The relationship between diffuse spectral reflectance of the soil and its cation exchange capacity is scale-dependent

Diffuse reflectance spectroscopy (DRS) is increasingly being used to predict numerous soil physical, chemical and biochemical properties. However, soil properties and processes vary at different scales and, as a result, relationships between soil properties often depend on scale. In this paper we report on how the relationship between one such property, cation exchange capacity (CEC), and the DRS of the soil depends on spatial scale. We show this by means of a nested analysis of covariance of soils sampled on a balanced nested design in a 16 km × 16 km area in eastern England. We used principal components analysis on the DRS to obtain a reduced number of variables while retaining key variation. The first principal component accounted for 99.8% of the total variance, the second for 0.14%. Nested analysis of the variation in the CEC and the two principal components showed that the substantial variance components are at the > 2000-m scale. This is probably the result of differences in soil composition due to parent material. We then developed a model to predict CEC from the DRS and used partial least squares (PLS) regression do to so. Leave-one-out cross-validation results suggested a reasonable predictive capability (R2 = 0.71 and RMSE = 0.048 molc kg− 1). However, the results from the independent validation were not as good, with R2 = 0.27, RMSE = 0.056 molc kg− 1 and an overall correlation of 0.52. This would indicate that DRS may not be useful for predictions of CEC. When we applied the analysis of covariance between predicted and observed we found significant scale-dependent correlations at scales of 50 and 500 m (0.82 and 0.73 respectively). DRS measurements can therefore be useful to predict CEC if predictions are required, for example, at the field scale (50 m). This study illustrates that the relationship between DRS and soil properties is scale-dependent and that this scale dependency has important consequences for prediction of soil properties from DRS data

Displacement of Zn through acidic light-textured soils

In order to gain understanding of the movement of pollutant metals in soil. the chemical mechanisms involved in the transport of zinc were studied. The displacement of zinc through mixtures of sand and cation exchange resin was measured to validate the methods used for soil. With cation exchange capacities of 2.5 and 5.0 cmol(c) kg(-1). 5.6 and 8.4 pore volumes of 10 mM CaCl2, respectively, were required to displace a pulse of ZnCl2. A simple Burns-type model (Wineglass) using an adsorption coefficient (K-d) determined by fitting a straight line relationship to an adsorption isotherm gave a good fit to the data (K-d=0.73 and 1.29 ml g(-1), respectively). Surface and subsurface samples of an acidic sandy loam (organic matter 4.7 and 1.0%. cation exchange capacity (CEC) 11.8 and 6.1 cmol(c) kg(-1) respectively) were leached with 10 mM calcium chloride. nitrate and perchlorate. With chloride. the zinc pulse was displaced after 25 and 5 pore volumes, respectively. The Kd values were 6.1 and 2.0 ml g(-1). but are based on linear relationships fitted to isotherms which are both curved and show hysteresis. Thus. a simple model has limited value although it does give a general indication of rate of displacement. Leaching with chloride and perchlorate gave similar displacement and Kd values, but slower movement occurred with nitrate in both soil samples (35 and 7 pore volumes, respectively) which reflected higher Kd values when the isotherms were measured using this anion (7.7 and 2.8 ml g(-1) respectively). Although pH values were a little hi-her with nitrate in the leachates, the differences were insufficient to suggest that this increased the CEC enough to cause the delay. No increases in pH occurred with nitrate in the isotherm experiments. Geochem was used to calculate the proportions of Zn complexed with the three anions and with fulvic acid determined from measurements of dissolved organic matter. In all cases, more than 91% of the Zn was present as Zn2+ and there were only minor differences between the anions. Thus, there is an unexplained factor associated with the greater adsorption of Zn in the presence of nitrate. Because as little as five pore volumes of solution displaced Zn through the subsurface soil, contamination of ground waters may be a hazard where Zn is entering a light-textured soil, particularly where soil salinity is increased. Reductions in organic matter content due to cultivation will increase the hazard. (C) 2004 Elsevier B.V. All rights reserved.

