Effects of physical and chemical properties of soils on adsorption of the insecticidal protein (Cry1Ab) from Bacillus thuringiensis at Cry1Ab protein concentrations relevant for experimental field sites

The adsorption of the insecticidal Cry1Ab protein of Bacillus thuringiensis (Bt) on Na-montmorillonite (M-Na) and soil clay fractions was studied. The aim of this study was not to find the adsorption capacity of the soils from the experimental field site, where Bt corn (MON810) was cultivated, but rather to characterize the adsorption behavior of the Cry1Ab protein at concentrations typically found at experimental field sites. In kinetic experiments, the Cry1Ab protein adsorbed rapidly (<60 min) on M-Na. As the concentration of M-Na was varied and the added Cry1Ab protein concentration was kept constant (20 and 45 ng ml⁻¹), the adsorption per unit weight of Cry1Ab protein decreased with increasing concentrations of M-Na. Adsorption of Cry1Ab protein on M-Na decreased as the pH value of the suspension increased. All adsorption isotherms could be described mathematically by a linear regression with the parameter k, the distribution coefficient, being the slope of the regression line. Although their mineralogical composition was nearly identical, the soil clay fractions showed different k values. The different k values were correlated with the physical and chemical properties of the soil clay fractions, such as the organic carbon content, the specific external surface area, and the electrokinetic charge of the external surfaces of the clays, as well as with the external surface charge density. An increase in the amount of soil organic matter, as well as an increase in the electrokinetic external surface charge of the soil clays, decreased the distribution coefficient k. An increase of the specific external surface areas of the soil clays resulted in a higher distribution coefficient k.Less than 10% of adsorbed Cry1Ab protein was reversibly adsorbed on the soil clays and, thus, desorbed. The desorption efficiency of distilled water was higher than that of a solution of CaCl₂ (2.25 mmol) and of dissolved organic carbon (50 mg C l⁻¹).     

Biodegradation and insecticidal activity of the toxin from Bacillus thuringiensis subsp. kurstaki bound on complexes of montmorillonite–humic acids–Al hydroxypolymers

The equilibrium adsorption and binding of the active toxin from Bacillus thuringiensis subsp. kurstaki on complexes of montmorillonite–humic acids–Al hydroxypolymers, as well as the biodegradation and the insecticidal activity of the bound toxin, were studied. Seventy percent of the total adsorption occurred within the first hour, and maximal adsorption occurred in <8 h. Adsorption of the toxin on a constant amount of the complexes increased as the amount of the toxin added increased, and equilibrium adsorption isotherms of the L-type were obtained. There was essentially no desorption of the toxin after extensive washing of the toxin–organomineral complexes with double distilled H₂O and 1 M NaCl. The bound toxin was resistant to utilization by mixed microbial cultures from soil and to enzymatic degradation by Pronase E. Free and bound toxin were active against the larvae of Manduca sexta; the bound toxin retained the same activity after exposure to microbes or Pronase, whereas the toxicity of the free toxin decreased significantly. The results of these studies indicate that the release of transgenic plants and microorganisms expressing truncated genes that encode active insecticidal toxins from B. thuringiensis could result in the accumulation of these toxins in soil as a consequence of binding on surface-active soil particles. This persistence could pose a hazard to nontarget organisms, enhance the selection of toxin-resistant target species, and increase the control of target insect pests.     

Adsorption-desorption of atrazine on four soils of Hyderabad

The adsorption-desorption equilibrium of atrazine (2-chloro, 4-ethylamino, 6-isopropyl amino-1, 3, 5 triazine) was studied by the batch equilibration method at 27 ± 1 °C on four soils of Hyderabad. Adsorption isotherms conformed to the Freundlich equation (A = KC^1/n ). K increased in the same order as the organic C content of the soils. Desorption studies were conducted by repeated replacement of 5 mL of the supernatant equilibrium solutions after adsorption, with 0.01 M CaCl₂. Desorption isotherms showed considerable hysteresis which was more prominent when the desorption was carried out with higher adsorbed concentration of atrazine. Desorption from the lowest level of adsorbed atrazine (3 to 5 μg g^?1 soil) was close to the adsorption isotherm. The cumulative desorption after four desorption steps covering five days was significantly different at the 1% level, for different initial adsorbed concentrations of atrazine. Desorption was significantly higher at the lowest adsorbed level of atrazine. The soils differed significantly at 6% level for desorption and the amount desorbed decreased in the inverse order of organic C. Desorption isotherms also conformed to Freundlich equation but K andn values were both higher than that for adsorption and increased with increase in initially adsorbed concentration of atrazine. Desorption thus confirmed the irreversible nature of the adsorption of atrazine on these soils. The quantitative factors and reasons for desorption are discussed.     

