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1.
The adsorption of Zn2+, Pb2+, Cu2+, Co2+, and Cd2+ (M2+) by soils was measured at concentrations ranging from 10-7 to 10-2 M in 10-3 to 10-2 M CaCI2. Exchange between Ca2+ and M2+, and solubility products [M2+][OH?]2 indicate that M2+ is not precipitated as hydroxide but is adsorbed on cation-exchange sites. The proportion of selective adsorption sites with specified values of the selectivity coefficient calculated using Ca as reference ion, increased in the order montmorillonite < humus, kaolinite, < allophane. imogolite < halloysite, iron oxides. Raising the soil pH by Ca-saturation increased both the amount and affinity of adsorption. Selectivity of adsorption increased in the order Mg, Ca < Cd, Co < Zn < Cu, Pb, and the selectivity coefficient varied from < 1 to > 10 000. The formation of the coordination complexes of heavy metal with deprotonoted OH and COOH groups as ligands is suggested as a possible mechanism of selective adsorption.  相似文献   

2.

Purpose

Understanding of the interactions between cations, mineral particles, and organic matter (OM) in soils is of paramount importance in plant nutrition and environmental science, and thus, these phenomena have been studied extensively. At present, an effective and simple tool to investigate these interactions does not exist. Based on previous studies of Wien effect in suspensions, the interactions of cations with soil mineral particles, complicated by the presence of organic matter, can be easily determined by means of Wien effect measurements, which was the objective of this study.

Materials and methods

A paddy soil originating from a yellow-brown soil, rich in organic matter, served as a test sample, from which the clay fraction of less than 2 μm in diameter was separated. Organic matter of aliquots of the clay fraction was removed by the oxidation with hot H2O2, and the natural and OM-free samples were saturated with various cations: Na+, K+, Ca2+, and Cd2+. The effects of OM present in the paddy soil on the interactions between the cations and the soil mineral particles were investigated by measuring the suspension Wien effect with a homemade apparatus, SHP-2.

Results and discussion

The weak electrical field electrical conductivities (EC0) of suspensions of the natural soils saturated with various cations were higher than those of the OM-free soils. The rate of increase in electrical conductivity of suspensions of the OM-free soil, except that of suspensions saturated with Na+, at electrical field strengths >50~100 kV?cm?1 was higher than those of the natural soil suspensions. The presence of OM increased the mean free binding energies of cations other than Na+. The increasing binding energies for K+ and Ca2+ were 0.56 and 0.57 kJ?mol?1, respectively, which were significantly larger than the increase for Cd2+ as only 0.03 kJ?mol?1. The binding energies of various cations on both natural and OM-free soils were all in the order: Na+?<?K+?<?Ca2+≈Cd2+. As opposed to its effect on the binding energies, the presence of OM reduced the mean free adsorption energies of the cations. Except for Na+, the adsorption energies of K+, Ca2+, and Cd2+ at field strengths >50 kV?cm?1 were lower in the natural soil as compared with the OM-free soil, and the differences between the adsorption energies became larger with increasing field strengths. The presence of OM made the zeta potential of the soil particles saturated with Na+ and K+ positive, and the particles saturated with Ca2+ and Cd2+ negative.

Conclusions

Organic matter affected the interactions of cations with soil mineral particles significantly. Binding and adsorption energies, which were quantitative measures of the interactions between cations and soil particles, could be determined by Wien effect measurements in suspensions. The binding energies on natural soils were larger than those on the corresponding OM-free soils, and the adsorption energies on the natural soils were lower than those on OM-free soils.  相似文献   

