Increasing pH releases colloidal lead in a highly contaminated forest soil

Colloids can play an important role in the leaching of lead (Pb) in soils, and liming to increase pH may produce conditions conducive to colloid release. We studied the effect of pH and the role of counterion valency on the mobilization of Pb in two topsoil horizons of a former shooting range. In batch experiments, the release of both dissolved and colloidal Pb was studied at a pH range between 3 and 7. The pH was adjusted with solutions of nitric acid (pH 3) and KOH and Ca(OH)₂ (pH 4–7) and the chemical composition, size and charge of the mobilized colloids were determined. In the presence of the monovalent K⁺‐ion concentrations of colloidal and dissolved Pb increased markedly with increasing pH. Colloids were stabilized not only by electrostatic but also by steric repulsion. Organic colloids seem to dominate at low pH of the KOH‐treatment; at pH > 4 mineral particles were also dispersed. Even though the presence of the Ca²⁺ ion reduced the concentrations of colloidal Pb more than did the K⁺ ion, our results of the Ca(OH)₂ treatment show that the relevance of both colloidal and dissolved Pb increases at a pH of about 5.8. Risk assessment on limed sites should therefore take into account both dissolved and colloidal Pb in judging the likelihood of Pb leaching.     

Small Scale Heterogeneity of Soil Chemical Properties: Effects on Spring Water Chemistry

Previous soil and spring water analyses in small catchments revealed low pH values in the spring water during high discharge events. This paper analyses the potential which small scale heterogeneity of soil acidity may have to explain decreasing spring water pH as a result of high discharge. Soil aggregates were collected from a C‐horizon of a Spodosol in the Fichtelgebirge. Exchangeable cations and soil solution were examined on both samples from the surfaces and the cores of aggregates which were obtained by a mechanical separation procedure. The Reuss‐Johnson soil chemical equilibrium model was used to predict soil and spring water pH values as a function of acidic input and soil air CO₂ concentration in equilibrium with both aggregate fractions. Ranges of acidic input from 160—570 μeq L⁻¹ and soil air CO₂ concentrations from 0.1 to 3 Vol. % were considered. The model predicted spring water pH values from 5.0 to 5.3 for the acidic aggregate surface samples (base saturation = 12.5%) and from 6.8 to 7.2 for the aggregate core samples (base saturation = 32.1%). The results suggest that small scale acidity gradients may expand the range of predictable spring water pH values. However, very low pH values (<5) still need additional explanation.     

Adsorption controls mobilization of colloids and leaching of dissolved phosphorus

Loss of phosphorus (P) from agriculture contributes to the eutrophication of surface waters. We have assessed the magnitude and controls of P leaching and the risk of colloid‐facilitated transport of P from sandy soils in Münster. Concentrations of soluble reactive P in drainage water and groundwater were monitored from 0.9 to 35 m depth. Total P concentrations, P saturation, and P sorption isotherms of soil samples were determined. Concentrations of dispersible soil P and colloidal P in drainage water and groundwater were investigated. The concentrations of soluble reactive P in drainage water and groundwater were close to background concentrations (< 20 µg P l^?1). Median concentrations in excess of 100 µg P l^?1 were found down to 5.6 m depth at one of four research sites and in the lower part of the aquifer. Experimentally determined equilibrium concentrations and the degree of P saturation were good predictors of P concentrations of drainage water. Large concentrations of dispersible P were released from soil with large concentrations of oxalate‐extractable P and addition of P induced further dispersion. Colloidal P was transported in a P‐rich subsoil when there was a large flow of water and after nitrate had been flushed from the soil profile and total solute concentrations were small. We conclude that the concentration of soluble reactive P in drainage water is controlled by rapid adsorption in the sandy soils. Subsurface transport of dissolved P contributes substantially to the loss of P from the soils we investigated. Accumulation of P in soils increases the risk of colloid‐facilitated leaching of P.     

Biochar application to sandy soil: effects of different biochars and N fertilization on crop yields in a 3-year field experiment

During the past years, most biochar studies were carried out on tropical soils whereas perennial field experiments on temperate soils are rare. This study presents a 3-year field experiment regarding the effects of differently produced biochars (pyrolyzed wood, pyrolyzed maize silage, hydrothermal carbonized maize silage) in interaction with digestate incorporation and mineral N fertilizer application on soil C and N, crop yields of winter wheat, winter rye and maize and the quality of winter wheat. Soil C and plant available potassium were found to be significantly positive affected by pyrolyzed wood biochar whereas the latter only in combination with N fertilization. Crop yields of winter wheat, winter rye and maize were not affected by biochar and showed no interaction effects with N fertilizer supply. Wheat grain quality and nutrition contents were significantly affected by biochar application, for example, highest amounts of phosphorus, potassium and magnesium were determined in treatments amended with pyrolyzed maize silage biochar. Biochar induced an improved availability of plant nutrients, which apparently were not yield limiting in our case. These results limit the potentials of biochar for sustainable intensification in agriculture by increasing crop yields for the temperate zones. However, detection of other environmental benefits requires further investigations.     