Cadmium Sorption and Desorption Characteristics of Tropical Alfisols from Different Land Uses

Cadmium (Cd) sorption and desorption characteristics by Alfisols from different land uses were examined, and the relationships between soil and sorption/desorption characteristics were investigated. Adsorption studies were done using Cd concentrations (0–100 mg Cd kg^?1) in 0.01 M CaCl₂. The Cd sorbed by the soils was then subjected to two desorption runs. The soils' adsorption conformed to Freundlich and Langmuir equations. The amount of Cd sorbed by the soils varied. Two desorption runs detached more than 95% of sorbed Cd, but the first accounted for more than 80% of the total. Desorption of Cd in degraded soils was more than in soils from other land uses. The amount of Cd desorbed correlated with amount applied (r = 0.90??), solution concentration (r = 0.83??), and amount sorbed (r = 0.70??). A positive relationship exists between the adsorption maxima of the soils and soil organic matter (r = 0.13, p = 0.87). The relationship between amount of Cd desorbed and sorbed is quadratic for all the soil.     

Behaviour of plant‐derived extracellular phytase upon addition to soil

The behaviour of phytase after addition to three soil types with different sorption capacities was investigated. Phytase was collected from the roots of transgenic Arabidopsis thaliana that express a phytase gene from Aspergillus niger. Phytase activity in solution and on the solid phase of the soil was monitored over time. Phytase added to the solution phase of a soil suspension (1:20, w/v) was almost completely lost within 10 min in all soil types, while phytase in non-soil controls remained active in solution. Phytase activity lost from solution was recovered on the soil solid phase, suggesting rapid adsorption of the enzyme. Adsorption of phytase was less in soil taken from the rhizosphere of transgenic plants expressing phyA, indicating that the rhizosphere environment may help maintain phytase activity in solution. The activity of adsorbed phytase declined with time at a rate 2-4 times slower than that in the absence of soil. Adsorption of phytase in soils was highest at pH 4.5, which is below the reported isoelectric point (pI) of the Aspergillus phytase. As soil pH increased, adsorption decreased until, at pH 7.5, all phytase was in solution. Where phytase remained in solution, activity was maintained for at least 8 d. In contrast, the activity of adsorbed phytase was increasingly inhibited with time, particularly at low pH. By increasing the pH in soil suspensions, phytase that had remained active on the soil solid phase for 28 d was almost totally desorbed. Rapid immobilisation of phytase in soil may limit its capacity to interact with phytate, and this may compromise the ability of transgenic plants which exude phytase from their roots to acquire P from endogenous soil phytate.     

Remediation of Metal-Contaminated Soil by Organic Metabolites from Fungi II—Metal Redistribution

Exudation of low molecular weight organic acids by fungi was studied in a project focusing on bioremediation of metal-contaminated soils. The production of acids (mainly oxalic and citric acid) as a response to nutrient variations and presence of metals has recently been reported (Arwidsson et al. 2009). A significant release of metals was observed and was related not only to the production of organic acids but also to the resulting pH decrease in the systems. The processes governing the release and redistribution of metals in the soil–water fungus system were the focus of the present continuation of the project, based on observations of Aspergillus niger, Penicillium bilaiae, and a Penicillium sp. The release of lead was 12% from the soil with the second highest initial load (1,600 mg kg^?1), while the release of copper was 90% from the same soil (140 mg kg^?1). The dominating mechanism behind the release and subsequent redistribution was the change in pH, going from near neutral to values in the range 2.1–5.9, reflecting the production of organic acids. For some of the systems, the formation of soluble complexes is indicated (copper, at intermediate pH) which favors the metal release. Iron is assumed to play a key role since the amount of secondary iron in the soils is higher than the total load of secondary heavy metals. It can be assumed that most of the heavy metals are initially associated with iron-rich phases through adsorption or coprecipitation. These phases can be dissolved, or associated metals can be desorbed, by a decrease in pH. It would be feasible to further develop a process in technical scale for remediation of metal-contaminated soil, based on microbial metabolite production leading to formation of soluble metal complexes, notably with copper.     