3.
The relationship between the main physicochemical properties of soils and the accumulation of natural Zn and 65Zn radionuclide has been studied, and the capacity of soils to limit the mobility of the element in the soil–plant system has been assessed. The contribution of each of the selected soil state parameters to the accumulation of zinc by barley has been determined, and the soil state parameters have been ranked. It has been found that the largest contributions to the variation of the resulting parameter (65Zn accumulation coefficient, Ka) are made by mobile Fe (25%), free carbonates (21%), and acid-soluble Zn (18%). The largest contributions to the ZnacKa are made by free carbonates (13%) and mobile Fe (8%). The contributions of physical clay and organic carbon in soils and qualitative composition of humic substances are almost similar (4% for each). No differences in the inactivating capacity of different soils (soddy-podzolic soils, gray forest soils, and chernozems) for 65Zn are observed. This is related to the fact that the transfer of 65Zn to plants is statistically significantly controlled by the contents of free carbonates, mobile iron, and potentially plantavailable forms of stable natural Zn (carrier of 65Zn) rather than the quantitative and qualitative composition of organic matter and the degree of dispersion of mineral particles. The analysis of the ZnacKa/65Zn Ka ratios has shown that the share of plant-available Zn in the acid-soluble form of the metal (1 M HCl) is 0.61 on the average for the studied soils, and its share in the total Zn content in the soils is only 0.14.  相似文献   

4.
5.
The adsorption of Zn, as compared with Mg, on two mineral soils, which differed in their major cation-exchange materials and with and without Ca-saturation, was measured in the presence of free CaCl2.

The adsorption of Zn as well as Mg occurred on cation-exchange sites. The Zn adsorption data conformed to a two-term Langmuir equation. The presence of two kinds of adsorption sites and their numbers and bonding energies were deduced. However, the Langmuir approach was not adopted on the basis of comparison between the total number of the adsorption sites for Zn deduced and the CEC of the soils.

As an alternative approach, the selectivity coefficient as defined by the equation:

was calculated for each adsorption equilibrium and plotted against the amount of Zn adsorbed. This [Zn]soil plot was used to estimate the capacities of the soil to adsorb Zn with specified affinities. The value varied between 1 and 1,000, whereas the corresponding value varied only between 0.5 and 1. The value was dependent upon the amount of Zn adsorbed, the status of exchangeable cations, and the major cation-exchange materials (montmorillonite VS. allophane-imogolite) in the soils. The importance of surface OH groups in allophane-imogolite as specific adsorption sites for Zn was suggested.  相似文献   

6.
The sorption and ion-exchange behavior of Co(II) and Zn in the soil-equilibrium solution system was studied for different types and varieties of native soils and their clay fractions before and after mild oxidation with H2O2 to remove the organic carbon. The parameters of the ion-exchange adsorption and the selectivity coefficients of the (Co(II), Zn)/Ca ion exchange were determined using different models for describing the relationship between the dissolved and sorbed forms of the metals. These were the empirical Langmuir and Freundlich adsorption isotherms and the model of the ion-exchange adsorption based on the acting mass law. It was found that the soil organic matter played an important role in the selectivity of the ion-exchange adsorption of Co(II) and Zn by the soils and their clay fractions. This was confirmed by an abrupt decrease (to almost 1) of the selectivity coefficients of the Co2+/Ca2+ and Zn2+/Ca2+ exchange after the treatment of the clay fraction with hydrogen peroxide.  相似文献   

7.
The adsorption of heavy metals [cadmium (Cd 2+), cobalt (Co2+), nickel (Ni2+), zinc (Zn2+), and lead (Pb)] and calcium (Ca2+) on humic acid and silica were investigated to understand the adsorptive selectivities of heavy metals on the constituents of soil. The experiments for the adsorption of Cd and Pb were carried out in a 0.1 mol L?1 (M) sodium nitrate (NaNO3) background solution, whereas those for the other metals were done in a 0.1 M sodium chloride (NaCl) solution. The adsorptive affinities of the metal ions on the humic acid and silica were ranked by the intrinsic surface complexation constants [K m 1(int)] that were calculated approximately from the adsorptive data using a constant capacitance model. The log [K m 1(int)] values of the metals were in the order Zn2+(?2.29) > Cd2+(?2.41) > Co2+(?2.74) > Ni2+(?2.92) ?> Ca2+ (?3.33) for the humic acid and Zn2+(?4.23) > Cd2+(?4.49) > Ni2+(?4.51) ? Co2+ (?5.99) > Ca2+(?6.37) for silica.  相似文献   

