change in the concentration of NO₃ ^? or NH₄ ⁺, indicating that microbes had utilized the organic pool of N preferentially. Decomposition of leached DOC (ranged between 7 and 66 mg C L^?1) and DON (ranged between 6 and 11 mg N L^?1) collected from large lysimeters (with perennial pasture; 50 cm diameter?×?80 cm deep) followed a similar pattern to that observed with soil extracts. Approximately 28 to 61 % of the DOC in leachates were respired as CO₂ by day 49. The concentration of DON in the leachates declined to below 1 mg N L^?1 within 7–14 days of the incubation, consistent with the observations made with extractable DON. Our results clearly show that DOC and DON components of the dissolved organic matter in pasture soils, whether extracted or leached, are highly decomposable and bioavailable and will influence local ecosystem functions and nutrient balances in grazed pasture systems and receiving water bodies.     

The seasonal variation in soil water acid neutralizing capacity in peaty podzols in Mid-Wales

Between 1985 and 1990, bulk precipitation and soil solution from the organic (Oh) and mineral (Bs) horizons of a well developed podzol were regularly sampled at a moorland catchment in Mid-Wales. Samples were analysed for pH, major cations, major anions, and dissolved organic carbon (DOC). Acid neutralizing capacity (ANC) was estimated by the charge balance method. Average monthly ANC of soil solutions from the Oh horizon varied seasonally, with a maximum in July and a minimum in February. In contrast, H⁺ concentrations varied little. Solute deposition, dominated by sodium and chloride, also varied seasonally with a winter maximum, which is reflected in the soil solution chemical composition. In the Oh horizon during winter, the increase in base cation (Na) concentrations led to release of H⁺ through ion exchange. ANC declined in the absence of any buffering mechanism. In summer, the depletion of exchangeable acidity that occurred in winter, was replenished by H⁺ produced by the dissociation of organic acids. During this period, organic anions contribute to an increase in ANC, while H⁺ concentrations remained similar to those in winter. These processes probably influenced the acidity and ANC of Bs horizon soil solutions but to a lesser extent than in the Oh horizon. Other mechanisms such as weathering and ion exchange involving H⁺ and Al may buffer solution acidity in the mineral soil.     

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.     

Adsorption of dissolved organic carbon and sulfate by acid forest soils in the Fichtelgebirge,FRG

The adsorption of dissolved organic carbon (DOC) and sulfate was examined in mineral horizons of acid soils from damaged (Oberwarmensteinach) and healthy (Wülfersreuth) Norway spruce forested sites in the Fichtelgebirge (NE-Bavaria). The A horizons of both sites desorbed DOC at all levels added, whereas the B horizons (Bs and Bv) retained added DOC at levels > 5 mmol C kg^?1. An initial mass isotherm used on the B horizon data indicated that these soils have a greater affinity for DOC than B horizons from Spodosols in the northeastern U.S. Sulfate was only retained at high solution levels, and retention was pH dependent. Nitrate and sulfate additions (1000 μeq L^?1 anion) had minor effects on DOC adsorption. Overall, there was little difference in DOC or sulfate retention at the two sites, indicating atmospheric deposition inputs have not affected these processes.     

The influence of organic acidity on the acid-base chemistry of surface waters in Maine,USA

Results from surveys of low-ANC lakes (high elevation, and seepage lakes), and of surface waters in dystrophic, acidic bogs, indicate that acidic precipitation and organic acidity are each generally necessary, but not solely sufficient, for chronically acidic status in Maine lakes. Acidic, low DOC (ANC < 0; DOC < 5 mg L^-1) lakes of all hydrologic types are acidic due largely to acidic deposition; high DOC (DOC > 30 mg L^-1) acidic seepage lakes are acidic due largely to organic acidity, and high DOC drainage lakes are acidic due to a combination of both factors. No low DOC drainage lakes are known with pH less than about 5.0, suggesting that organic acidity is necessary to depress lake pH values to below 5 in Maine at current deposition loadings,The dominant anion of low DOC, acidic waters is sulfate. Acidic waters with intermediate concentrations of DOC (5 to 30 mg L^-1), may be dominated by S04 and/or organic acidity. Seepage-input lakes were the only group to include both organically-dominated (37% of the acidic lakes) and S0₄-dominated members (63% of the acidic lakes). High DOC systems are typically low pH bogs, and are all organic acid-dominated.     