应用穆斯堡尔(Mössbauer)谱学方法研究Fe+++, Fe++与胡敏酸结合的性质

本文应用穆斯堡尔谱学方法,研究了在不同pH条件下Fe⁺⁺⁺,Fe⁺⁺与胡敏酸结合的性质。计算机拟合的pH3.0⁵⁷Fe-胡敏酸络合物泥浆的穆斯堡尔谱和参数表明,三对四极双峰(图1,AA',BB',CC')是合理的。在pH3.0 Fe⁺⁺⁺以高自旋态存在,它和胡敏酸的结合多于一种环境类型。在pH1.0的⁵⁷Fe-胡敏酸络合物中,观察到了Fe⁺⁺⁺的穆斯堡尔谱信号,但没有Fe⁺⁺的信号,在这个样品离心分离出的液体部分检测到了加入量的59.7%的铁,表明在pH1.0时相当数量的Fe⁺⁺⁺被胡敏酸还原成Fe⁺⁺,Fe⁺⁺并不与胡敏酸牢固结合。在30伏电析过的⁵⁷Fe-胡敏酸络合物样品中(pH2.8)出现了Fe⁺⁺⁺,Fe⁺⁺的穆斯堡尔谱,这一结果指示出,在电析过程中由于⁵⁷Fe⁺⁺⁺-胡敏酸络合物悬浮液pH的降低,一部分Fe⁺⁺⁺还原成Fe⁺⁺,在pH2.8相当数量的Fe⁺⁺与胡敏酸牢固结合。根据在80K记录的穆斯堡尔谱,在pH1—3的范围出现了磁有序成份,但在室温记录的穆斯堡尔谱没有磁分裂。     

Effects of Organic Acids,o-Phenylenediamine and Pyrocatechol on Cadmium Adsorption and Desorption in Soil

This article studied the interaction of cadmium (Cd) and lowmolecular weight organics in Indicotic black (IB) soil.Cadmium adsorption isotherm in this soil was satisfactorilysimulated using Freundlich equation as Q = 905.6C^0.49 with high correlation (r² = 0.984), and its adsorption quantity increased with increasing pH. The presence of citricacid and EDTA significantly reduced Cd adsorption in soil,which was due to the formation of soluble Cd-organic complex. Concentration of cadmium ions in equilibrium solution was determined and percentages of [CdH₂Cit⁺]/[Cd-complex_Total],[CdHCit]/[Cd-complex_Total] and [CdCit^-]/[Cd-complex_Total] vs. pH were successfully calculated. Desorption percentage ofCd, adsorbed in the presence of citric acid and EDTA decreased, compared with that adsorbed in NaNO₃ media. It suggeststhat free sites for Cd adsorption in soil increased in thepresence of organic acid. When o-phenylenediamine, pyrocatechol and aminoethonic acid appeared in Cd equilibrium media, Cd adsorption quantity increased by increasing cation exchange ofpositively charged cadmium complex with soil at low pH. Compared with that performed in the absence of these organics, the exchangeable Cd, desorbed by 0.1 mol L^-1 NaNO₃, reduced obviously, which suggests that Cd-complex was moredifficult to be desorbed than Cd²⁺. Moreover, % Cd desorbedwas linearly correlated with the reverse of the total Cd adsorptionunder unsaturated adsorption.     