8.
The effect of Cl?,SO 4 2? , CH3COO?, and NO 3 ? anions on the adsorption of copper, lead, and zinc by an ordinary chernozem has been studied. The effect of the anions on the adsorption of Cu2+, Pb2+, Zn2+ ions is significant but uncertain. It has been shown that the attendant anions affect the shape of the adsorption isotherms, which are described by the Langmuir, Freundlich, or Henri equations. The constants of the adsorption from a nitrate solution calculated from the Langmuir equation (K L) decrease in the following order: Cu2+ > Pb2+ >> Zn2+. The values of the maximum adsorption (C max) decrease in the following order: Cu2+ ≥ Zn2+ > Pb2+ for acetate solutions and in the series Pb2+ > Zn2+ ≥ Cu2+ for nitrate solutions. The values of the Henry constants (K H) calculated for the adsorption of the same cations from chloride solutions decrease in the same order as the values of K L. The CH3COO? anion has the highest effect on the constant values. The NO 3 ? and Cl? anions “switch their places” depending on the attendant cation, but their effect is always lower than that of the acetate anion. The values of C max for copper and zinc are most affected by the CH3COO? anion, and the adsorption of zinc is most affected by the Cl? and NO 3 ? anions. The assessment of the mobility of the adsorbed cations from the extraction with ammonium acetate (pH 4.8) has shown that the content of the desorbed metals is always lower than the content of the adsorbed cations and varies from 0.025 to 83%. According to their mobility, the adsorbed metals form the following order: Zn2+ > Pb2+ > Cu2+. The effect of the attendant anions on the extractability of the adsorbed cations decreases in the following order: chlorides > sulfates > acetates > nitrates.  相似文献   

9.
Zinc (Zn) sorption curves were established for 11 cultivated sandy soils from central Vietnam. Soil samples (10 g) were equilibrated with 5 mM calcium chloride (CaCl2) solutions (50 mL) at five zinc chloride (ZnCl2) concentrations (0 to 80 mg Zn L–1). The experimental sorption data were fitted with the Freundlich equation. The amounts of Zn sorbed by soil (QZn) at different Zn concentrations in the equilibrium solution (CZn) were closely related to cation exchange capacity (CEC) and pH, that is, to the available exchange sites at given pH values. More specifically, an excellent correlation was found between Zn sorption and exchangeable calcium (Caex), which evidently also depends on CEC and pH. A unique equation was proposed to predict QZn from CZn and Caex in the range of Zn loading covered in our research, that is, from traces to QZn ≈ 60 mg Zn kg–1.  相似文献   

10.
11.

Purpose

Field survey and sampling of vegetable greenhouse soils were conducted in Shouguang, Shandong Province, and Ningbo, Zhejiang Province to study the acidification and salinization characteristics of soils with different initial soil pH values and greenhouse cultivation time.

Materials and methods

The pH, electrical conductivity (EC), and ion composition of 74 composite soil samples were analyzed to evaluate their relation to soil acidification and salinization.

Results and discussion

Compared with their corresponding open-field soils, acidification and salinization of the greenhouse soils occurred in both 0-20 cm and 20-40 cm soil layers for the Shouguang and Ningbo soils. The soil pH decreased gradually at different rates as greenhouse cultivation time increased in the two surveyed regions, but the opposite trend was observed for soil EC. For the Shouguang soils, while the percentages of K+ and NO3 ? increased dramatically and Ca2+ and HCO3 - decreased significantly after the soils were converted to greenhouse use, the correlation between soil pH and EC was significant, and the stepwise multiple regression analysis further showed that there was a significant correlation between pH and the percent of Ca2+ and HCO3 ?.