Zinc sorption in selected soils

The adsorption of nutrient elements is one of the most important solid- and liquid-phase interactions determining the retention and release of applied plant nutrients and the efficiency of fertilization. The study showed that the soils with high cation exchange capacity (CEC), CaCO3 , organic matter contents, and heavy texture adsorbed more zinc (Zn). The alkaline soils from Pakistan adsorbed more Zn than English acidic soils. Langmuir and Freundlich isotherm fit was excellent, and r(2) values for the Langmuir isotherm were highly significant (r(2) =0.84 to 0.99). The Langmuir b values, representing the adsorptive capacity of a soil, increased as the texture fineness increased in the soil, with increases in the concentration of adsorptive material (such as organic matter and CaCO3) and with increases in CEC and pH. The alkaline soils from Pakistan had higher bonding energy constant and higher log Kf values than the acidic English soils. Sequential extraction of Zn in these soils showed that most of the Zn was held in CaCO3 pool in the alkaline soils, whereas in acidic soils adsorbed Zn was in exchangeable form.

Effect of pH on the development of acidic sites in clayey and sandy loam Oxisol from the Cerrado Region, Brazil

Titration curves were determined for soil from horizon samples of a clayey and a sandy loam Oxisol by (a) adding NaOH to soil suspensions and (b) incubating moist soils with Ca(OH)(2). The organic fraction was primarily responsible for buffering in both soils. Humic acids were more important than fulvic acids in buffering against NaOH additions. With Ca(OH)(2), greater buffer capacities were found due to carboxyl sites, primarily on fulvic acids, becoming complexed with Ca2+ so that in the clay soil humic and fulvic acids were equally important as buffering components while fulvic acids were more important in the sandy loam soil. The buffer capacity of organic matter against Ca(OH)(2) additions was 1.1 mol(c) kg(-1) pH(-1). In the incubated soils, exchangeable cations were also determined and changes in the amounts of exchangeable and non-exchangeable Ca2+ acidity and effective cation exchange capacity were calculated. Up to half the added Ca2+ became complexed and was nonexchangeable. Aluminum complexed by organic matter appears to be an important buffering component, together with non exchangeable H+. With the increase of pH the dissociated sites from the carboxyl groups could complex Ca2+. (c) 2005 Elsevier B.V. All rights reserved.

Effects of metals on life cycle parameters of the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils

Two control and eight field-contaminated, metal-polluted soils were inoculated with Eisenia fetida (Savigny, 1826). Three, 7, 14, 21, 28 and 42 days after inoculation, earthworm survival, body weight, cocoon production and hatching rate were measured. Seventeen metals were analysed in E.fetida tissue, bulk soil and soil solution. Soil organic carbon content, texture, pH and cation exchange capacity were also measured. Cocoon production and hatching rate were more sensitive to adverse conditions than survival or weight change. Soil properties other than metal concentration impacted toxicity. The most toxic soils were organic-poor (1-10 g C kg(-1)), sandy soils (c. 74% sand), with intermediate metal concentrations (e.g. 7150-13, 100 mg Ph kg(-1), 2970-53,400 mg Zn kg(-1)). Significant relationships between soil properties and the life cycle parameters were determined. The best coefficients of correlation were generally found for texture, pH, Ag, Cd, Mg, Pb, Tl, and Zn both singularly and in multivariate regressions. Studies that use metal-amended artificial soils are not useful to predict toxicity of field multi-contaminated soils. (c) 2007 Elsevier Ltd. All rights reserved.

Factors influencing the dissolution of phosphate rock in a range of high P-fixing soils from Cameroon

