Reaction kinetics of the adsorption and desorption of nickel, zinc and cadmium by goethite. I. Adsorption and diffusion of metals

The reactions of Ni, Zn and Cd with goethite were studied over a range of initial metal concentrations (10⁻⁶ to 10⁻⁴M), pH values (4 to 8), reaction times (2h to 42d) and temperatures (5 to 35°C). The adsorption of metals increased with pH, reaction time and temperature. Adsorption of Ni increased relative to Zn and Cd with increasing time and temperature. The initially rapid adsorption of metals within a few hours was followed by a much slower reaction linearly related to time^1/2, interpreted as diffusion–controlled penetration of goethite. The pH–dependent relative diffusion rates (Ni > Zn > Cd) were influenced by both affinity for goethite surfaces and by ionic radius. Diffusion coefficients of the three metals ranged from about 10⁻¹⁹to 10⁻²⁰cm²s⁻¹. The corresponding activation energies of diffusion were also calculated (Ni 35, Cd 55, Zn 90 kJ mol⁻¹). Our view about the reactions of heavy metals with goethite involves (i) adsorption of metals on external surfaces, (ii) solid–state diffusion of metals from external to internal binding sites, and (iii) metal binding and fixation at positions inside the goethite particles. The general parameters of these processes are related to the hydrolytic properties (p K values) and the ionic radii of the metals. The results show that goethite may be an efficient sink for trace metals.     

Characterization and stability of transition metal complexes of chestnut (Castanea sativa L.) leaf litter

The water- and acid-insoluble fractions of a chestnut ( Castanea sativa L.) leaf litter sample and their complexes with Cu(II), Fe(III), and Mn(II) prepared in the laboratory were characterized by major elemental analysis, total Cu, Fe, and Mn content, infrared (IR), and electron spin resonance (ESR) spectroscopy. The IR spectra revealed a broad typology of functional groups (particularly carboxyls) in the solid litter, whereas the ESR spectra showed the existence of indigenous organic free radical species, inner-sphere Fe³⁺ complexes, and outer-sphere Mn²⁺ complexes. The litter exhibited a high residual binding capacity for Cu, Fe, and Mn in chemical forms of differing stability against water leaching and proton exchange. The ESR spectra of the metal complexes prepared in the laboratory indicated that Fe³⁺ and Cu²⁺ formed highly water-stable, inner-sphere complexes, whereas Mn²⁺ formed water-labile, outer-sphere complexes. Oxygen ligands of the litter were involved in metal complexation in all cases. The litter showed the highest affinity for Cu²⁺, followed by Fe³⁺ and Mn²⁺, when it was reacted with a single metal, whereas it complexed Fe³⁺ preferentially in the presence of both Cu²⁺ and Fe³⁺. Only a limited portion of the metal ions retained at the pH of distilled water remained bound in stable forms by the litter when the pH was lowered. Thus, variations of pH in forest soils will significantly affect micronutrient metal content and mobility in leaf litter.     

Influence of pH on copper, lead and cadmium binding by an ombrotrophic peat

The effect of pH on the adsorption of copper (Cu), lead (Pb) and cadmium (Cd) by a peat soil was studied, and the results compared with those corresponding to cation binding by a dissolved peat humic acid (HA), and interpreted with a NICA–Donnan model. A potentiometric titration technique was used to determine the adsorption isotherms for H⁺, at different ionic strengths, and for Cu²⁺, Pb²⁺ and Cd²⁺ at different pH values, in a peat soil. The effect of the ionic strength on proton binding was similar for the soil (solid) organic matter and for dissolved HA. The adsorption isotherms for cation–peat and the binding curves cation–dissolved HA are almost parallel, although more cation was adsorbed per kg of C in the dissolved HA. The effect of pH on cation binding is similar for dissolved organic matter and for the organic soil. At low metal concentration the amount of adsorbed metal followed the order Cu²⁺ > Pb²⁺ > Cd²⁺. The cation-binding parameters obtained with the NICA–Donnan model allow excellent simulation of the effect of pH on the adsorption of Cu, Pb and Cd ions in the studied peat soil. The binding constants for the peat suspension were greater than the corresponding generic parameters for dissolved HA. Speciation calculations showed that for Cu and Pb, the most abundant fraction was the metal adsorbed on peat, whereas for Cd the most abundant fraction was dissolved metal.     

