Cadmium adsorption on hydroxyaluminosilicate-montmorillonite complex as influenced by oxalate and citrate

The hydroxyaluminosilicate (HAS)-montmorillonite (Mt) and hydroxyaluminum (HyA)-Mt complexes are important constituents of soil colloidal complexes in acidic environments. Oxalate and citrate are dominant organic acids in the root exudates of many plants. These acids, among other factors, strongly influence the adsorption behavior of HAS-Mt and HyA-Mt complexes. In this study, we investigated the adsorption phenomena of Cd on the HAS-Mt and HyA-Mt complexes as influenced by oxalate and citrate. Without addition of oxalate and citrate, the adsorption of Cd on Mt was easy. However, in the presence of oxalate and citrate, the adsorption was strongly inhibited. In contrast, the HAS-Mt and HyA-Mt complexes in the absence of oxalate and citrate hardly adsorbed Cd. In the presence of oxalate, the HAS-Mt and HyA-Mt complexes were able to adsorb Cd. Thus, optimal concentration of oxalate for Cd adsorption on both complexes could be determined. Similarly, the HyA-Mt complex showed an optimal concentration of citrate for Cd adsorption. However, the HAS-Mt complex did not adsorb Cd in the presence of citrate. We concluded that the optimal concentrations of oxalate and citrate for Cd adsorption depended on the form of Cd ions and their proportion in the solution. Based on the amount of Cd adsorbed and the distribution of Cd species in the solution, the adsorption of Cd on the HAS-Mt and HyA-Mt complexes took place in various chemical forms.     

Cadmium,copper, and zinc adsorption by a forest soil in the presence of sludge leachate

Samples from three genetic horizons of an acidic forest soil were equilibrated with solutions containing Cd, Cu, and Zn in the presence and absence of a municipal sewage sludge leachate. Copper adsorption was greater than Cd and Zn in all three horizons, while Cd and Zn adsorption was quite similar. Relative to a NaN0₃ background solution, sludge leachate reduced Cu adsorption in all horizons; however, in the presence of leachate Zn adsorption increased in the B2 and C horizons, while Cd adsorption decreased in the Al and was unaffected in the B2 and C horizons. Distribution coefficients generally increased as solution concentration and adsorption increased. In all horizons additions of Cd and Zn were able to reduce apparent surface charge. Copper not only reduced surface charge in the Al horizon, but caused a charge reversal in the 132 and C horizons. Adsorption data were best fit by linear or Freundlich equations. Differences in adsorption between sludge leachate and NaN0₃ solutions could not be explained simply by differences in metal activities as calculated using the GEOCHEM program. Competition from cations and organics present m the sludge leachate appears to contribute to lower metal adsorption.     

三种林木凋落叶淋滤液性质及对赤红壤硼锌的影响

采用室内淋洗方法研究了尾叶桉、藜蒴和湿地松3种林木凋落叶分解过程中淋滤液性质及其对赤红壤B、Zn吸附-解吸的影响。每2个月淋洗一次凋落叶,共6次。结果表明,尾叶桉、藜蒴和湿地松凋落叶失重率分别为29.37%、13.37%和4.68%;3种凋落叶淋滤液均呈酸性,pH值介于5.08~6.37,其中藜蒴最高,尾叶桉最低;淋滤液电导率,B、Zn浓度均以藜蒴最大,湿地松最小,树种间差异显著(p<0.05);各指标在分解过程中呈先降后回升的趋势。用淋滤液浸提赤红壤时,前3次淋滤液中的B被土壤吸附,平均吸附量尾叶桉(0.821 mg/kg)>藜蒴(0.428 mg/kg)>湿地松(0.394 mg/kg);后3次淋滤液使土壤B解吸,平均解吸量尾叶桉(0.419 mg/kg)>湿地松(0.392 mg/kg)>藜蒴(0.238 mg/kg)。与B不同,土壤从3种凋落叶的各次淋滤液中均吸附Zn,平均吸附量藜蒴(0.522 mg/kg)>尾叶桉(0.391 mg/kg)>湿地松(0.100 mg/kg)。表明3个树种的凋落叶淋滤液性质相似,对B、Zn的影响规律基本一致,但影响程度有显著差异。3种凋落叶分解均能增加赤红壤Zn含量,但无助于提高土壤原有Zn的有效性;对B的影响则因分解期而异。     

