Speciation of Cu and Zn in drainage water from agricultural soils

Inputs of copper and zinc from agricultural soils into the aquatic system were investigated in this study, because of their heavy agricultural usage as feed additives and components of fertilizers and fungicides. As the mobility and bioavailability of these metals are affected by their speciation, the lipophilic, colloidal and organic fractions were determined in drainage water from a loamy and a humic soil treated with fungicides or manure. This study therefore investigates the impact of agricultural activity on a natural environment and furthers our understanding of the mobility of metals in agricultural soils and aquatic pollution in rural areas. Marked increases in the total dissolved metal concentrations were observed in the drainage water during rain events with up to 0.3 microM Cu and 0.26 microM Zn depending on the intensity of the rainfall and soil type. The mobile metal fractions were of a small molecular size (<10 kD) and mainly hydrophilic. Lipophilic complexes originating from a dithiocarbamate (DTC) fungicide could not be observed in the drainage water; however, small amounts of lipophilic metal complexes may be of natural origin. Cu was organically complexed to > 99.9% by abundant organic ligands (log K 10.5-11.0). About 50% of dissolved Zn were electrochemically labile, and the other 50% were complexed by strong organic ligands (log K 8.2-8.6). Therefore very little free metal species were found suggesting a low bioavailability of these metals in the drainage water even at elevated metal concentrations.     

Speciation and release kinetics of zinc in contaminated paddy soils

Zinc is an important nutrient for plants, but it can be toxic at high concentrations. The solubility and speciation of Zn is controlled by many factors, especially soil pH and Eh, which can vary in lowland rice culture. This study determined Zn speciation and release kinetics in Cd-Zn cocontaminated alkaline and acidified paddy soils, under various flooding periods and draining conditions, by employing synchrotron-based techniques and a stirred-flow kinetic method. Results showed almost no change in Zn speciation and release kinetics in the two soils, although the soils were subjected to different flooding periods and draining conditions. The mineral phases in which Zn is immobilized in the soil samples were constrained by linear least squares fitting (LLSF) analyses of bulk X-ray absorption fine structure (XAFS) spectra. Only two main phases were identified by LLSF, i.e., Zn-layered double hydroxides (Zn/Mg-hydrotalcite-like, and ZnAl-LDH) and Zn-phyllosilicates (Zn-kerolite). Under all soil pHs, flooding, and draining conditions, less than 22% of Zn was desorbed from the soil after a two-hour desorption experiment. The information on Zn chemistry obtained in this study will be useful in finding the best strategy to control Cd and Zn bioavailability in the Cd-Zn cocontaminated paddy soils.     

A WHAM-based kinetics model for Zn adsorption and desorption to soils

A novel model has been developed to describe the kinetics of Zn adsorption and desorption to soils. The model incorporates the mechanistic-based equilibrium model WHAM (Windermere humic aqueous model) to account for the chemical variation during the reaction (e.g., pH and Zn2+ concentration), the heterogeneity of binding sites of soil organic matter (SOM), and the nonlinear binding of Zn to SOM. To test the model, kinetic experiments were conducted using a stirred-flow method. Six soils, with low clay fractions and covering a wide range in SOM concentrations, and various Zn concentrations and pHs were studied. Under these experimental conditions, SOM is found to be the major adsorbent for Zn binding. The fast and slow Zn reactions with soils were associated, respectively, with the monodentate and bidentate binding sites of humic substances in WHAM. The model has only three fitting parameters, the two desorption rate coefficients for the fast (monodentate) and slow (bidentate) reaction sites which are constant and independent of soil type, and the reactive organic matter fraction of the total SOM in each soil. All other parameters are derived from WHAM. The model is able to predict Zn release from spiked soils including the effects of Ca competition.     