Conclusions

Soil acidification and salinization are common in greenhouse soils with different initial soil pH. Soil acidification in the Shouguang soils is a result of decrease in the percent of Ca2+, HCO3 ? due to over application of N and K fertilizers. Future research should be devoted to understanding the relevant mechanisms in greenhouse soils with lower initial soil pH values to assess if there are correlations between soil acidification and salinization under greenhouse cultivation.  相似文献   

12.
Summer solarization of six wet field soils of four different textures raised soil temperatures by 10–12°C at 15cm depth. Soil solarization increased concentrations of NO?3N and NH+4N up to six times those in nontreated soils. Concentrations of P, Ca2+, Mg2+ and electrical conductivity (EC) increased in some of the solarized soils. Solarization did not consistently affect available K+, Fe3+, Mn2+, Zn2+, Cu2+, Cl? concentrations, soil pH or total organic matter. Concentrations of mineral nutrients in wet soil covered by transparent polyethylene film, but insulated against solar heating, were the same as those in nontreated soil. Increases in NO?3N plus NH+4N were no longer detected in fallowed soils 9 months after solarization. No significant correlation between mineral-nutrient concentration in plant tissue and plant growth was found. Fresh and dry weights of radish, pepper and Chinese cabbage plants usually were greater when grown in solarized soils than in nontreated soils. Fertilization of solarized soils sometimes resulted in greater plant growth responses than observed in solarized but nonfertilized soils.  相似文献   

13.
ABSTRACT

Two field experiments (2000–2001 and 2001–2002) were conducted at two nearby fields in the Qanavat region of Qom province, central Iran, to investigate the effects of zinc (Zn) fertilization on production of sunflower. The experiment was conducted in a randomized complete block design with six treatments in three replicates. Treatments were: Zn0 (non-Zn fertilized), Zn10, Zn20, Zn30, and Zn60 (soil application of 10, 20, 30, and 60 kg Zn ha?1, respectively), and ZnSpray (foliar spraying of 0.5 kg Zn ha?1 using ZnSO4). Seeds of sunflower (Helianthus annuus cv. ‘Record’) were planted on June 20, 2000 and June 15, 2001. At harvest, shoot and seed yields as well as concentration of Zn, iron (Fe), manganese (Mn), sodium (Na), and chloride (Cl) in leaves of sunflower were determined. Addition of 20 kg Zn ha?1 significantly increased seed production and shoot dry-matter yield of sunflower, while other Zn treatments had no significant effect on shoot dry-matter yield, or decreased it. The thousand-seed weight was the yield component most affected by Zn fertilization, while plant height and head diameter did not change. The maximum content of seed oil was achieved under the Zn10 treatment, then decreased at higher rates of soil-applied Zn such that oil content of seed under the Zn30 and Zn60, treatments was significantly lower than that of the control. Seed oil content was unaffected by foliar spraying of Zn. The concentration of Zn in sunflower leaves was increased with an increase in soil-added Zn of from 0 to 60 kg Zn ha?1. The highest leaf concentrations of Zn (162 and 175 mg kg?1 day matter (DM) in the first and second year, respectively) were achieved by foliar application of ZnSO4. Leaf concentration of Fe was significantly increased in the Zn20 treatment compared with the control but decreased at the higher rates of soil-added ZnSO4. Soil addition of different levels of ZnSO4 decreased concentration of Na and Cl in leaves. The lowest concentration of Na and Cl in leaves was observed under Zn20. The results of this study suggest that soil application of a suitable amount of Zn has a positive effect on both quantitative and qualitative yield of sunflower in saline, calcareous soils.  相似文献   

14.

Purpose

For agricultural production and environment protection, it is cations loosely bound to the soil particles that have a great significance in short-term processes of adsorption–desorption, exchange, and transport. It is beneficial to be able to evaluate the fractions of these cations in order to correctly predict potential pollution of soils by heavy metals and availability of plant nutrients.

Materials and methods

The homionic suspensions of yellow-brown soil (YB) and black soil I (BI) saturated with Na+ and Ca2+ and three subsamples of black soil II (BII) saturated with Ca2+ and Cd2+ were prepared to determine the electrical conductivity (EC) of the suspensions. On the basis of electrical conductivity vs. field strength (EC-E) curve, the fraction of electrically associated cations on surfaces of soil particles was evaluated by extrapolation of strong-field Wien effect measurements in dilute suspensions.