Correlations between extractable Na, K, Mg, Ca, P & N from fresh and dried samples of two Aquults

Significant increases in extractable ions resulted from air-drying and grinding samples of two infertile Aquults. Effects of the sample preparation differed markedly between ions and between the two soils. Regression equations were calculated to predict extractable ions in dried, ground samples from extractable ions in fresh, unground samples and the relationships were compared between the two soil series. Regressions were significantly different between soils for extractable PO³₄, Mg⁺⁺, and K⁺, but not for Ca⁺⁺ and Na⁺. Extractable NH ⁺₄ and NO-₃ in fresh, unground samples were not correlated with those in air-dry, ground samples of either soil. Differences in response to preparation between soil types appeared to be related to the oxidative status of these soils in the field, wherein constituents of more poorly-drained soils may be less stable to the oxidizing conditions of air-drying and grinding. Such complexities suggest that effects of sample preparation should be considered when interpreting soil nutrient data for studies of forest nutrient cycling and forest soil fertility.     

Caesium and strontium diffusion through sodium montmorillonite at elevated temperature

Counter ionic migration rates of dilute Cs⁺ and Sr²⁺ against sodium in a Na-montmorillonite gel are measured using a radially perfused diffusion cell. Enhanced or surface diffusion for caesium is observed both at ambient and elevated temperature. To quantify these surface diffusivities the ion-exchange properties of the diffusing species are required. Thus, exchange isotherms for caesium against sodium on montmorillonite at 22 and 90°C are given for 10⁻¹, 10⁻², and 10⁻³M background NaCl concentrations. Caesium counterion surface diffusivities at 22 and 90°C are 2.2*10⁻⁶ and 8.0 * 10⁻⁶ cm² s⁻¹, respectively. These values are found to be essentially independent of background ionic strength over the range 10⁻³ to 10⁻¹ m NaCl. Experimental evidence of enhanced transport through Na-montmorillonite for the divalent cation Sr²⁺ is also confirmed with a surface diffusivity of 2 * 10⁻⁶ cm² s⁻¹ at 22°C and in 10⁻¹ m NaCl.     

Physiological responses and adaptive strategies of wheat seedlings to salt and alkali stresses

Effects of salt (NaCl : Na₂SO₄) and alkali (NaHCO₃ : Na₂CO₃) stresses on the contents of inorganic ions and organic solutes in wheat shoots were compared to explore the physiological responses and adaptive strategies of wheat to these stresses. Wheat significantly accumulated Na⁺ and simultaneously accumulated Cl⁻, soluble sugars and proline to maintain osmotic and ionic balance under salt stress. Compared with salt stress, the high pH from alkali stress enhanced Na⁺ accumulation and affected the absorption of inorganic anions. To maintain ionic and osmotic balance, wheat accumulated organic acids, soluble sugars and proline. The accumulation of Cl⁻ and organic acids was the main difference in the physiological responses and adaptive mechanisms to salt and alkali stresses, respectively.     

Causes of soil acidification: a summary

Abstract. A review of recent data shows that (i) dissolved CO₂ has its greatest acidifying effect in soils with pH values above about 6.5, (ii) fertilizers containing NH₋₁⁺ ions or urea will acidify soil whether the ions are taken up directly by plants or are first nitrified, (iii) oxidation of nitrogen and sulphur in soil organic matter causes acidification especially after deforestation, and (iv) the acidifying effect of rainfall and dry deposition is due to sulphuric and nitric acids, SO₂ and NH₋₁⁺ ions. A table is given showing the order of magnitude of each source of acidification.     

Ca2+ Effects on K+ Fluxes in Arabidopsis Seedlings Exposed to Al3+

Potassium transport was investigated in the root elongation zone of Arabidopsis seedlings during the first minutes of Al³⁺ exposure, using the non-invasive MIFE microelectrode technique. To prevent pH changes during Al³⁺ application, and to separate aluminium from acidic stress, plants were pre-treated with 5 mM homoPIPES before addition of AlCl₃ (pH 4.2). The 30-min treatment with 50 or 500 μM AlCl₃ led to a significant increase in K⁺ efflux in solutions containing 100 μM CaCl₂. This efflux was suppressed by high concentrations of Ca²⁺ (10 mM) in the bathing solution. Our results suggest that elevated external Ca²⁺ activities can sustain K⁺ influx in the root elongation zone during Al³⁺ exposure either by maintaining [Ca²⁺]_cyt or by affecting Al³⁺ uptake across the plasma membrane.     

