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.     

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.     

Formation of 2,4–D complexes on montmorillonites – an ab initio molecular dynamics study

Sorption of the anionic form of the pesticide 2,4–D (2,4–dichlorophenoxyacetic acid) on the surface of the clay mineral montmorillonite was investigated using a short-time ab initio molecular dynamics (MD) simulation at room temperature. Three different situations were modelled: sorption on a dry surface, on a hydrated surface and an intercalation between montmorillonite layers. In all three cases, the calcium cation compensates the excess negative charge of the montmorillonite layer and the negative charge of the 2,4–D anion. It was found that in all models with direct contact of the Ca²⁺ cation with the montmorillonite layer, the most stable position of Ca²⁺ is above the ditrigonal hole of the mineral layer. While in the case of a dry surface very stable bidentate binding is created between the 2,4–D anion and the Ca²⁺ cation, the formation of the monodentate complexes is preferred in all models that include water molecules. Hydrogen bonds formed between water molecules and the 2,4–D anion make a considerable contribution to the formation of the monodentate complexes. Tetrahedral substitutions in the montmorillonite layer have a significant effect on the formation of the complexes of any type. However, the MD simulations did not support the role of Ca²⁺ as a cation bridge in the adsorption mechanism. Calculations showed that hydrated 2,4–D···Ca²⁺ complexes are thermodynamically more stable than complexes in which the Ca²⁺ cation acts as a bridge to the surface. On the other hand, it is possible that phyllosilicates with a greater concentration of isomorphic substitutions (e.g. mica) will be able to form stable surface complexes with a cation bridge mechanism.     

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.     

Influence of the nature of clay minerals on the fixation of radiocaesium traces in an acid brown earth–podzol weathering sequence

The magnitude of radiocaesium fixation by micaceous clay minerals is affected by their transformation, which depends on weathering in soil. The net retention of radiocaesium traces was quantified by sorption–desorption experiments in the various horizons of four sandy soils forming an acid brown earth–podzol weathering sequence derived from sandy sediments and characterized by marked changes in mineral composition. The features of the 2:1 minerals of the four soils, resulting from an aluminization process in depth and a desaluminization process towards the surface, had a strong influence on Cs⁺ fixation. Beneath the desaluminization front, which deepens from the acid brown earth to the podzol, hydroxy interlayered vermiculite was dominant and the ¹³⁷Cs⁺ fixation was the weakest. At the desaluminization front depth, vermiculite was responsible for the strongest ¹³⁷Cs⁺ fixation. In the upper layers, smectite appeared in the podzolized soils and the ¹³⁷Cs⁺ fixation decreased. The magnitude in Cs⁺ fixation therefore appeared as a tracer of the transformation process affecting the 2:1 clay minerals in the acid brown earth–podzol weathering sequence. This magnitude was positively correlated with the vermiculite content of the studied soil materials estimated by the rubidium saturation method.     

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.     

Effect of Inorganic N Composition of Fertilizers on Nitrous Oxide Emission Associated with Nitrification and Denitrification

We studied the effect of repeated application (once every 2 d) of a fertilizer solution with different ratios of NH₄⁺ - and NO₃⁻-N on N₂O emission from soil. After the excess fertilizer solution was drained from soil, the water content of soil was adjusted to 50% of the maximum water-holding capacity by suction at 6 × 10³ Pa. Repeated application of NH₄⁺- rich fertilizer solution stimulated nitrification in soil more than NO₃⁻-rich fertilizer. Although the evolution of N₂O through nitrifier denitrification tended to increase with the repeated addition of a fertilizer solution rich in NH₄⁺ rather than in NO₃⁻, the contribution of nitrifier denitrification remained at levels of 20 to 36% of the total emission regardless of the inorganic N composition. The total emission of N₂O also tended to increase with the application of NH₄⁺- rather than NO₃⁻-rich fertilizer. It was suggested that the coupled process of nitrification and denitrification at micro-aerobic sites became important when fertilizer rich in NH₄⁺ was applied to soil under relatively aerobic conditions.     

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⁺.     