Desorption kinetics of Cd, Zn, and Ni measured in soils by DGT

DGT (diffusive gradients in thin films) was used to measure the distribution and rates of exchange of Zn, Cd, and Ni between solid phase and solution in five different soils. Soil texture ranged from sandy loam to clay, pH ranged from 4.9 to 7.1, and organic carbon content ranged from 0.8% to 5.8%. DGT devices continuously remove metal to a Chelex gel layer after passage through a well-defined diffusion layer. The magnitude of the induced remobilization flux from the solid phase is related to the pool size of labile metal and the exchange kinetics between dissolved and sorbed metal. DGT devices were deployed over a series of times (4 h to 3 weeks), and the DIFS model (DGT induced fluxes in soils) was used to derive distribution coefficients for labile metal (Kdl) and the rate at which the soil system can supply metal from solid phase to solution, expressed as a response time. Response times for Zn and Cd were short generally (<8 min). They were so short in some soils (<1 min) that no distinction could be made between supply of metal being controlled by diffusion or the rate of release. Generally longer response times for Ni (5-20 min) were consistent with its slow desorption. The major factor influencing Kdl for Zn and Cd was pH, but association with humic substances in the solid phase also appeared to be important. The systematic decline, with increasing pH, in both the pool size of Ni available to the DGT device and the rate constant for its release is consistent with a part of the soil Ni pool being unavailable within a time scale of 1-20 min. This kinetic limitation is likely to limit the availability of Ni to plants.     

Kinetics of Zn release in soils and prediction of Zn concentration in plants using diffusive gradients in thin films

Effective concentrations (CE) of Zn measured by the technique of DGT (diffusive gradients in thin films) were compared, along with total concentrations of Zn and the concentrations of Zn in soil solutions, to Zn concentrations in plants. Soils variously contaminated with Zn were collected in the vicinity of two galvanized electrical transmission towers (pylons) and two motorway crash barriers. Lepidium sativum was grown in each soil and in corresponding control soils amended with ZnCl2 to similar total Zn concentrations. CE, concentrations in soil solution, and total Zn were measured in all soils, and total Zn was measured in the plant shoots. The CE values, soil solution Zn, and shoot Zn concentrations were all larger in ZnCl2 amended soils than in field contaminated soils at corresponding total Zn. Correlations between the concentration of Zn in the plants and the measured soil parameter followed the order CE > soil solution > total Zn. The low scatter in the plot of log plant concentration versus log CE revealed a relationship with two distinct features. Plant Zn was between 100 and 300 mg/kg up to an effective Zn concentration of about 2 mg/L, above which plant Zn increased steadily with increasing CE. Use of a dynamic model to interpret the DGT measurement suggests that the intrinsic rate of release of Zn from solid phase to solution, expressed as a rate constant, is much higher for soils that receive fresh supplies of Zn. This finding provides a mechanistic basis for reconciling laboratory experiments, where metal is freshly amended, to data obtained in the field. The potential of DGT as a surrogate for metal availability to plants is further confirmed by this work.     

花生种子铜锌超氧物歧化酶的纯化及理化性质研究

花生种子铜锌超氧物歧化酶经氯仿-乙醇处理、硫酸铵盐析、凝胶过滤和离子交换柱层析等步骤被分离纯化到均一程度。该酶相对分子量为31500Da,由两个相同亚基组成,亚基分子量为16010Da,它在紫外区最大吸收波长为253nm,等电点为4.2,每摩尔酶含2个原子Cu和2个原子Zn,2mmol/L H2O2和0.2mmol/L KCN能完全抑制其活性,该酶由303个氨基酸残基组成,含有较高的丝氨酸和缬氨酸,不含色氨酸和半胱氨酸。纯化后的SOD比活性为5029U/mg,活力回收率为34%。     

Modeling the primary size effects of citrate-coated silver nanoparticles on their ion release kinetics