Effects of throughfall and litterfall manipulation on concentrations of methylmercury and mercury in forest‐floor percolates

The forest floor was shown to be an effective sink of atmospherically deposited methylmercury (MeHg) but less for total mercury (Hg_total). We studied factors controlling the difference in dynamics of MeHg and Hg_total in the forest floor by doubling the throughfall input and manipulating aboveground litter inputs (litter removal and doubling litter addition) in the snow‐free period in a Norway spruce forest in NE Bavaria, Germany, for 14 weeks. The MeHg concentrations in the forest‐floor percolates were not affected by any of the manipulation and ranged between 0.03 (Oa horizon) and 0.11 (Oi horizon) ng Hg L^–1. The Hg_total concentrations were largest in the Oa horizon (24 ng Hg L^–1) and increased under double litterfall (statistically significant in the Oi horizon). Similarly, concentrations of dissolved organic C (DOC) increased after doubling of litterfall. The concentrations of Hg_total and DOC correlated significantly in forest‐floor percolates from all plots. However, we did not find any effect of DOC on MeHg concentrations. The difference in the coupling of Hg_total and MeHg to DOC might be one reason for the differences in the mobility of Hg species in forest floors with a lower mobility of MeHg not controlled by DOC.     

Effects of acid sulphate on DOC release in mineral soils: the influence of SO42− retention and Al release

Dissolved organic carbon (DOC) in acid‐sensitive upland waters is dominated by allochthonous inputs from organic‐rich soils, yet inter‐site variability in soil DOC release to changes in acidity has received scant attention in spite of the reported differences between locations in surface water DOC trends over the last few decades. In a previous paper, we demonstrated that pH‐related retention of DOC in O horizon soils was influenced by acid‐base status, particularly the exchangeable Al content. In the present paper, we investigate the effect of sulphate additions (0–437 µeq l^?1) on DOC release in the mineral B horizon soils from the same locations. Dissolved organic carbon release decreased with declining pH in all soils, although the shape of the pH‐DOC relationships differed between locations, reflecting the multiple factors controlling DOC mobility. The release of DOC decreased by 32–91% in the treatment with the largest acid input (437 µeq l^?1), with the greatest decreases occurring in soils with very small % base saturation (BS, < 3%) and/or large capacity for sulphate (SO₄^2?) retention (up to 35% of added SO₄^2?). The greatest DOC release occurred in the soil with the largest initial base status (12% BS). These results support our earlier conclusions that differences in acid‐base status between soils alter the sensitivity of DOC release to similar sulphur deposition declines. However, superimposed on this is the capacity of mineral soils to sorb DOC and SO₄^2?, and more work is needed to determine the fate of sorbed DOC under conditions of increasing pH and decreasing SO₄^2?.     

Hydrochemical modelling of a stream dominated by organic acids and organically bound aluminium

An existing hydrogeochemical model, the Birkenes model (BIM), has been extended to include production of dissolved organic carbon (DOC) in the soil/water system and its chemical interactions with H⁺ and A1³⁺. The model has been calibrated and verified using precipitation and runoff data from the Svartberget catchment in northern Sweden. The catchment is impacted by moderate amounts of sulphur deposition (6 kg S ha^?1 a^?1; the stream is high in DOC (7–35 mg L^?1) and experiences episodically low pH-values (～4.0). The refined BIM is able to simulate the main variations in major chemical components of the stream water (H⁺, Ca²⁺, Mg²⁺, Al_i, Al₀, Cl^?, SO₄ ^?2 and DOC), as well as stream discharge and ¹⁸O, while Na⁺ is not well reproduced. Although very simplified relationships are used for the chemical interactions between DOC and H⁺ and aluminium, the model shows that these interactions are essential to stream acidity and aluminiumspecies content. Some of the model parameters are poorly determined by calibration with runoff data only. Soil and soil water investigations may contribute to the evaluation and development of the model structure and the representation of chemical processes. Further improvements of the model should emphasize DOC-production/absorption, detailed studies on DOC chemical behaviour and hydrological structure.     

Acidity of podzolic soils subjected to sulphur pollution near a Cu-Ni smelter at the Kola Peninsula

The acidity of the podzolic soils in coniferous forests on the northern tree line (Kola Peninsula) subjected to severe sulphur pollution is considered. The pH values of precipitation were positively correlated with the distance from the pollution point source. There was also a correlation between base saturation of the organic horizon and distance. The long-term SO₂-emissions have resulted in the higher leachability of base cations and dissolution of fulvic acids in the humus horizon. In polluted areas the flux of H⁺ from the organic layer could be stronger owing to higher proportion of hydrolysable humus compounds. Inputs of H⁺ from the atmosphere and humus horizon have resulted in the higher concentrations of the exchangeable aluminium in the illuvial horizon.     