Comparing the effects of pH on the sorption of metals by soil and by goethite, and on uptake by plants

The effects of soil pH on sorption of cadmium, zinc, nickel and cobalt were studied by changing the pH of a soil and measuring sorption. Results were compared with published results for effects of pH on sorption of cadmium, zinc and nickel by goethite. In a further experiment, the effects of pH on the uptake of zinc and cobalt by subterranean clover were measured. Effects of pH on sorption were described in terms of the concentration of metal ions required to produce equal sorption. Where the metal ions were incubated with the soil, unit increase in pH decreased the concentration of metal ions required about 10-fold for zinc, about 7-fold for nickel, about 6-fold for cobalt, and about 4-fold for cadmium. When the soil was mixed with a large volume of solution, the effects were similar for zinc and cadmium but slightly smaller for cobalt and slightly larger for nickel. In all cases, the magnitude of the effect varied somewhat with pH. Sorption was greater with a dilute background electroiyte than with a concentrated one and the effects of pH were greater. The effects for soil were smaller than effects of pH on sorption by iron oxides for which unit increase in pH can decrease the required concentration of Zinc 35-fold and cadmium 11-fold. These results are consistent with adsorption of divalent ions on a variable charge surface that is negatively charged. They are not consistent with the adsorption of monovalent metal ions on a variable charge surface. This mechanism requires at least a 10-fold effect of pH. They show that the change in electric potential with change in pH is smaller for reacting surfaces in soil than for goethite. The effects of changing pH on the amounts of zinc and cobalt fertilizer required for equal uptake by plants was even smaller with unit increase in pH, causing a 1.4-fold increase in the amount of fertilizer required, that is, a 1.4-fold decrease in fertilizer effectiveness.     

Effects of the nitrification inhibitor dicyandiamide on potassium, magnesium and calcium leaching in grazed grassland

Abstract. Leaching of calcium (Ca), potassium (K) and magnesium (Mg) from urine patches in grazed grassland represents a significant loss of valuable nutrients. We studied the effect on cation loss of treating the soil with a nitrification inhibitor, dicyandiamide (DCD), which was used to reduce nitrate loss by leaching. The soil was a free-draining Lismore stony silt loam (Udic Haplustept loamy skeletal) and the pasture was a mixture of perennial ryegrass ( Lolium perenne ) and white clover ( Trifolium repens ). The treatment of the soil with DCD reduced Ca²⁺ leaching by the equivalent of 50%, from 213 to 107 kg Ca ha⁻¹ yr⁻¹ on a field scale. Potassium leaching was reduced by 65%, from 48 to 17 kg K ha⁻¹ yr⁻¹. Magnesium leaching was reduced by 52%, from 17 to 8 kg Mg ha⁻¹ yr⁻¹. We postulate that the reduced leaching loss of these cations was due to the decreased leaching loss of nitrate under the urine patches, and follows from their reduced requirement as counter ions in the drainage water. The treatment of grazed grassland with DCD thus not only decreases nitrate leaching and nitrous oxide emissions as reported previously, but also decreases the leaching loss of cation nutrients such as Ca²⁺, K⁺ and Mg²⁺.     

Fixation of radiocaesium traces in a weathering sequence mica → vermiculite → hydroxy interlayered vermiculite

Radiocaesium fixation in soils is reported to occur on frayed edge sites of micaceous minerals. The weathering of mica in acid soils may therefore influence the Cs⁺ fixation process and thereby the mobility of the radiopollutant. We produced a laboratory weathering model biotite → trioctahedral vermiculite → oxidized vermiculite → hydroxy interlayered vermiculite (HIV) and quantified the Cs⁺ fixation of each mineral both in a fixed K⁺–Ca²⁺ background and in acid conditions. The transformation process was achieved through K depletion by Na-tetraphenylboron, oxidation with Br₂ and Al-intercalation using NaOH and AlCl₃. In a constant K⁺–Ca²⁺ background, vermiculite fixed 92–95% of the initial ¹³⁷Cs⁺ contamination while biotite and HIV fixed only 18–33%. In acid conditions, the interlayer occupancy by either potassium (biotite) or hydroxy-Al groups (HIV) strongly limited Cs⁺ fixation to 1–4% of the initial ¹³⁷Cs⁺ contamination. Cs⁺ fixation occurred on vermiculitic sites associated with micaceous wedge zones. Though both oxidized and trioctahedral vermiculites fixed similar Cs⁺ amounts in a constant K⁺–Ca²⁺ background (92–95%), the oxidized vermiculite retained much more radiocaesium in acid conditions (78–84% against 54–59%), because of its dioctahedral character.     