Ion release is an important environmental behavior of silver nanoparticles (AgNPs), and characterization of Ag(+) release is critical for understanding the environmental fate, transport, and biological impacts of AgNPs. The ion release kinetics of AgNPs with three primary diameters (20, 40, and 80 nm) were studied by dispersing them in quarter-strength Hoagland medium at two initial concentrations (300 and 600 μg/L). Ag(+) release rates were found to depend on primary particle size and concentration, when other environmental factors (e.g., dissolved oxygen and protons) were kept constant. A kinetic model was developed to describe the Ag(+) release based on the hard sphere theory using the Arrhenius equation. The model fitted the experimental data well with correlation coefficients of 0.97-0.99, and the model usefully interpreted the dependence of ion release kinetics on the primary particle size and concentration. Moreover, the effects of environmental factors (e.g., dissolved oxygen, pH, temperature, and salinity) potentially can be interpreted as well. This model provides fundamental insight into the ion release kinetics of AgNPs in aqueous environments, allowing us to better understand and predict the nanotoxicity of AgNPs.     

Modeling controlled nutrient release from polymer coated fertilizers: diffusion release from single granules

A comprehensive model describing the complex and "non-Fickian" (mathematically nonlinear) nature of the release from single granules of membrane coated, controlled release fertilizers (CRFs) is proposed consisting of three stages: i. a lag period during which water penetrates the coating of the granule dissolving part of the solid fertilizer in it ii. a period of linear release during which water penetration into and release out occur concomitantly while the total volume of the granules remains practically constant; and iii. a period of "decaying release", starting as the concentration inside the granule starts to decrease. A mathematical model was developed based on vapor and nutrient diffusion equations. The model predicts the release stages in terms of measurable geometrical and chemophysical parameters such as the following: the product of granule radius and coating thickness, water and solute permeability, saturation concentration of the fertilizer, and its density. The model successfully predicts the complex and "sigmoidal" pattern of release that is essential for matching plant temporal demand to ensure high agronomic and environmental effectiveness. It also lends itself to more complex statistical formulations which account for the large variability within large populations of coated CRFs and can serve for further improving CRF production and performance.     

Modeling the kinetics of the competitive adsorption and desorption of glyphosate and phosphate on goethite and gibbsite and in soils

The herbicide glyphosate and inorganic phosphate compete for adsorption sites in soil and on oxides. This competition may have consequences for the transport of both compounds in soil and hence for the contamination of groundwater. We present and evaluate six simple, kinetic models that only take time and concentrations into account. Three of the models were found suitable to describe the competition in soil. These three models all assumed both competitive and additive adsorption, but with different equations used to describe the adsorption. For the oxides, three additional models assuming only competitive adsorption were also found suitable. This is in accordance with the observation that the adsorption in soil is both competitive and additive, whereas the adsorption on oxides is competitive. All models can be incorporated in transport models such as the convection-dispersion equation.     

Chemical speciation of Zn,Cd, Cu,and Pb in pore waters of agricultural and contaminated soils using Donnan dialysis

Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. Numerous analytical methods have been utilized for determining trace metal speciation in aqueous environmental matrixes; however, most of these methods suffer from significant interferences. The Donnan dialysis membrane technique minimizes these interferences and has been used in this study to determine free Zn2+, Cd2+, Cu2+, and Pb2+ activities in pore waters from 15 agricultural and 12 long-term contaminated soils. The soils vary widely in their origin, pH, organic carbon content, and total metal concentrations. Pore water pM2+ activities also covered a wide range and were controlled by soil pH and total metal concentrations. For the agricultural soils, most of the free metal activities were below detection limit, apart from Zn2+ for which the fraction of free Zn2+ in soluble Zn ranged from 2.3 to 87% (mean 43%). Five of the agricultural soils had detectable free Cd2+ with fractions of free metal ranging from 59 to 102% (mean 75%). For the contaminated soils with detectable free metal concentrations, the fraction of free metal as a percentage of soluble metal varied from 9.9 to 97% (mean 50%) for Zn2+, from 22 to 86% (mean 49%) for Cd2+, from 0.4 to 32.1% (mean 5%) for Cu2+, and from 2.9 to 48.8% (mean 20.1%) for Pb2+. For the contaminated soils, the equilibrium speciation programs GEOCHEM and WHAM Model VI provided reasonable estimates of free Zn2+ fractions in comparison to the measured fractions (R2 approximately 0.7), while estimates of free Cd2+ fractions were less agreeable (R2 approximately 0.5). The models generally predicted stronger binding of Cu2+ to DOC and hence lower fractions of free Cu2+ as compared with the observed fractions. The binding of Cu2+ and Pb2+ to DOC predicted by WHAM Model VI was much strongerthan that predicted by GEOCHEM.     