The effect of pH on the total and free ionic concentrations of mnganese, zinc and cobalt in soil solutions

Samples of five soils whose pH in the field had been adjusted to between 5.0 and 7.5 were incubated with water or 0.01 m CaCl₂ at 90% field capacity. Additional samples of the most acid soil were limed to various pH values immediately before incubation. Manganese, zinc and cobalt concentrations in the soil solutions, collected by displacement, decreased as the pH increased; the concentrations in calcium chloride solutions were higher than those in water solutions. The free divalent ions Mn²+, Zn²+ and Co²+ were the major metal species in solution at pH 5 but the proportion of the metals present as the free ion decreased as the pH increased. Differences in the manganese and zinc concentrations in the solutions were due not only to the pH of these solutions but also to the original pH of the soil in the field.     

Adsorption kinetics of zinc in a calcareous soil as affected by pH and temperature

Abstract

Sorption of zinc (Zn) in a calcareous soil was studied using a miscible displacement procedure. Sorption of Zn in soil can be described by a second‐order equation and by a diffusion equation based on the overall higher value of correlation coefficient and the lower value of standard error. The results show that the sorption of Zn in soil was increased by elevated temperature and pH. The maximum of Zn sorbed in soil increased, but the rate coefficient decreased with increasing pH. The maximum of sorbed Zn and rate coefficient tended to increase with elevated temperature. The value of activation energy (E_a) estimated with different kinetic equations was found to be variable and in the range of 5.0–17 kJ.mol^‐1. The relative diffusion rate coefficient (D/r²), estimated using a diffusion equation, was found to be in the order of 10^‐6 sec^‐1. The intra‐aggregate diffusion and/or film diffusion of Zn may be a rate‐limiting process in the sorption of Zn in soils.     

Ionic strength effect on heavy metal adsorption by soil

Abstract

The adsorption of Cd and Cu by three different soils was studied in the presence of variable concentrations of calcium chloride. Cadmium adsorption fitted the Freundlich equation while Cu better fitted the Langmuir equation. Increasing ionic strength decreased metal adsorption because of the competition of Ca‐ions for the adsorption sites of the soils.

Results could be useful from the standpoint of correct management of sewage sludges and animal slurries applied to agricultural soils because they have an electrolyte concentration greater than that found in normal soil solutions.     

The effect of soil pH and high urea concentrations on urease activity in soil

The rate of hydrolysis of urea in soil over the wide range of concentrations, up to 10 moles N per dm³ soil solution, found in fertilizer practice, was examined in Begbroke sandy loam adjusted to different pH values. On rewetting air-dry soil, urease activity increased rapidly, reached a maximum within the first 24 h and then decreased slowly to level off after about 4 days. Pretreatment of the soil with urea or ammonium had no effect on the urease activity. Urease activity increased with substrate concentration, reached an optimum value and then decreased with rising urea concentration. The results could be explained by substrate inhibition at higher urea concentrations, and the data are well described by a modified Michaelis-Menten equation involving three parameters, V_max, K_m and K_i where K_i is an inhibition constant. K_m decreased linearily with rise in pH whereas K_i increased slightly between pH 4.9 and 7.0 and steeply between 7.0 and 8.4. V_max increased with rise in pH, reached a maximum value at pH 6.0 and then declined at higher pHs. There was a further reaction, reaching a maximum rate at a urea concentration of about 0.2 molar N in the soil solution, that followed Michaelis-Menten kinetics. K_m for this high affinity reaction increased up to pH 7.2 and then decreased at higher pH values; V_max increased up to pH 6.8 and then decreased. The contribution of the high affinity reaction was small except at low concentrations of urea.     