灰葡萄孢霉角质酶粗提液酶学特性研究

为探究灰葡萄孢霉角质酶的酶学性质以及角质酶对植物角质层的降解作用,以灰葡萄孢霉为材料,采用角质诱导的方法得到角质酶发酵液,上清液经过分离得到角质酶粗提液,采用分光光度法探究温度、pH值、金属离子及有机溶剂对角质酶活力的影响,并通过扫描电镜探究角质酶粗提液对葡萄角质层的作用。结果表明,灰葡萄孢霉角质酶的最适反应温度为35℃,最适反应pH值为7.5,此条件下能够保持较高的热稳定性;Na⁺、Mg²⁺、Ca²⁺对酶活有促进作用,而Zn²⁺、Cu²⁺、Fe³⁺对酶活有抑制作用;甲醇、丙酮、异丙醇对酶活具有促进作用,乙醇、乙腈和三氯甲烷对酶活具有抑制作用;角质酶粗酶液对葡萄角质层具有明显的降解作用。本研究结果为果蔬采后病害的控制提供了理论依据。     

Long-term application of animal slurries to grassland alters soil cation balance

Abstract. Soil samples from a 32-year grassland field experiment were taken from 0–5, 5–10, and 10–15 cm soil depths in February 2002. Plots received annual treatments of unamended control, mineral fertilizer, three rates of pig slurry and three rates of cow slurry, each with six replicates. Samples were analysed for cation exchange capacity (CEC), exchangeable cations (Na⁺, K⁺, Ca²⁺, Mg²⁺), pH and Olsen P. Exchangeable sodium percentage (ESP) was calculated as a sodicity indicator. Mean ESP was generally greater for slurry treatments than the control, with a trend of increasing ESP with application rate. This was particularly marked for cow slurry. At 0–5 cm depth ESP increased from 1.18 in the control to 1.75 at the highest rate of pig slurry and 5.60 at the highest rate of cow slurry. Similar trends were shown for CEC, exchangeable Na⁺, K⁺ and Mg²⁺, Ca²⁺ and Olsen P. The build-up of soil P due to slurry applications, together with this combination of physical and chemical factors, may increase the risk of P loss to surface waters, particularly from soils receiving high rates of cow slurry.     

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.     

Interaction forces between soil particles: shear moduli of the < 2 μm size fraction

The shear moduli of the < 2 μm size fraction of three soils have been measured for samples of 10–35% w/w solid. Samples were thixotropic, the shear modulus increasing with time. This increase can be described by simple models and visualized in terms of the formation of links between particles. For a given soil the shear modulus increases with ionic form in the order Ca²⁺∼Mg²⁺ + + < Li⁺ and varies in a complex manner with electrolyte concentration.     

Removal of Cu2+ and Cd2+ from Aqueous Solution by Bentonite Clay Modified with Binary Mixture of Goethite and Humic Acid

Pre-modification of bentonite clay with goethite, humic acid, and a binary mixture of goethite and humic acid reagents increased its cation exchange capacity from 95 to 105.32, 120.4, and 125.8 meq/100 g of bentonite clay, respectively. The effective pre-modification of bentonite clay with goethite, humic acid, and goethite–humic acid reagents was confirmed from their Fourier transform infrared spectra which suggested that modification was effective on the AlAlOH and Si–O sites for goethite and humic acid modification and AlAlOH for goethite–humic acid modification. The presence of 0.001 M NaNO₃ electrolyte increased the adsorption capacity of bentonite clay. Temperature was observed to favor the adsorption of Cu²⁺ and Cd²⁺ onto both the raw and modified bentonite clay samples. The goethite–humic acid-modified bentonite gave the best adsorption capacity of ≈10 and 16 mg/g at 30 and 50°C, respectively, for both metal ions. The inner sphere complexation mechanism was suggested for the adsorption of both metal ions onto the modified adsorbents. Modifying bentonite clay with a binary mixture of goethite and humic acid reduced the selectivity of bentonite clay for either Cu²⁺ or Cd²⁺. Preadsorbed goethite and humic acid on bentonite clay will further reduce the mobility of heavy metal ions in soils and in aquatic environments.     