Fractions affected and probabilistic risk assessment of Cu, Zn, Cd, and Pb in soils using the free ion approach

The free ion approach quantifies the toxic effects of cationic metals on soil biota as a function of chemistry. The approach is here extended to calculate the general relationship among toxic effects as the Fraction Affected (FA), soil solution pH, and soil organic matter content (SOM) for Cu, Zn, Cd, and Pb within toxicity data sets from literature. The dependence of FA on SOM is strong, with the FA decreasing as the SOM increases. The dependence of FA upon pH varies; Cd and Zn show strong dependences while for Cu and Pb dependences are weaker. The FA usually decreases as the soil pH increases. When the free ion approach is applied, risks across soils due to different metals can be compared using the FA. The free ion approach may also be applied to probabilistic risk assessment. Risk values, using the joint probability curve approach, were derived for Pb using two field soil data sets. One data set, with higher SOM than that of the Pb toxicity data set, gave a lower risk with the free ion approach than that when the soil chemistry was not considered. The other data set had lower SOM than that of the toxicity data set and gave a higher risk with the free ion approach. Since literature toxicity tests are biased toward low SOM soils of circumneutral pH, using such data to perform classical risk assessment for soils of differing chemical composition can lead to misestimation of risk due to neglecting soil chemistry, especially in soils with extreme pH and/or SOM.     

Competitive Cu and Cd sorption and transport in soils: a combined batch kinetics, column, and sequential extraction study

The competitive effect influenced the transport behavior of Cu and Cd contrastingly in soils, as illustrated by the experimental findings obtained from column, batch kinetics, and sequential extraction tests. Of particular interest, Cd transport behavior changed from nonequilibrium in a single-metal system to equilibrium in a binary-metal system, whereas Cu exhibited a slightly greater degree of nonequilibrium transport under competition.The equilibrium time of specific sorption (approximately 7 days) was found to be much longer than that of nonspecific sorption (approximately 30 min). While there was a competitive effect on nonspecific sorption for both Cu and Cd, the majority of rate-limited specific sorption of Cd on oxide and organic matter fractions (contributing to approximately 20% of total sorption) was dramatically displaced by Cu. Such a strong suppression of specific sorption of Cd bythe presence of Cu resulted in a shorter equilibrium time of overall sorption, which probably accounts for its equilibrium transport. In contrast, the competitive effect on rate-limited sorption and transport behavior of Cu was less significant. This study demonstrated a correlation between the competitive effect of Cu and Cd on their nonspecific and specific sorption and the corresponding significance of rate-limited sorption and nonequilibrium transport behavior.     

Availability of Cu,Zn and Mn in soils: I.—Influence of soil pH,organic matter,and extractable phosphorus