Results and discussion

The maximum dissociation degree (α max) of Na+ adsorbed on surfaces of yellow-brown soil and black soil I was about 0.21, which is approximately twice as much as those of Ca2+ (0.07–0.10) adsorbed on surfaces of two soils. The soil type was not the main factor in evaluating α max, and the valence of the cations was. For divalent cations, α max of Ca2+ and Cd2+ adsorbed on soil particles with different contents of organic matter descended in the order: top black soil II?>?bottom black soil II?>?OM-free bottom black soil II.

Conclusions

The relatively small fractions of electrically adsorbed cations—about 0.2 for Na+ and 0.1 for Ca2+ on yellow-brown and black soils particles indicated that even for the more loosely adsorbed Na+ ions, most of the cations in the double layers of soil particles were adsorbed strongly by other, more specific mechanisms and cannot be stripped off into the solution, which would increase its electrical conductivity in a strong applied field.
  相似文献   

15.
Proto-imogolite sols can be considered as highly dispersed forms of proto-imogolite allophane, the most widespread type of allophane in volcanic and non-volcanic soils world-wide. The solubility characteristics of such sols define the conditions of precipitation of allophanes in soils, and the maximum concentrations of aluminium released during acidic episodes from soils, such as podzols, that contain allophane. Direct measurement of Al, Si and pH values in equilibrium with proto-imogolite sols, approached from higher and lower pH, indicated a solubility equation: where log*Kso lay in the range 7.14 to 7.23 after equilibration for 4–24 weeks at 22 + 2°C in 17 of the 20 systems studied. The mean value of log *KSO at 298 K was calculated as 7.02. This value indicates that proto-imogolite will be more stable than amorphous aluminium hydroxides at H4SiO4 concentrations above 5 × 10?6m , but less stable than bayerite below 10?3m H4SiO4, and than gibbsite below 10?2m . Proto-imogolite is more stable than micro-crystalline gibbsite in 10?4m H4SiO4, a typical minimum concentration in soil solutions and streams in landscapes where podzols are present. The rapid formation of proto-imogolite effectively prevents the formation of gibbsite seeds in soil, except in highly leached and warm environments, i.e. in older landscapes in the tropics. Although the presence of 10?4m silicic acid has been found to eliminate the acute toxicity to fish exhibited by solutions containing 6–7 μm Al at pH 4.96, little or no proto-imogolite would form under these conditions. Silicic acid would, however, prevent the precipitation of aluminium hydroxides, and could inhibit the formation of the A113 polycation. These polymeric species are a likely cause of the increased toxicity exhibited by partially neutralized aluminium solutions.  相似文献   

16.
Comamonas sp. UVS was able to decolorize Reactive Blue HERD (RBHERD) dye (50 mg L?1) within 6 h under static condition. The maximum dye concentration degraded was 1,200 mg L?1 within 210 h. A numerical simulation with the model gives an optimal value of 35.71?±?0.696 mg dye g?1 cell h?1 for maximum rate (Vmax) and 112.35?±?0.34 mg L?1 for the Michaelis constant (Km). Comamonas sp. UVS has capability of decolorization of RBHERD in the presence of Mg2+, Ca2+, Cd2+, and Zn2+, whereas decolorization was completely inhibited by Cu2+. Metal ions also affected the levels of biotransformation enzymes during decolorization of RBHERD. Comamonas sp. UVS was also able to decolorize textile effluent with significant reduction in COD. The biodegradation of RBHERD dye was monitored by UV–vis spectroscopy, FTIR spectroscopy, and HPLC.  相似文献   