The effects of phosphate on zinc sorption by a soil

Zinc sorption curves were obtained after treatment of a soil with several rates of phosphate and with two rates of lime. The lime permitted evaluation of the effects of phosphate on Zn sorption via its effects on pH. The phosphate was either incubated with the soil at a high temperature before reaction with Zn or was supplied at the same time as the Zn. This produced treatments with similar concentration of phosphate in solution but different amounts of sorbed phosphate.
Two distinct effects of phosphate addition on Zn sorption were detected. One arose from effects of phosphate on pH. This effect could be large and could either increase or decrease Zn sorption depending on the direction of the pH effect. A second effect was correlated with the amount of sorbed phosphate and was assumed to operate through the effects of phosphate on charge. The effects were small at low levels of Zn but larger at higher levels. This suggested that Zn and phosphate were sorbed at opposite ends of a spectrum of electrostatic potentials and overlap only occurred when the level of application was high. A third possible effect, due to reaction of the soil with zinc phosphate complexes in solution, was not proved.     

The effect of aging biosolids on the availability of cadmium and zinc in soil

A major concern with the safe re‐use of biosolids on land is the potential for release of metals from organic matter in the biosolids, due to decomposition proceeding as biosolids age. To quantify the effects of biosolid aging on Cd and Zn bioavailability, two sewage sludges (Lagoon sludge and Filtered sludge) and a garden compost were incubated at 25°C and 35°C for 100 days. Changes in availability of Cd and Zn were determined using isotope dilution principles, with the materials being labelled with carrier‐free ¹⁰⁹Cd and ⁶⁵Zn. We determined isotopically exchangeable metal pools (E values) and plant available metal pools (L values) by measuring specific activities of Cd and Zn in soil extracts and in wheat plants, respectively. Changes in carbon content over time were determined using ¹³C‐NMR spectroscopy and chemical extraction methods, and related to changes in availability of metal pools as determined by isotopic procedures. Hot‐water‐extractable carbon content, assumed to represent easily decomposable organic matter, decreased during the 100 days by 80–190 mg kg^?1. The Compost and Lagoon sludge showed no change in L values for Cd or Zn with time, but in the Filtered sludge the L values for Cd and Zn increased significantly, by 43% and 56%, respectively. The isotopically exchangeable pools of Cd and Zn did not change with incubation treatment of the biosolids. These data indicate that the potential for metal release from biosolids as organic matter decomposes depends to a large extent on the biosolid composition.     

土壤pH值和含水量对土壤硝化抑制剂效果的影响

硝化抑制剂如2-氯-6-三氯甲基吡nitrapyrin,通常与氮肥配施来抑制硝化作用提高农田中肥料的利用率,但是其抑制效果会受到土壤理化性质的影响。采用新工艺重新合成后的新型nitrapyrin纯度高达98%,由于杂质减少而具有更好的硝化抑制效果。为了研究土壤pH值和含水量对新型nitrapyrin抑制效果的影响,明确nitrapyrin适合施用的土壤条件,采用室内培养试验,研究了在不同的土壤pH值和含水量下nitrapyrin对无机氮含量动态变化和硝化作用强度的影响,以及其硝化抑制率的变化规律。结果表明:随着土壤pH值的升高,铵态氮含量降低,硝态氮含量和表观硝化率呈现上升的趋势,并且在所有pH值处理下氮肥配施nitrapyrin均显著地降低了矿质氮库铵态氮的转化量,均不同程度地抑制了硝化作用;在培养的第9天,nitrapyrin在pH值7.70处理下对硝化作用抑制效果最好,硝化抑制率达到91.53%,但硝化抑制率的降低速率在高pH值处理上更快;在培养的第45天,当pH值为4.66时,硝化抑制率为36.43%,显著高于其他处理;在整个培养过程中,施用nitrapyrin能显著抑制各处理的硝化作用,硝化抑制率在不同土壤含水量上的表现为:40%WHC60%WHC80%WHC。可见,nitrapyrin更加适合施用在酸性土壤以及旱地土壤上,该研究可以为新型硝化抑制剂nitrapyrin在农田中施用的最优条件提供理论依据。     