Adsorption and desorption of monomeric Bt (Bacillus thuringiensis) Cry1Aa toxin on montmorillonite and kaolinite

Genetically modified crops, which produce pesticidal proteins from Bacillus thuringiensis, release the toxins into soils through root exudates and upon decomposition of crop residues. Although the phenomena of gene transfer and emergence of resistance have been well documented, the fate of these toxins in soil has not yet been clearly elucidated. The aim of this study was to elucidate the adsorption and the desorbability of the Cry1Aa Bt insecticidal protein in contact with two sodium-saturated clays: montmorillonite and kaolinite. Because the toxin is released into soil in small quantities, it was assumed that it will be in a monomeric state in solution until it oligomerized on cell membranes. The originality of this study was to focus on the monomeric form of the protein. Specific sample conditions were required to avoid polymerisation. A pH above 6.5 and an ionic strength of at least 150 mM (NaCl) were necessary to keep the protein in solution and in a monomeric state. The adsorption isotherms obtained were of the L-type (low affinity) for both clays and fitted the Langmuir equation. The adsorption maximum of the toxin, calculated by the Langmuir nonlinear regression, decreased with increasing pH from 6.5, which was close to the isoelectric point, to 9. At pH 6.5, the calculated adsorption was 1.7 g g⁻¹ on montmorillonite and 0.04 g g⁻¹ on kaolinite. Desorbability measurements showed that a small fraction of toxin could be desorbed by water (up to 14%) and more by alkaline pH buffers (36 ± 7%), indicating that it was not tightly bound. Numerous surfactants were evaluated and the toxin was found to be easily desorbed from both clays when using zwitterionic and nonionic surfactants such as CHAPS, Triton-X-100, and Tween 20. This finding has important implications for the optimization of detection methods for Bt toxin in soil.     

可变电荷或永久电荷土壤上的电荷特征与土壤对Cu2+的吸附－解吸之间的交互作用

Charge characteristics and Cu^2 adsorption-desorption of soils with variable charge(latosol)and permanent charge(brown soil)and the relationship between them were studied by means of back-titration and adsorption equilibrium respectively.The amount of variable negative charge was much less in variable-charge soil than in permanent-charge soil and increased with the pH in the system,but the opposite trend occurred in the points of zero charge(PZCs).The amount of Cu^2 ions sorbed by permanent-charge soil was more than that by variable-charge soil and increased with the increase of Cu^2 concentration within a certain range in the equilibrium solution.The amount of Cu^2 ions desorbed with KCl from permanent-charge soil was more than that from variable-charge soil,but the amount of Cu^2 ions desorbed with de-ionized water from permanent-charge soil was extremely low whereas there was still a certain amount of desorption from variable-charge soil.The increase of PZC of soils with variable or permanent change varied with the increment of Cu^2 ions added.When the same amount of Cu^2 ions was added,the increments of PZC and variable negative surface chargc of permanent-charge soil were different from those of variable-charge soil.     

Adsorption‐desorption of zinc in mollisols and their relationship with uptake of fertilizer‐applied zinc by rice

Abstract

Zinc (Zn) adsorption in mollisols conformed to the linear form of Freundlich equation. The log K values were positively correlated with silt, clay, and carbonate contents and soil pH, but negatively correlated with sand content. Sequential desorption of adsorbed Zn in 0.05M Ca(NO₃)₂, 0.1M Mg(NO₃)₂, 0.005M DTPA, and 0.1M HCl revealed that weakly and specifically bound fractions of added Zn, which could easily equilibrate with soil solution, were low and decreased with silt and carbonate contents and soil pH. Weakly bound fraction increased with sand content. Strongly bound and complexed fraction of applied Zn was the maximum and increased with clay, soil organic carbon and carbonate contents and specific surface area, but decreased with sand content. The mineral bound fraction of applied Zn was intermediate and increased with silt, clay and carbonate contents, and soil pH and specific surface area. Zinc uptake due to added Zn fertilizer by rice crop (Y) negatively correlated with log K, but positively related to Zn content in the equilibrium soil extract and Zn desorbed in 0.05M Ca(NO₃)₂. Both log K and l/n values together explained 59.5% of the total variation in Y, while Zn content in the equilibrium soil extract, Zn desorbed in 0.05M Ca(NO₃)₂, 0.005M DTPA and 0.1M HCl collectively accounted 79.6% of the total variation in Y.     