Insecticide dissipation after repeated field application to a Northern Thailand Ultisol

Nontarget effects of pesticides may occur when the active ingredients have a long persistence in the environment. The half-lives of six insecticides commonly used in Thai fruit orchards under tropical field conditions were determined. A mixture of endosulfan-alpha and -beta, chlorpyrifos, malathion, dimethoate, and mevinphos was applied five times in 10-day intervals onto an Ultisol (lychee plantation ground-covered with grass vegetation, northwestern Thailand). On days 1, 3, 5, 7, and 10 after each application, composite samples of the topsoil (0-10 cm) were collected and exhaustively extracted. Fitting a first-order model to the datasets revealed rapid initial dissipation [half-lives from 2.2 +/- 0.4 (malathion) to 5.4 +/- 1.3 days (chlorpyrifos)]. Volatilization appeared to be a major process of pesticide dissipation, especially for malathion and mevinphos. Because 8% of the applied endosulfan-alpha and -beta had been converted to the sulfate metabolite within 1 day after the first application, also microbial degradation contributed significantly to pesticide dissipation. Nevertheless, no trend in half-lives over the five application cycles could be observed, indicating that accelerated microbial degradation did not occur for these insecticides following the five applications. Precipitation and soil moisture were key parameters of dissipation, but dissipation processes were too complex to be generalized for all substances studied. Despite their short half-lives, all pesticides except mevinphos accumulated in soil (up to 656%; endosulfan-alpha), and this accumulation correlated significantly with the hydrophobicity of the substances (r = 0.88). This was interpreted as an aging process, and it was concluded that pesticide aging must be considered relevant also in tropical environments, where it has received very limited attention so far.     

Sulfuric acid rain treatment of Picea abies (Karst. L): Effects on nutrient solution,throughfall chemistry,and tree nutrition

To determine acid rain effects on nutrient solution, throughfall chemistry and nutrition of Picea abies, three years old saplings were treated with sulfuric acid (pH 2.7 and 2.4; 200 ml/tree and day) three times a day during a period of 10 days. The major effects on nutrient solution chemistry include significant increases of total acidity and sharp decreases in contents of phosphorus. Besides, the leaching of K, Ca and Mg out of the canopy clearly increases with precipitation acidity, resulting in significant lower Mg-contents of acidic treated spruce needles.     

Small Scale Heterogeneity of Soil Chemical Properties. I. A Technique for Rapid Aggregate Fractionation

Several recent studies have observed physical, chemical and microbiological heterogeneities on the scale of soil aggregates. The publications emphasize the ecological importance of these small scale gradients. This paper introduces a method for the rapid fractionation of soil structure units into a surface fraction and a core fraction. The technique combines a rapid freezing in liquid N₂ and standardized wet sieving of the structure units. During the sieving process the aggregate surfaces begin to thaw and are consequently washed through the sieve. The soil passing the sieve during a specified time is termed aggregate surface fraction, the remainder is the aggregate core fraction. Samples from 18 forest soil profiles were taken to study the precision and accuracy of the method, as well as factors determining the efficiency of fractionation. The precision of aggregate fractionation as determined by parallel fractionations yielded coefficients of variability of 5.3 to 7.5% and 6.5 to 11.4% for the amount of core and surface fraction, respectively. Furthermore, the proposed technique yielded results comparable to those obtained by manual razor-peeling of the aggregate surfaces. The variation of concentrations of chemical parameters in water extracts of both aggregate fractions was up to six times greater than in soil solutions obtained from mixed samples. Increasing soil organic C resulted in a decrease in the proportion of the aggregate surface soil collected under fixed sieving conditions, while clay content correlated positively with the amount of the aggregate surface fraction collected.     