A laboratory incubation experiment was conducted to evaluate the soil factors that influence the dissolution of two phosphate rocks (PRs) of different reactivity (Gafsa, GPR, reactive PR; and Togo-Hahotoe, HPR, low reactivity PR) in seven agricultural soils from Cameroon having variable phosphorus (P)- sorption capacities, organic carbon (C) contents, and exchangeable acidities. Ground PR was mixed with the soils at a rate of 500 mg P kg 21 soil and incubated at 30 degrees C for 85 days. Dissolution of the PRs was determined at various intervals using the Delta NaOH-P method ( the difference of the amount of P extracted by 0.5 M NaOH between the PR-treated soils and the control). Between 4 and 27% of HPR and 33 and 50% of GPR were dissolved in the soils. Calcium (Ca) saturation of cation exchange sites and proton supply strongly affected PR dissolution in these soils. Acid soils with pH-(H2O), < 5 (NKL, ODJ, NSM, MTF) dissolved more phosphate rock than those with pH-(H2O) > 5 (DSC, FGT, BAF). However, the lack of a sufficient Ca sink in the former constrained the dissolution of both PRs. The dissolution of GPR in the slightly acidic soils was limited by increase in Ca saturation and that of HPR was constrained by limited supply in protons. Generally, the dissolution of GPR was higher than that of HPR for each soil. The kinetics of dissolution of PR in the soils was best described by the power function equation P At B. More efficient use of PR in these soils can be achieved by raising the soil cation exchange capacity, thereby increasing the Ca sink size. This could be done by amending such soils with organic materials.

Production and dissolution rates of earthworm-secreted calcium carbonate

Earthworms secrete granules of calcium carbonate. These are potentially important in soil biogeochemical cycles and are routinely recorded in archaeological studies of Quaternary soils. Production rates of calcium carbonate granules by the earthworm Lumbricus terrestris L. were determined over 27 days in a range of soils with differing chemical properties (pH, organic matter content, water holding capacity, bulk composition, cation exchange capacity and exchangeable cations). Production rate varied between soils, lay in the range 0–0.043 mmolCaCO3 (0–4.3 mg) earthworm−1 d−1 with an average rate of 8 × 10−3 mmolCaCO3 (0.8 mg) earthworm−1 d−1 and was significantly correlated (r = 0.68, P ≤ 0.01) with soil pH. In a second experiment lasting 315 days earthworms repeatedly (over periods of 39–57 days) produced comparable masses of granules. Converting individual earthworm granule production rates into fluxes expressed on per hectare of land per year basis depends heavily on estimates of earthworm numbers. Using values of 10–20 L. terrestris m−2 suggests a rate of 18– 3139 molCaCO3 ha−1 yr−1. Data obtained from flow-through dissolution experiments suggest that at near neutral pH, granule geometric surface areanormalised dissolution rates are similar to those for other biogenic and inorganic calcium carbonate. Fits of the data to the dissolution relationship r = k(1 − ˝)n where r = dissolution rate, k = a rate constant, ˝ = relative saturation and n = the reaction order gave values of k = 1.72 × 10−10 mol cm−2 s−1 and n = 1.8 for the geometric surface area-normalised rates and k = 3.51 × 10−13 mol cm−2 s−1 and n = 1.8 for the BET surface area-normalised rates. In 196 day leaching column experiments trends in granule dissolution rate referenced to soil chemistry corresponded to predictions made by the SLIM model for dissolution of limestone in soil. If soil solution approaches saturation with respect to calcium carbonate granule dissolution will slow or even stop and granules be preserved indefinitely. Granules have the potential to be a small but significant component of the biogeochemical cycling of C and Ca in soil.

Isolation of lactoperoxidase using different cation exchange resins by batch and column procedures

Lactoperoxidase (LP) was isolated from whey protein by cation-exchange using Carboxymethyl resin (CM-25C) and Sulphopropyl Toyopearl resin (SP-650C). Both batch and column procedures were employed and the adsorption capacities and extraction efficiencies were compared. The resin bed volume to whey volume ratios were 0.96:1.0 for CM-25C and ≤ 0.64:1.0 for SP-650 indicating higher adsorption capacity of SP-650 compared to CM-25C. The effluent LP activity depended on both the enzyme activity in the whey and the amount of whey loaded on the column within the saturation limits of the resin. The percentage recovery was high below the saturation point and fell off rapidly with over-saturation. While effective recovery was achieved with column extraction procedures, the recovery was poor in batch procedures. The whey-resin contact time had little impact on the enzyme adsorption. SDS PAGE and HPLC analyses were also carried out, the purity was examined and the proteins characterised in terms of molecular weights. Reversed phase HPLC provided clear distinction of the LP and lactoferrin (LF) peaks. The enzyme purity was higher in column effluents compared to batch effluents, judged on the basis of the clarity of the gel bands and the resolved peaks in HPLC chromatograms.