柠檬酸盐和磷酸盐存在下酸性磷素酶在矿物和土壤胶体上的吸附

The aim of this work was to study the influence of phosphate and citrate, which are common inorganic andorganic anions in soils, on the adsorption of acid phosphatase by kaolin, goethite and the colloids separatedfrom yellow-brown soil (YBS) and latosol (LS) in central-south China. The YBS colloid has the major claymineral composition of 1.4 nm mineral, illite and kaolinite while the LS colloid mainly contains kaolinite andoxides. The adsorption isotherm of acid phosphatase on the examined soil colloids and minerals fitted tothe Langmuir model. The amount of enzyme adsorbed in the absence of ligands was in the order of YBScolloid ＞LS colloid＞kaolin≈goethite. In the presence of phosphate or citrate, the amounts of the enzymeadsorbed followed the sequence YBS colloid＞kaolin＞LS colloid＞goethite. The presence of ligands alsodecreased the binding energy between the enzyme and soil colloids or minerals. With the increase of ligandconcentration from 10 mmol L-1 to 400 m mol L-1, different behaviors for the adsorption of enzyme werefound in the colloid and mineral systems studied. A sharp decrease in enzyme adsorption was observed ongoethite while gradual decreases of enzyme adsorption were recorded in the two soil colloid systems. However,no any decrease was found for the amount of enzyme adsorbed on kaolin at higher ligand concentrations.When phosphate or citrate was introduced to the system before the addition of enzyme, the ligands usuallyenhanced the adsorption of enzyme. The results obtained in this study suggested the important role ofkaolinite mineral in the adsorption of enzyme molecules in acidic soils in the presence of various ligands.     

The effect of pH on zinc transformation in autoclaved soils treated with pyrophosphate

Abstract

Zinc solubility in soils can be affected by both pH and pyrophosphate (PP), yet the reaction of PP is influenced by pH, thus there is a need to evaluate pH effect on Zn transformation in soils treated with PP. Samples of three autoclaved soils, a Dalhousie (DT) clay, a St. Bernard (ST) loam, and an Uplands (UT) sand were equilibrated first with PP (0.0 and 9.0 P mM), then with Zn (0.0, 0.5, 1.0 Zn mM) and followed by 0.03 M KC10₄ solutions at the initial pH of 4.5, 6.0, and 7.5 with constant ionic strength. The first equilibration was for PP sorption, the second for Zn sorption and PP desorption, and the third for Zn desorption and further PP desorption. And finally, Zn of selected samples were extracted with 0.5 M KNO₃ (exchangeable Zn, Zn_KNO3), 0.5 M NaOH (organic and Fe oxides associated Zn, Zn_NaOH) solutions, and concentrated HNO₃+H₂O₂ (residual Zn, ZnHNO₃).

Increases in pH reduced PP sorption in the UT and the ST soils while high or low pH values tended to reduced it in the DT soil, indicating a competition between PP and OH ions for sorption sites. Zinc sorption was linearly related to solution pH, the slopes varied from 0.10 to 1.06, lower values were associated with PP addition, with low Zn rate, with finer textured soils, with high contents of Fe and Al materials, and with high pH buffer capacity. The values of Zn desorption and Zn_KN03 were greater at low than high pH while the reverse was true for Zn_NaOH. The pH effects on Zn sorption‐desorption and fraction distributions were less significant in soil with than without PP. The overall effect of high pH and the presence of the sorbed PP was the increased Zn specific sorption, compared to the pH or PP effect alone.     

Testing a mechanistic model. X. The effect of pH and electrolyte concentration on borate sorption by a soil

Borate sorption by a soil was measured with 0.01, 0.1, or 1.0 M sodium chloride as background electrolyte and samples of soil with a range of pH values achieved by incubating with either calcium carbonate or hydrochloric acid for 24 h at 60°C.
Borate sorption generally increased with increasing pH. The more concentrated the electrolyte, the steeper the increase. At low pH, increasing the salt concentration decreased borate sorption; at high pH, it increased sorption. There was an intermediate pH at which salt had no effect on borate sorption. The point of zero salt effect on borate sorption was at a higher pH than the point of zero salt effect on pH. This result was explained by a mechanism in which borate ions react with variable charge surfaces which are heterogeneous and for which part of the heterogeneity is in the electric potential of the surfaces. It cannot be explained by mechanisms which do not take into account the effects of the electric potential of the reacting surfaces on the reaction with borate ions. Although the behaviour of borate was broadly consistent with that of other anions, it differed in that about half of the heterogeneity had to be allocated to the binding constant for borate ions. It was suggested that this was because reaction with organic matter was more important for borate than for other anions.     