Equilibria of weak acids and organic Al complexes explain activity of H+ and Al3+ in a salt extract of exchangeable cations

Two sequential extractions with unbuffered 0.1 m BaCl₂ were done to study the release of salt-exchangeable H⁺ and Al from mineral horizons of five Podzols and a Cambisol. Released Al was found to have a charge close to 3+ in all horizons and in both extractions. This finding was supported by the near-equality of the titrated exchangeable acidity (EA_T) and the sum of exchangeable acids (EA = H_e + 3Al_e, calculated from the pH and Al concentration of the extract). The ratio between EA of the second and the first extraction was over 0.50 in the Bs2 and C horizons and smaller in the other horizons. H⁺ was assumed to be in equilibrium with weak acid groups, and the modified Henderson–Hasselbach equation, pK_HH = pH ? n log (α/(1 ? α)), was used to explain pH of the extract. The degree of dissociation (α) was calculated as the ratio between effective and potential cation exchange capacity. Value of the empirical constant n was found to be near unity in most horizons. When the monoprotic acid dissociation was assumed in all horizons, pK_HH had the same value in both extractions. For Al³⁺, two equilibrium models were evaluated, describing (i) complexation reactions of Al³⁺ with soil organic matter, and (ii) equilibrium with Al(OH)₃. Apparent equilibrium constants were written as (i) pK_o = xpH ? pAl³⁺, and (ii) log Q_gibbs= log Al³⁺ ? 3log H^+. The two extractions gave an average reaction stoichiometry x close to 2 in all horizons. Results suggest that an equilibrium with organic Al complexes can be used to express dissolved Al³⁺, aluminium being apparently bound to bidentate sites. The value of log Q_gibbs was below the solubility of gibbsite (log K_gibbs = 8.04) in many horizons. In addition, log Q_gibbs of the second extraction was greater than that of the first extraction in all horizons except the C horizon. This indicates that equilibrium with Al(OH)₃ cannot explain dissolved Al³⁺ in the soils. We propose that the models of pK_HH and pK_o can be used to simulate exchangeable H⁺ and Al³⁺ in soil acidification models.     

Desorption of DDT from a Contaminated Soil using Cosolvent and Surfactant Washing in Batch Experiments

1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (p,p′-DDT) is a recalcitrant organic compound that is difficult to remove from contaminated soil due to its low solubility. In this study we investigated the effectiveness of both cosolvents and surfactants in enhancing the solubility of p,p′-DDT from a soil that has been contaminated with DDT for nearly 40 yr. The presence of selected surfactants removed less than 1 to 11% of p,p′-DDT compared to cosolvents, which removed less than 1 to 77% of p,p′-DDT from the same soil. The low solubility of p,p′-DDT in the presence of surfactants was attributed to the decreased surfactant concentration to below critical micelle concentrationfollowing sorption by soil surfaces. Enhanced solubility of p,p′-DDT was achieved with the use of cosolvents that releasedup to 77% of p,p′-DDT from a contaminated soil. Increasing the solution concentration and hydrophobicity of the cosolvent increased the amount of p,p′-DDT desorbed. For example, the amount of p,p′-DDT desorbed increased in the order 5% 1-propanol << 50% ethanol << 50% 1-propanol. Repeated washing of the soil with various cosolvents, in all but two cases, markedly increased the total amount of p,p′-DDT desorbed from the soil. For example, repeated washing of the soil with 50% ethanol increased the amount of p,p′-DDT removed by 42% while repeated washings of the soil with 50% 1-propanol had little effect on the amount of p,p′-DDT desorbed. Increasing the soil-solution ratio from 1:2 to 1:10 in the presence of 40% 1-propanol increased the amount of p,p′-DDT desorbed by 100%; suggesting that the soil-solution ratio was an important parameterin controlling the amount of p,p′-DDT desorbed.     