17.
The effectiveness of lime-ammonium-nitrate (LAN) as a nitrogen (N) fertilizer in weathered soils depends on the respective selectivity for ammonium (NH4) and calcium (Ca) by the soils. The study assessed Ca2+/NH4+ exchange selectivity of two benchmark soils from Botswana and examined the soil fertility management implications. Surface horizons (0–20 cm) of Pellustert and Haplustalf were equilibrated with 50 ml stock solution containing variable concentrations of Ca2+ and NH4+. The Ca2+/NH4+ exchange data were fitted into the Vanselow (KV), Gaines and Thomas (KGT), Davies (KD), and the regular solution (KRS) equations. The selectivity coefficients for the Ca2+/NH4+ exchange reactions varied widely with the soil exchanger composition except for the relatively stable KRS. The selectivity coefficients indicated strong preference for NH4+ to Ca2+. The thermodynamic exchange constant, Kex, was 5.75 ± 1.24 in the Pellustert, indicating preferential adsorption of NH4+, but not in the Haplustalf with Kex = 0.92 ± 0.27. The free energy for Ca2+/NH4+ exchange (ΔG°ex) was negative (?4.26 ± 0.59 kJ mol?1) in the Pellustert but slightly positive in the Haplustalf (0.34 ± 0.87 kJ mol?1). In conclusion, the soil-NH4 complex was more stable than soil-Ca complex in the Pellustert, indicating LAN as a N fertilizer would have greater potential effectiveness in the Pellustert than in the Haplustalf.  相似文献   

18.
Zinc (Zn) desorption from an exchange complex to solution, the release of Zn from organic matter (OM), crystalline minerals and other precipitates into the solution phase, is the process that controls Zn mobility in soils. An experiment was conducted to determine the pattern of Zn desorption and the soil characteristics affecting it. Desorption of Zn in 15 calcareous soils from southern Iran, treated with 10 mg Zn kg soil?1 as zinc sulfate (ZnSO4?7H2O) and 10 g organic matter (OM) kg?1 as feedlot cattle manure, equilibrated and extracted with diethylenetriamine pentaacetic acid (DTPA), was studied. Eight kinetic models were evaluated to describe the rate of Zn desorption of soil extracted with DTPA. There was a rapid rate of desorption during the first 4 h followed by a slower rate during the next 12 h. Two-constant rate and simple Elovich models were determined as the best models describing Zn desorption kinetics. Zinc desorption increased as Zn was applied, whereas it decreased with applied OM. The constants of the simple Elovich (βs) and two-constant rate equations (a and b) were closely correlated with cation-exchange capacity (CEC), OM and pH, which affect Zn solubility, sorption–desorption and diffusion in soils.  相似文献   

19.
The performance of various filters used for determining inorganic species (heavy metals, light metals, anions and ammonium ion) in airborne particulates was comparatively assessed. Filters used in the determination of Ca2+, Mg2+, Na+, K+, Fe3+, Zn2+, Pb2+, Cr3+, Ni2+, V (V), Mn2+ and Cd2+ were attacked by acid extraction (glass microfibre filters, GF/A), acid extraction and microwave oven digestion (quartz filters, QM-A), and muffle furnace calcination and microwave oven digestion (Whatman-41 cellulose filters, W-41). The behaviour of the different filters tested towards aqueous extraction for the determination of anions (Cl?, NO 3 ? , SO 4 ? , ammonium ion and light metals (Ca2+, Mg2+, Na+ and K+) was also studied and the results obtained for the light metals were compared with those provided by acid attack. All metals except vanadium were determined by ICP-AES; cadmium, lead and vanadium were analysed for by GFAAS; anions were quantified by ion chromatography (SO 4 ? was also measured by ICP-AES); and ammonium ion was determined by the Indophenol Blue method.  相似文献   

20.
Zinc as ZnSO4 was added to three soils at rates of 0, 10, 100 and 1000 μg Zn g?1 soil. The soils were uniformly treated with 100 μg Ng?1 as nh4cl, incubated at 30°C and NH4+-N and (NO3? + NO2?)-N determined weekly for 7 weeks. Nitrification in all three soils was totally inhibited by 1000 μg Zn g?1. At the 100 μg Zn g?1 rate, nitrification was significantly reduced in two of the three soils during some part of the incubation. This differential effect on nitrification at the 100 μg Zn g?1 rate was related to differences in soil properties. These results imply that, with respect to nitrification, care should-be taken not to apply Zn-containing materials indiscriminately to soils.  相似文献   

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