Samples from Ap horizons of 36 cultivated Wisconsin fields were tested for concurrent availability of Cu, Zn and Mn. The effects of soil pH, organic matter, and available P were evaluated by using four chemical extract ants. Oats were used as the test crop and were grown using a self-watering pot-culture technique in a plant-growth room. The divergent soils had the following averages: pH, 6–4; organic matter, 2–6%; available P, 37 ppm; total Cu, 20 ppm; total Zn, 35 ppm; and total Mn, 631 ppm. Concentrations of the micronutrient elements in plants and soils were determined by atomic absorption spectrophotometer. NPK fertilisation resulted in greater plant uptake of Cu, Zn and Mn. Significant interactions between the soil properties and the different chemical fractions influenced the plant uptake of each micro-element; interactions between Cu, Zn and Mn in the same chemical fraction also influenced their individual uptake. Copper uptake was best predicted by inclusion particularly of soil pH, or the same chemical fractions of Zn and Mn in the regression equation; Zn uptake by inclusion of soil organic matter and available P, Mn uptake, or the chemical fractions of Cu and Mn; and Mn uptake by inclusion of available P, Cu chemical fraction, or Zn uptake in the equation. The extractants N ammonium acetate (pH 7) 10 · 01 M EDTA and 0·1 N -HCI show promise in soil tests for the simultaneous availability of Cu, Zn and Mn.     

Molecular-scale speciation of Zn and Ni in soil ferromanganese nodules from loess soils of the Mississippi Basin

Determining how environmentally important trace metals are sequestered in soils at the molecular scale is critical to developing a solid scientific basis for maintaining soil quality and formulating effective remediation strategies. The speciation of Zn and Ni in ferromanganese nodules from loess soils of the Mississippi Basin was determined by a synergistic use of three noninvasive synchrotron-based techniques: X-ray microfluorescence (microXRF), X-ray microdiffraction (microXRD), and extended X-ray absorption fine structure spectroscopy (EXAFS). We show that Ni is distributed between goethite (alpha-FeOOH) and the manganese oxide lithiophorite, whereas Zn is bound to goethite, lithiophorite, phyllosilicates, and the manganese oxide birnessite. The selective association of Ni with only iron and manganese oxides is an explanation for its higher partitioning in nodules over the soil clay matrix reported from soils worldwide. This could also explain the observed enrichment of Ni in oceanic manganese nodules. The combination of these three techniques provides a new method for determining trace metal speciation in both natural and contaminated environmental materials.     

Purification and characterization of Cu,Zn superoxide dismutase from pumpkin (Cucurbita moschata) pulp

From ethyl acetate fraction of olive pomace, solid residue from olive oil extraction, a new compound was isolated and purified through solid-phase extraction using silica Cartridge column chromatography. The structure of the new compound was established as a deoxyloganic acid lauryl ester by spectroscopic data including one- and two-dimensional NMR, electrospray ionization mass spectrometry, infrared analysis and UV spectra. The antioxidant activity of the purified compound was evaluated by measuring the radical-scavenging effect on 2,2-diphenyl-1-picrylhydrazyl and by using the ferric reducing antioxidant power assays. The pure compound has not been previously identified in the genus Olea and could be used as for studying the biosynthetic pathway of oleuropein aglycon.     

Potassium retention and release in rothamsted and saxmundham soils

The retention and release of K from ‘No K ’and K-treated soils from the Rothamsted Classical Experiments and Saxmundham Experiment were examined using K-Ca exchange equilibria and the kinetics of K release to Ca-saturated resin. Free energies and enthalpies of Ca→K exchange showed that Saxmundham soils had the greater preference for K, and that residual K from long-term manuring significantly decreased K binding strength and preference. K release kinetics showed that residual K increased the rate of K release chiefly from the ‘surface’ region, and the amount of K released from ‘surface’ and ‘peripheral’ regions of 2:1 layer silicates in soils. The increased K release from ‘peripheral’ regions of K fertilised soils, together with their decreased K preference, was associated with slowly reversible K fixation on the weathered periphery of 2:1 layer silicates.     

A simplified method for the extraction of the metals Fe,Zn, Cu,Ni, Cd,Pb, Cr,Co and Mn from soils and sewage sludges

The method described for digestion of soil samples with aqua regia is simple, flexible and safe to operate with large sample throughout. At least nine metals can be determined in the resulting solutions with errors of <5%. The results compare favourably with those from reflux aqua regia and averaged 88% of the certified total values for reference soils and 88% of those for reference sewage sludges.