Study of Interaction Between Glyphosate and Goethite Using Several Methodologies: an Environmental Perspective

Glyphosate (N-(phosphonomethyl) glycine) is one of the most widely used herbicides in the world. Experiments using distilled water or CaCl₂ extractor resulted in as much as 60% of glyphosate being desorbed from goethite. When Mehlich 1 extractor was used, desorption could reach up to 73%. At pHs 2.0, 4.0, 6.0, and 8.0, an increase in salt content decreased the adsorption of glyphosate onto goethite. This indicates that most of the glyphosate is bound weakly to goethite through an outer-sphere complex. Thus, in soils with a high goethite content, glyphosate will contaminate groundwaters or rivers easily. FT-IR spectra showed that glyphosate interacts with goethite through the phosphate group and, at high pH, the amine group could be involved. Evidences of the interaction of the amine group of glyphosate with goethite were also obtained from the EPR spectra that showed, at high pH, a distortion in the octahedral symmetry of iron. In addition to the adsorption decrease with an increase in pH, a decrease of desorption at high pH occurs. This probably occurs because, at high pH, glyphosate interacts with goethite as a monodentate complex and through the amine group. The adsorption results fit best to a Freundlich isotherm model. This is in good agreement with the desorption results, indicating the presence of at least two adsorption sites—one for outer-sphere complexes and the other of inner-sphere complexes. The experimental results fit well with both pseudo-second-order and diffusion-limited models. The experimental results also fit well with a diffusion-limited model; however, the C value was different from zero. Therefore, the adsorption process was not controlled by diffusion only. Adsorption of glyphosate onto goethite is a complex process that could involve intra-particle diffusion. After adsorption of glyphosate onto goethite, a large decrease of pH_pzc was observed. The surface area and pore volume of goethite did not change with the adsorption of glyphosate.     

Adsorption of glycerophosphate on goethite (α‐FeOOH): A macroscopic and infrared spectroscopic study

Adsorption, desorption, and precipitation reactions at environmental interfaces govern the bioavailability, mobility, and fate of organic phosphates in terrestrial and aquatic environments. Glycerophosphate (GP) is a common environmental organic phosphate, however, surface adsorption reactions of GP on soil minerals have not been well understood. The adsorption characteristics of GP on goethite were studied using batch adsorption experiments, zeta (ζ) potential measurements, and in situ attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR). GP exhibited fast initial adsorption kinetics on goethite, followed by a slow adsorption. The maximum adsorption densities of GP on goethite were 2.00, 1.95, and 1.44 μmol m^?2 at pH 3, 5, and 7, respectively. Batch experiments showed decreased adsorption of GP with increasing pH from 3 to 10. Zeta potential measurements showed a remarkable decrease in the goethite isoelectric point upon GP adsorption (from 9.2 to 5.5), suggesting the formation of inner‐sphere surface complexes. In addition, the ATR‐FTIR spectra of GP sorbed on goethite were different from those of free GP at various pH values. These results suggested that GP was bound to goethite through the phosphate group by forming inner‐sphere surface complexes.     

Adsorption and activity of chitinase on kaolinite

Chitinase is adsorbed on kaolinite below the isoelectric point of the enzyme, pH 6.8. Maximum adsorption is reached below pH 4.6. The amount of chitinase adsorbed to kaolinite depends on the concentration and on the ratio of enzyme to kaolinite. Adsorption results in reduction of chitinase activity. the extent of which depends on the amount of kaolinite present, on pH, and on the length of exposure time. Upon sorption of chitinase on kaolinite the optimal pH for activity is increased from pH 4.7 to 5.7.     

Activity and stability of urease-hydroxyapatite and urease-hydroxyapatite-humic acid complexes

In agricultural calcareous soils, hydroxyapatite (APA) may well represent an important support for urease immobilisation and could be present in both mineral and organo-mineral complexes. In this paper we studied the formation of APA-urease-humic acid (HA) complexes after the addition of urease either before or after HAs. We then proceeded to evaluate the role of HAs on the activity and stability of the complexes as compared to the APA-urease complexes and free urease. When increasing amounts of HAs were added after urease, they did not affect the activity of the enzymes that had already adsorbed onto the complexes. On the contrary, adding the same amount of HA before the enzyme caused a significant reduction in the amount of enzyme adsorbed. However, when urease adsorption onto the APA-HA complexes was carried out in the presence of NaCl, the enzyme activity of the complexes increased sharply to 86% of the initial activity. The immobilisation of the enzyme on the support increased urease stability against pronase treatment as well as directly in soil over time. The inhibition of urease activity by Cu ²⁺was reduced by urease immobilisation. However, the presence of HA did not alter the stabilisation capability of APA when alone.     