The effect of penetrating agents and pH modification on the permeability of a loam soil to water

Abstract

Five commercially available penetrating agents and sulfuric acid were tested for their ability to facilitate water penetration in soil using soil column and/or field experiments. Only one of these, “Charge”;, increased water penetration in soil column tests; all five compounds were ineffective under field conditions. While initial treatment with sulfuric acid resulted in slower penetration, periodic rewetting of treated soil indicated that water penetration was significantly enhanced.     

Aluminium speciation and pH of an acid soil in the presence of fluoride

The aim was to determine whether the addition of F to an acid soil reduces the concentration of free Al³⁺ and other forms that have been shown to be toxic to plants. The ability of two different extracts to reflect Al speciation in the soil solution was also investigated. Addition of F (0-5.2μmolg⁻¹) to an acid soil (pH 4.15, soil solution) increased the pH and total concentrations of Al and F in the soil solution whereas Al³⁺ remained constant or decreased. Soil solution pH, total soluble Al and Al extracted by 0.01 m CaCl₂ are not good predictors of the likelihood of aluminium toxicity in soils containing soluble fluoride.     

Influence of soil pH and application of zinc on the yield and uptake of selected nutrient elements by rice

Abstract

Rice grown on a recently water‐leveled Crowley silt loam that contained less than 1.8 μg g^‐1 of 0.1 N HCl‐extractable Zn with pH levels ranging from 6.8 to 7.7, responded to Zn application. Each kg ha of applied Zn as Zn chelate, 14.2 % Zn, resulted in increases of +673, +477, and +2026 kg rice ha^‐1 at pH 6.8, 7.3, and 7.7, respectively. There was a critically low concentration of Zn in rice plants at the midtillering, first joint, and panicle differentiation stages of plant development when no Zn was applied. A yield response to applied Zn was obtained when the concentration of Zn in rice tissue was less than 15 μg g^‐1.

Application of Zn resulted in a significant increase in the uptake of N by rice plants at each of the three stages of plant development. Application of Zn also resulted in relatively large and significant increases in the uptake of Zn from the soil irrespective of soil pH. The uptake of Zn by rice plants at each of the growth stages showed a two‐ to three‐fold increase following Zn application when soil pH was 6.8 and 7.3. Also, the uptake of Zn by rice plants following Zn application showed a four‐fold increase at midtillering, a five‐fold increase at first joint, and a six‐fold increase at panicle differentiation, respectively, when soil pH was 7.7.     

Effect of pH of ammonium oxalate extracting solutions on prediction of plant available molybdenum in soil

Abstract

Molybdenum (Mo) is an essential element of plants and animals and is of concern from human nutrition and environmental standpoints. Rational applications to soil of Mo in fertilizers, sewage sludges, or other soil amendments requires information of the concentrations of Mo in soils and plants. Two greenhouse experiments were conducted at Lexington, Kentucky, using surface samples of 12 soils (11 soil types) derived from diverse parent materials in Kentucky with soil pH ranging from 5.18 to 7.46. Molybdenum (Na₂MoO₄.2H₂O) was added at rates equivalent to 0, 0.3, and 0.6 mg Mo kg^‐1 soil. Tobacco (Nicotiana tabacum L., cv. Ky14) and soybean [Glycine max. (L.) Merrill cv. McCall] were grown to provide plant Mo data for Mo soil test correlations and comparisons. The primary purpose of these investigations was to determine the effect of pH of NH₄‐oxalate extractant solution on the relationship of soil Mo and Mo uptake by tobacco and soybeans, and to evaluate the automated KI‐H₂O₂ procedure for use in determining Mo in soil extracting solutions. The mean dry weight and Mo concentration of tobacco and soybean were increased by applications of Mo fertilizer to soil in the greenhouse. Dry matter of tobacco was increased 11 to 25% and concentration of Mo from 40 to 82% by each increment of added Mo fertilizer. The results of this study suggest that many soils in Kentucky are not meeting the requirements for Mo sufficiency for tobacco and soybean plants. The average amount of soil Mo extracted by NH₄‐oxalate decreased with increasing pH of extractant. Regression estimates for the relationship of Mo uptake by tobacco or soybean and extractable soil Mo show that the slope and the coefficients of determination increased with pH of NH₄‐oxalate solution from pH 3.3 to 6.0 and then decreased again at pH 6.4. The greatest amounts of variation in Mo uptake by plants (67% and 20%, respectively, for tobacco and soybean) were accounted for by the soil Mo data at pH 6.0. Soil Mo values for the NH₄‐oxalate extractant (pH 6.0) were related to values for anion exchange resin extractant (r² = 0.61**), but not soil pH. However, values for anion exchange resin were more closely related to Mo uptake by tobacco (r² = 0.86**) and soybean (r² = 0.60**) than were values for NH₄‐oxalate (r² = 0.65** and r² = 0.27**, respectively). Results of this study indicate that the automated KI‐H₂O₂ method used previously in analysis for plant Mo can be used to analyze Mo in soil extracts. Other instrumentation such as GFAAS and ICP may be effective in the analysis of extracts obtained by the NH₄‐oxalate (pH 6.0) or by anion exchange resin procedures when the Mo concentration of extracts falls within the detection limits of the instrument.     