Pollution of carbonate soils in a Mediterranean climate due to a tailings spill

The retention walls in a pond containing the residues from the pyrite mine of Aznalcóllar (southern Spain) broke open on 25 April 1998, spilling approximately 6 × 10⁶ m³ of polluted water and toxic tailings, which affected some 55 km². Drying and aeration of the tailings resulted in oxidation, forming an acidic solution with high pollutant contents, the effects of which were studied in a calcareous soil. The infiltration of this solution markedly affected only the first 12 mm of the soil, where strong acidification caused the weathering of the carbonates, and where the fine mineral particles were hydrolysed. The SO₄²⁻ ions in the acidic solution precipitated almost entirely at this depth, forming gypsum, hydroxysulphates and complex sulphates. The Fe³⁺ ions also precipitated there, mainly in amorphous or poorly crystallized forms, adsorbing to As, Sb, Tl and Pb dissolved in the acidic solution. The Al³⁺ ions, though partly precipitating in the acidic layer, accumulated mostly where the soil pH exceeded 5.5 (12–14 mm in depth). They did so primarily as amorphous or poorly crystallized forms, adsorbing to Cu dissolved in the acidic solution. The Zn²⁺ and Cd²⁺ ions accumulated mainly at pH > 7.0 (19–21 mm in depth), being adsorbed chiefly by clay mineral. After 15 months, only the first 20 mm of the soil were acidified by the oxidation of the tailings and most of the pollutants did not penetrate deeper than 100 mm. Consequently, the speed of the cleanup of the toxic spill is not as important as a thorough removal of tailings together with the upper 10 cm of the soil.     

Cation type and ionic strength effects on the solution composition of an acidic subsoil

Sodium, potassium, magnesium and calcium chloride solutions of four concentrations (0.4, 1.0, 4.0, l0.0meq dm⁻³) and distilled water were equilibrated with the highly weathered, acidic subsoil of a Plinthic Paleudult from Natal at a soil:solution ratio of 2.2:1, then separated by centrifugation with an immiscible liquid and analysed for inorganic solutes. With each salt, increasing ionic strength resulted in lower solution-pH (the maximum pH was 4.95 in the distilled water equilibration) and higher aluminium concentration and activity. These effects were much less marked for sodium (maximum ΔpH of 0.47) than for the other cations (maximum ΔpH of 0.83) and both the concentration and activity of aluminium were correspondingly lower (by tenfold at the highest chloride concentration) in the sodium solutions.
Irrespective of the nature or concentration of the electrolyte added, pH and the activities of A1³⁺ and silica in solution were consistently interrelated in a way which suggests that equilibrium with the gibbsite and poorly crystalline kaolinite in this soil had been closely approached. The results provide a basis for anticipating the effect of infiltrating solutions of fertilizer salts on subsoil acidity and suggest that a beneficial effect may accrue from the presence of sodium in the cation suite of acid soils.     

Adsorption of sulphate and fluoride by variable charge soils

The adsorption of sulphate and fluoride by three variable charge soils was studied. Adsorption increased with increase in the amount of sulphate added at constant _pH, and decreased with increase of _pH.
The ratios of the amount of released OH⁻to that of the adsorbed SO^2-₄ at pH 5–0 were 0.12, 0.14 and 0.20 for the three soils, respectively, much lower than the corresponding OH⁻/F⁻ ratios which ranged from 0.3 to 1.0. For a ferric acrisol the OH⁻ released accounted, on average, for only 15% of the SO^2-₄ adsorbed, leaving more than 60% to be explained by the decrease in positive charge and the increase in negative charge carried by the soil.     

不同pH、电解质浓度条件下草酸对针铁矿吸附Cd(II)的影响及机制

用吸附平衡法研究了不同草酸浓度、体系pH对针铁矿 (G)吸附Cd2+的影响与机制以及电解质 (KNO3)浓度对针铁矿、草酸化针铁矿 (G+40 )吸附Cd2+的影响差别及原因。结果表明 ,低浓度草酸 (1mmolL-1 )促进Cd2+的吸附 ;高浓度草酸 (1mmolL-1/sup )抑制Cd2+的吸附。已吸附在针铁矿表面的草酸对Cd2+ 吸附的影响与液相中草酸的影响不同 ,这主要与草酸引起的针铁矿表面电荷性质的变化、草酸在固液两相间的分配、草酸与Cd2+的配合作用和竞争作用有关。电解质 (KNO3)浓度对针铁矿和草酸化针铁矿吸附Cd2+的影响明显不同 ,随KNO3 浓度的提高 ,针铁矿的Cd吸附率由 44.5%增至 95%以上 ,而草酸化针铁矿吸附率由 29%降至6.2% ,这主要决定于二者的电荷零点 (PZC)和体系pH变化的不同。