Heavy Metals Leachability as Affected by pH of Compost-Amended Growth Medium Used in Container-Grown Rhododendrons

The leaching of heavy metals from plant growth medium, admixed with different amounts of compost (prepared from sewage sludge and yard waste) at pH 5, 6 and 7 was determined over a six-month period. Twelve-week old rhododendron cuttings were planted in 2-L containers and rainfall was supplemented with irrigation to supply two centimeters of water per day. Leachates collected over each two to four week period were analyzed for Cd, Cr, Cu, Ni, Pb and Zn using atomic spectrometry. The concentrations of Cd, Cu, Ni and Zn in the leachates increased with increasing proportions of compost in the medium and decreased with increasing time of leaching. Decreasing media pH dramatically increased the concentrations of Cd, Ni and Zn in the leachates, but had no effect on the Cu concentrations. For example, as the proportion of the compost in the pH 5 medium increased from 0 to 100 percent, the concentrations of metals (μg L^?1) in the leachates collected during the first two weeks increased from 1 to 33 (Cd), 10 to 123 (Cu), 8 to 113 (Ni) and 300 to 24,000 (Zn). Corresponding increases at pH 7 were 0.4 to 0.8 (Cd), 14 to 141 (Cu), 8 to 28 (Ni) and 100 to 400 (Zn) μg L^?1. The concentrations of Cr and Pb in the leachates remained below the detection limits regardless of media pH and amounts of compost.     

Temperature and soil moisture effects on dissolved organic matter release from a moorland Podzol O horizon under field and controlled laboratory conditions

Organic upland soils store large amounts of humified organic matter. The mechanisms controlling the leaching of this C pool are not completely understood. To examine the effects of temperature and microbial cycling on C leaching, we incubated five unvegetated soil cores from a Podzol O horizon (from NE Scotland), over a simulated natural temperature cycle for 1 year, whilst maintaining a constant soil moisture content. Soil cores were leached with artificial rain (177 mm each, monthly) and the leachates analysed for dissolved organic carbon (DOC) and their specific C‐normalized UV absorbance determined (SUVA, 285 nm). Monthly values of respiration of the incubated soils were determined as CO₂ efflux. To examine the effects of vegetation C inputs and soil moisture, in addition to temperature, we sampled O horizon pore waters in situ and collected five additional field soil cores every month. The field cores were leached under controlled laboratory conditions. Hysteresis in the monthly amount of DOC leached from field cores resulted in greater DOC on the rising, than falling temperature phases. This hysteresis suggested that photosynthetic C stimulated greater DOC losses in early summer, whereas limitations in the availability of soil moisture in late summer suppressed microbial decomposition and DOC loss. Greater DOC concentrations of in‐situ pore waters than for any core leachates were attributed to the effects of soil drying and physico‐chemical processes in the field. Variation in the respiration rates for the incubated soils was related to temperature, and respiration provided a greater pathway of C loss (44 g C m⁻² year⁻¹) than DOC (7.2 g C m⁻² year⁻¹). Changes in SUVA over spring and summer observed in all experimental systems were related to the period of increased temperature. During this time, DOC became less aromatic, which suggests that lower molecular weight labile compounds were not completely mineralized. The ultimate DOC source appears to be the incomplete microbial decomposition of recalcitrant humified C. In warmer periods, any labile C that is not respired is leached, but in autumn either labile C production ceases, or it is sequestered in soil biomass.     

Effects of Changed Soil Conditions on the Mobility of Trace Metals in Moderately Contaminated Urban Soils

Changes in the soil chemical environment can be expected to increase the leaching of trace metals bound in soils. In this study the mobility of trace metals was monitored in a column experiment for two contaminated urban soils. Four different treatments were used (i.e. rain, acid rain, salt and bark). Leachates were analysed for pH, dissolved organic carbon (DOC) and for seven trace metals (cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn)). The salt treatment produced the lowest pH values (between 5 and 6) in the effluent whereas the DOC concentration was largest in the bark treatment (40–140 mg L^?1) and smallest in the salt and acid treatments (7–40 mg L^?1). Cadmium, Ni and Zn were mainly mobilised in the salt treatment, whereas the bark treatments produced the highest concentrations of Cu and Pb. The concentrations of Cu, Cr, and Hg were strongly correlated with DOC (r ²?=?0.90, 0.91 and 0.96, respectively). A multi-surface geochemical model (SHM-DLM) produced values for metal dissolution that were usually of the correct magnitude. For Pb, however, the model was not successful indicating that the retention of this metal was stronger than assumed in the model. For all metals, the SHM-DLM model predicted that soil organic matter was the most important sorbent, although for Pb and Cr(III) ferrihydrite was also important and accounted for between 15 and 50% of the binding. The results confirm the central role of DOC for the mobilization of Cu, Cr, Hg and Pb in contaminated soils.     