Analysis of Potassium Uptake by Rice Roots Treated with Aluminum Using a Positron Emitting Nuclide, 38K

We investigate the effect of Al on K⁺ uptake by rice roots. Potassium-38 (³⁸K), a positron emitting nuclide (the half-life: 7.61 min), was used to trace K⁺ behavior. When a rice root was treated with 10μM Al for 24 h, the uptake of ³⁸K in the root was increased in the range of 1 to 2 cm from the root tip compared with that of the control sample. Because the root continued to grow without showing any damage of plasma membrane during the Al treatment, it was suggested that the ³⁸K uptake was not occurred through diffusion into the cells. The uptake of ³⁸K in both treatments, with/without Al, was decreased by VO₄^3- (inhibitor of H⁺-ATPase on plasma membrane) and DNP (H⁺ ionophore) treatment, which suggested that the K⁺ uptake was performed through an active transport, such as H⁺:K⁺ transport or H⁺ gradient promoted by an Al treatment.     

Acid inputs from the atmosphere in the United Kingdom

Abstract. Inputs of acidity to the ground arise through two distinct routes: wet deposition which includes all acidity deposited in rain and snow and dry deposition, the direct sorption of SO₂, NO₂ or HNO₃ gases by vegetation or soil surfaces. The acidity from dry deposition of SO₂ and NO₂ is created during the oxidation of deposited SO₂ and NO₂ to SO²₄ and NO₃⁻ respectively. The areas of Britain experiencing the largest wet deposition of acidity are the high rainfall areas of the west and north, in particular the west central highlands of Scotland, Galloway and Cumbria where inputs exceed 1 kp H⁺ ha⁻¹ annually. Wet deposited acidity in the east coast regions of Britain is in the range 0.3–0.6 kg H⁺ ha⁻¹ a⁻¹. Monitoring data for rainfall acidity at rural sites throughout northern Britain show a decline in deposited acidity of about 50% during the last six years. Dry deposition is largest in the industrial midlands and southeast England and in the central lowlands of Scotland, where concentrations of SO₂ are largest. In these regions the dry deposition of SO₂ following oxidation may lead to acid inputs approaching 3 kg H⁺ ha⁻¹ a⁻¹ and greatly exceeding wet deposition.     

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.     

Effect of Oxidizing Power of Roots on Iodine Uptake by Rice Plants

Although iodine is harmful to plants, rice plants ( Oryza sativa L.) absorbed iodine more selectively than bromine. To explain this selective absorption, the authors proposed the following hypothesis based on the fact that the standard redox potential for (I₂+ 2e = 2I⁻) is lower than that for (Br₂+ 2e = 2Br⁻) and (Fe³⁺+ e = Fe²⁺), and the roots of rice plants are able to oxidize ferrous ion (Fe²⁺) into ferric ion (Fe³⁺), namely rice plants oxidize iodide ion (I⁻) to form molecular iodine (I₂) via the oxidizing power of their roots, and absorb the molecular iodine formed more selectively than iodide ion. Bromine, by contrast, is absorbed by rice plants only in the form of ion (Br⁻). According to this hypothesis, there should be a significant correlation between the oxidizing power of the rice roots and the amount of iodine absorbed. Therefore, the relationship between the oxidizing power of the roots and the concentration of iodine absorbed was studied in a water culture using 8 varieties of rice plants. Rice seedlings, 14 d after germination, were cultured in a solution containing 1 mg L⁻¹ each of iodide and bromide ions for 3 d. The oxidizing power of the rice roots was evaluated based on the amount of 1-naphthylamine oxidized by the roots. A significant correlation (0.78, n = 16, 0.1% significant level) was found between the oxidizing power and the concentration of iodine absorbed by the roots. However, no relationship was found between the oxidizing power of the roots and the amount of bromine absorbed.     