Effect of dissolved organic matter on the precipitation and mobility of the lead compound chloropyromorphite in solution

Chloropyromorphite, CPM, Pb₅(PO₄)₃Cl, is one of the most insoluble lead minerals. Inducing the formation of CPM by application of phosphate to soil has been suggested for immobilizing Pb at contaminated sites. We have examined the effect of organic matter on the completeness and the rate of CPM precipitation and on the particle size and the mobility of CPM crystals. We did experiments at pH 3–7 and with varying content of dissolved organic C, 0–72 mg C l^?1, mixing Pb(NO₃)₂ (0.5 mmol l^?1) and phosphate (2 mmol l^?1) solutions. The organic matter was extracted from samples of a forest floor. The precipitates were identified by X‐ray diffraction, and their size and shape were analysed by scanning electron microscopy and by photon correlation spectroscopy. The presence of organic matter in the solutions did not affect the mass of CPM that precipitated within 30 minutes at pH 5, 6 and 7. At pH 3 and 4, however, organic matter strongly inhibited the precipitation. The particles were markedly smaller in solutions containing organic matter than without at all pHs and passed through water‐saturated columns filled with calcareous sand, whereas the precipitates from the carbon‐free solutions did not. We suggest that the organic matter blocked the surfaces of crystal seeds and impaired crystal growth. At high pH, organic matter may additionally decrease the crystal size of the individual crystals by increasing the number of crystal seeds. We conclude that organic matter in the solution might limit the potential of phosphate to immobilize Pb in soil because it favours the formation of mobile colloids.     

Molybdenum fractions and mobilization kinetics in acid forest soils

We extracted molybdenum (Mo) from eight acid forest soils (19 A, E, and B horizons) in NE-Bavaria and from one site in the Ore Mountains, using (1) anion exchange-resin, (2) 0.2 M ammonium oxalate, and (3) ascorbic acid/ammonium oxalate. The Mo concentrations in the anion exchange-resin fraction varied between 5 and 28 μg kg^-1. Oxalate-extractable Mo ranged from 44 to 407 μg kg^-1 and after reduction of iron (Fe) with ascorbic acid, 135 to 1071 μg Mo kg^-1 were extracted. The lowest concentrations of Mo were measured in acid and sesquioxide impoverished E horizons. The total concentrations of Mo in spruce needles correlated with ion exchange resin extractable Mo, indicating that this fraction represents Mo readily available to plants. The Mo and Fe dissolution kinetics during oxalate extraction were studied on 8 of the soil samples to obtain further information on Mo mobilization. Oxalate extractable iron (Fe_o) was mobilized within a few hours. A first order equation was applicable to the Fe dissolution kinetics with the rate constants ranging between 0.9 and 9.0 h^-1. The mobilization of Mo occurred in two distinct stages. An initially rapid dissolution was followed by a further increase in extractable Mo but with slower kinetics. A combined first order-diffusion equation was found to be appropriate for modelling the results. The first order rate constants for Mo mobilization ranged from 0.6 to 11.4 h^-1. However, correlations between the rates of reaction of Mo and Fe could not be established, indicating that Mo is either not distributed equally along Fe minerals or that there is another pool, possibly the organic substance of the soil, from which Mo is extractable by oxalate.     

Salts and acids as determinants of the solution composition of acidic forest soils — anion effects

The study aimed at evaluating whether salt-induced mobilization of acidity may be modified by the type of anion. For this purpose, the effects of different neutral salts on the solution composition of acid soils were investigated. The results were compared with those of the addition of acids. Two topsoil (E and A) and two subsoil horizons (Bs and Bw) were treated with NaCl, Na₂SO₄, MgCl₂, MgSO₄, HCl, and H₂SO₄ at concentrations ranging from 0 to 10 mmol dm^?3. With increasing inputs of Cl^? the pH of the equilibrium soil solution dropped, the concentrations of Al and Ca increased, and the molar Ca/(Al³⁺ + AlOH²⁺ + Al(OH)₂⁺) ratios decreased. These effects were the least pronounced when NaCl was added and the most at the HCl treatments. According to the release of acidity, the topsoils were more sensitive for salt-induced soil solution acidification whereas on base of the molar Ca/(Al³⁺ + AlOH²⁺ + Al(OH)₂⁺) ratios, the salt effect seems to be more important for the subsoils. Addition of S0₄^2? salts and H₂SO₄ induced higher pH and lower Al concentrations than the corresponding Cl^? treatments due to the SO₄^2? sorption, especially in the subsoils. The Ca/(Al³⁺ + AlOH²⁺ + Al(OH)₂⁺) ratios were higher than those of the corresponding Cl^? treatments. In subsoils even after H₂SO₄ additions these ratios were not higher than those of the NaCl treatments. The results indicate (I) that speculation about the effects of episodic salt concentrations enhancement on soil solution acidification not only need to consider the ionic strength and the cation type but also the anion type, (II) that salt-induced soil solution composition may be more crucial in subsoils than in topsoils, and (III) that in acid soils ongoing input of HNO₃ due to the precipitation load may induce an even more acidic soil solution than the inputs of H₂SO₄ of the last decade.