Influence of pH and soil copper on adsorption of metalaxyl and penconazole by the surface layer of vineyard soils

The upper horizons of old vineyard soils have substantial copper contents due to the traditional use of copper-based fungicides. Total copper levels in eight vineyard soils in the Rías Baixas area of Galicia (northwestern Spain) ranged from 60 to 560 mg kg(-1) (mean +/- SD = 206 +/- 170 mg kg(-1)). The adsorption of the fungicides metalaxyl (pK(a) = 1.41) and penconazole (pK(a) = 2.83) by these soils was determined using fungicide solutions of pH 2.5 and 5.5, and desorption of fungicide adsorbed at pH 5.5 was also determined. In all cases, Freundlich equations were fitted to the data with R (2) > 0.96. Penconazole was adsorbed and retained more strongly than metalaxyl, with K(F) values more than an order of magnitude greater. In the desorption experiments, both fungicides exhibited hysteresis. Soil copper content hardly affected the adsorption of metalaxyl, but K(F) values for adsorption of penconazole increased at a rate of about 0.1 mL(n) (microg of penconazole)(1-n) (microg of Cu)(-1), which is attributed to the formation of Cu(2+)-penconazole complexes with greater affinity for soil colloids than penconazole itself. Because the dependence of K(F) for penconazole adsorption on copper content was the same at both pH values, complex formation appears not to have been affected by the solubilization of 6-17% of soil copper at pH 2.5. A similar copper dependence, or lack of dependence, was observed when 100-1000 mg kg(-1) of copper was added as Cu(NO(3))(2).2H(2)O to the solutions from which the fungicides were adsorbed.     

Effects of zinc complexes on the distribution of zinc in calcareous soil and zinc uptake by maize

The movement and availability of Zn from six organic Zn sources in a Typic Xerorthent (calcareous) soil were compared by incubation, column assay, and in a greenhouse study with maize (Zea mays L.). Zinc soil behavior was studied by sequential, diethylenetriaminepentaacetate, and Mehlich-3 extractions. In the incubation experiment, the differences in Zn concentration observed in the water soluble plus exchangeable fraction strongly correlated with Zn uptake by plants in the greenhouse experiment. Zinc applied to the surface of soil columns scarcely moved into deeper layers except for Zn-ethylenediaminetetraacetate (EDTA) that showed the greatest distribution of labile Zn throughout the soil and the highest proportion of leaching of the applied Zn. In the upper part of the column, changes in the chemical forms of all treatments occurred and an increase in organically complexed and amorphous Fe oxide-bound fractions was detected. However, the water soluble plus exchangeable fraction was not detected. The same results were obtained at the end of the greenhouse experiment. Significant increases were found in plant dry matter yield and Zn concentration as compared with the control treatment without Zn addition. Increasing Zn rate in the soil increased dry matter yield in all cases but Zn concentration in the plant increased only with Zn-EDTA and Zn-ethylenediaminedi-o-hydroxyphenyl-acetate (EDDHA) fertilizers. Higher Zn concentration in plants (50.9 mg kg(-)(1)) occurred when 20 mg Zn kg(-)(1) was added to the soil as Zn-EDTA. The relative effectiveness of the different Zn carriers in increasing Zn uptake was in the order: Zn-EDTA > Zn-EDDHA > Zn-heptagluconate >/= Zn-phenolate approximately Zn-polyflavonoid approximately Zn-lignosulfonate.