Nutrient fluxes in runoff on reseeded blanket bog, limed and fertilized with urea, phosphorus and potassium

Abstract. Studies have been made of the effects of 15 g N/m² as urea in two dressings during April and June on annual nutrient fluxes in runoff from reseeded blanket bog also receiving annually 6 g P/m² as granular superphosphate and 6 kg K/m² as potassium chloride. Urea applications increased significantly ( P < 0.05) the mean annual ammonium-N flux from 17 mg/m² for the P + K plots to 245 mg/m² for the N + P + K plots. Annual fluxes of total P, K and Ca were also increased ( P < 0.05) by the addition of urea. This was attributed to the effects of increased acidity around grass roots following N uptake as ammonium-N. In contrast, nitrate-N was removed from rainwater throughout the year and concentrations in runoff were at the limit of detection (< 0.01 mg/1) on many occasions. Concentrations of organic-N in runoff exceeded those of ammonium-N, but were not significantly changed by fertilization.     

Inhibition of nitrate accumulation in tropical grassland soils: effect of nitrogen fertilization and soil disturbance

In acid soils in the Eastern Plains of Colombia, forage grasses planted on land prepared before the previous dry season produced 40–50% more dry matter than when land was prepared immediately before planting. Virtually no NO₃⁻ accumulated in surface (0–10 cm) soil from three native undisturbed savanna sites. Where land was ploughed before the dry season, NO₃⁻ levels increased gradually after a 2–3 month lag, and dropped at the beginning of the rains. In samples incubated for 4 weeks, more NO₃⁻ accumulated in the wet than the dry season. A similar 2–3-month lag occurred when land was ploughed after the dry season. NH₄⁺ levels were higher in ploughed than savanna soils, and rose in all soils at the beginning of the rains. More NO₃⁻ and NH₄⁺ accumulated on incubation in pots than in soil cores. Forage grasses inhibited NO₃⁻ accumulation in the soil, relative to plant-free plots, and legumes stimulated it. N fertilization overcame this inhibition except in the case of Brachiaria humidicola .     

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.     

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.     

Metal binding with root exudates of low molecular weight

Root exudates were collected from maize plants ( Zea mays L .), grown under sterile and hydroponic conditions. Exudates of low molecular weight were isolated by filtration and dialysis (MW 1000) of the nutrient solution and analysed. Metal binding properties of the exudates were investigated at 25°C in 0.1 m NaCIO₄ ionic medium, using a potentiometric method. The total acidity of the exudates and the successive stability constants of complexes formed with Cu²⁺, Pb²⁺ and Zn²⁺ were determined.
Sugars and organic acids were the major components of the exudates. Measured total acidity was resolved into strong (5.85meq g⁻¹C), weak (2.10meq g⁻¹C) and very weak (2.20 meq g⁻¹ C) acidities. Mono-complexes were formed with Cu, Pb and Zn and bis-complexes with Cu. At pH 5, stability constants followed the order Cu>Pb>Zn.     

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.     

Protective role of proline against salt stress is partially related to the improvement of water status and peroxidase enzyme activity in cucumber

A salt-sensitive cucumber cultivar "Jinchun No. 2" ( Cucumis sativus L.) was used to investigate the role of proline in alleviating salt stress in cucumber. Proline was applied twice (day 0 and day 4 after salt treatment) as a foliar spray, with a volume of 25 mL per plant at each time. Plant dry weight, leaf relative water content, proline, malondialdehyde (MDA), Na⁺, K⁺ and Cl⁻ contents, as well as superoxide dismutase (SOD), peroxidase (POD), catalase (CAT) and ascorbate peroxidase (APX) activities in the plants were determined at day 8 after salt treatment. The results showed that 100 mmol L^–1 NaCl stress significantly decreased plant dry weight, leaf relative water and K⁺ contents, and increased leaf MDA, Na⁺ and Cl⁻ contents and SOD, POD, CAT and APX activities. However, leaf proline accumulation was not affected by salinity. The exogenous application of proline significantly alleviated the growth inhibition of plants induced by NaCl, and was accompanied by higher leaf relative water content and POD activity, higher proline and Cl⁻ contents, and lower MDA content and SOD activity. However, there was no significant difference in Na⁺ and K⁺ contents or in CAT and APX activities between proline-treated and untreated plants under salt stress. Taken together, these results suggested that the foliar application of proline was an effective way to improve the salt tolerance of cucumber. The enhanced salt tolerance could be partially attributed to the improved water status and peroxidase enzyme activity in the leaf.     

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.