The UV‐absorbance of dissolved organic matter predicts the fivefold variation in its affinity for mobilizing Cu in an agricultural soil horizon

It is well established that dissolved organic matter (DOM) mobilizes copper (Cu) in soils but it is unknown to what extent variable DOM quality affects this. During a 5 month period, 250 leachates of an uncontaminated agricultural soil were sampled at 45 cm depth using passive capillary wick samplers. The dissolved Cu and organic carbon (DOC) concentrations varied sevenfold and were weakly correlated (r = 0.56). The [Cu] : [DOC] ratio varied fivefold and exhibited a significant positive correlation (r = 0.77) with the specific UV‐absorbance of DOM at 254 nm (SUVA), indicating that the more aromatic DOM had higher Cu affinity. The dissolved Cu concentrations were predicted by an assemblage model in WHAM6 using the composition of the solid phase above the wick samplers and that of the solution, including DOC. The predicted [Cu] : [DOC] ratio was almost constant when assuming default DOM properties with 65% of all DOM active as fulvic acid (%AFA). The %AFA was subsequently varied proportionally to the SUVA of DOM and using the SUVA of pure FA (SUVA_FA) as a fitting parameter. In that case, the variation in the predicted [Cu] : [DOC] ratio was much larger and the predicted Cu concentrations were within a factor of 1.4 of the measured values for 90% of the samples. The fitted SUVA_FA was 38 l g^?1 cm^?1, in excellent agreement with that of Suwannee River FA (SUVA_FA = 37 l g^?1 cm^?1). It is concluded that the DOM quality, e.g. the aromaticity, should be taken into account when estimating Cu mobility in soils.     

Influence of added ammonium sulphate on the leaching of aluminium,nitrate and sulphate —A laboratory experiment

Relationships between the concentrations of sulphate, nitrate and Al were studied in leachates from reconstructed soil profiles of a previously N fertilized Haplic Podzol. Half of the profiles were covered with the grassDeschampsia fexuosa (Trin.), and the other half were not. The soil profiles were subjected to different N loads, in the form of ammonium sulphate. The doses were 0.5 mmol ammonium-N during the first part of the experiment and 1.0 mmol ammonium-N during the later part. Uptake of N by the vegetation almost completely eliminated the effects of added ammonium, even when the soil profile was strongly nitrifying. Fertilizer treatment caused nitrate to leach from the non-covered soil profiles, although there was a net retention of N. The concentration of Al in leachates was positively correlated with nitrate. Fertilizer treatment increased the proportion of inorganic monomeric Al in leachates. Most sulphate retention seemed to take place in the O horizon. In the presence of vegetation sulphate concentration was enhanced to a greater degree than could be explained from differences in evapotranspiration estimated from the Cl^?/S0₄ ^2? ratio in the leachates. Soil N dynamics on a forest clear-cutting are discussed with reference to the present findings.     

Efficiency of gypsum application to acid Andosols estimated using aluminum release rates and plant root growth

Abstract

A great deal of information on the efficiency of gypsum or phosphogypsum to ameliorate acidity in highly weathered soils is available, but only limited information is available on the efficiency in acid Andosols, which possess large amounts of active aluminum (Al). We examined the effectiveness of gypsum application to non-allophanic Andosols (one humus-rich A horizon and two B horizons poor in humus) using extractable soil Al analyses (batch and continuous extraction methods) and a cultivation test using burdock (Arctium lappa). With gypsum amendment, pH(H₂O) values of the soil decreased from 4.5–4.7 to 4.2–4.4, whereas the treatment made almost no difference to the values of pH(KCl). Total active Al (acid oxalate-extractable Al) was hardly affected by gypsum for all samples. Potassium chloride-extractable Al definitely decreased with the addition of gypsum in all soils; however, the decrease was small (0.1–1.4 cmol_c kg^?1) and the values still exceeded “the threshold of 2 cmol_c kg^?1” for inducing Al toxicity in sensitive plants (4.4–8.6 cmol_c Al kg^?1). The change in Al solubility with gypsum application represented by Al release rates from soils using continuous extraction methods with a dilute acetate buffer solution (10^?3 mol L^?1, pH 3.5) differed greatly among the soil samples: The release rate of one of the B horizon samples decreased by 71%, certainly showing the insolubilization of Al compounds, whereas the release rates of the A horizon sample showed almost no change. These changes in Al solubility were well correlated with the plant root growth. Root growth was improved with gypsum in the B horizon sample, whereas improvement was not observed in the A horizon soil. The decrease in the rate of Al release of another B horizon soil with gypsum treatment was smaller (by 20–34%), possibly because of lower pH values after gypsum application (pH[H₂O] of 4.2–4.3). In the B horizon soil, root growth improved only slightly. Thus, the effectiveness of gypsum application to acid Andosols appeared to be largely influenced by soil humus contents and slight differences in soil pH values, and corresponded to a decrease in Al release rates using the continuous extraction method.