Adsorption of atrazine and metolachlor in three soils from Blue Creek wetlands, Waterville, Ohio

Atrazine and metolachlor are extensively used pesticides in agricultural activities in northwest Ohio. Adsorption coefficients are often used to model pesticide fate and transport. Many physical-chemical parameters, such as organic matter, clay content, pH, and ionic strength, affect pesticide adsorption. Adsorption kinetics and adsorption isotherms were studied by batch experiment. Effects of humic acid, solution pH, and ionic strength on atrazine and metolachlor adsorption were also approached. After 24 h, both atrazine and metolachlor reached adsorption equilibrium in three local soils. Adsorption isotherms were described by Freundlich equations. The Freundlich coefficient (Kf) ranged from 0.14 to 4.47 (L kg^–1) for atrazine, and 0.04 to 5.30 (L kg^–1) for metolachlor. Adsorption capacity decreased in the order Sloan loam > Del Rey loam > Ottokee fine sand. Koc values varied considerably for both pesticides: metolachlor > in Sloan loam, atrazine metolachlor in Del Rey loam, and atrazine > metolachlor in Ottokee fine sand. In addition to organic matter content, clay played a key role in adsorption in the Del Rey loam and Ottokee fine sand. Higher adsorption was observed at pH 5 for both pesticides. As pH decreased to 3 and increased to 11, adsorption decreased. Adsorption increased as ionic strength increased.     

砂壤中铜的吸附行为及其影响因素研究

研究了果园附近砂壤中Cu的吸附行为，并探讨了pH值及土壤有机质对吸附的影响。结果表明，供试土壤对Cu的吸附行为可用Freundlieh方程拟合，电性吸附态Cu较易解吸；而专性吸附态Cu较难解吸。动力学实验表明，最初4h内的吸附量占总吸附量的60％以上，8h后达到平衡；而解吸在最初30min内占了近80％，2h后可达平衡。低pH值时，H^＋和Cu发生竞争吸附，可明显抑制土壤对Cu的吸附；随pH值的升高，抑制作用减弱，其logKd与pH呈线性正相关；在中性和偏碱性范围，pH值对土壤吸附Cu的影响不大。原土去除有机质后对Cu的分配系数降低了10倍。     

Microdetermination of protease activity in humic bands of different sizes after analytical isoelectric focusing

Summary Extracellular benzoyl-l,-argininamide (BAA)-hydrolysing protease was extracted with neutral pyrophosphate from an arable soil and fractionated by membrane ultrafiltration. There were three fractions: A₁ (molecular weight > 10⁵), A_II (molecular weight 10⁴–10⁵), and R (molecular weight < 10⁴). Analytical isoelectric focusing (IEF) of the fractions was carried out on polyacrylamide gels with a restricted pH gradient of 4.0 to 5.0. Two extracellular proteases characterized soil extract E, with one peak (Ip 4.44) bound to a large amount of humic matter and the other (Ip 4.06) bound to a small amount of humus. Following ultrafiltration, the humus-enzyme complex of extract E (Ip 4.44) split into the fractions A_I, A_II, and R, and was displaced at Ip values that depended on the electrophysical properties of bound organic matter, whereas that at Ip 4.06 was completely removed from the extract E and accumulated only into the low-molecular-weight fraction R. High recoveries of absolute activity were obtained after IEF of the whole extract E, and fractions A_II and R, but only about 50% was recovered from fraction A_I.It appears that humic substances have reversible inhibitory effects on extracellular proteases, since the maximum recoveries of activity were obtained from fractions where high amounts of protease non-active organic matter had been removed by IER IEF was able to fractionate humic molecules and purify humic-protease complexes on the basis of smaller differences in Ip, and even smaller differences of 0.05 pH units. The present results show that BAA hydrolysing proteases were preferentially linked with a specific class of humic molecules with an Ip of close to 4.44.Joint program CNR (Italy) — C.S.I.C. (Spain), no. 7, 1985–1986. This paper is part of the doctoral thesis of Prof. M. Bonmati