Reactions of nucleic acid bases with inorganic soil constituents

The adsorption at pH's 4, 6 and 8 of adenine, guanine, cytosine, thymine and uracil on clays (montmorillonite, illite and kaolinite), Fe- and Al-oxides (goethite, hematite and gibbsite), a soil, and on a laboratory-prepared fulvic acid-montmorillonite complex was investigated. Portions of the clays and soil were saturated with H⁺, Fe³⁺ and Ca²⁺.Quantitatively, the extent of adsorption of nucleic acid bases by the clays was proportional to their exchange capacities, but the nature of the dominant cation had only minor effects. By contrast, the adsorption was strongly affected by pH, tending to decrease with increase in pH. Adsorption on goethite and gibbsite was lower than that on clays, while adsorption of nucleic acid bases on soils was slightly lower than that on oxides. The fulvic acid-montmorillonite complex adsorbed substantial, although smaller amounts of purines and pyrimidines, than did montmorillonite alone. The main adsorption mechanism at pH 4 appeared to be cation exchange whereas at pH 8 complex formation between the nucleic acid bases and cations on inorganic surfaces seemed to occur.The results of this and earlier work show that both inorganic and organic soil constituents adsorb nucleic acid bases. Which adsorption reaction predominates will depend on the clay and organic matter content and on the pH.     

Detection and decay of the Bt endotoxin in soil from a field trial with genetically modified maize

Genetically modified plants and their residues may have direct effects on ecosystem processes. We aimed to determine the amount in soil of the insecticidal δ‐endotoxin, originally from the bacterium Bacillus thuringiensis, introduced into soil by root exudates and residues from genetically modified maize, to compare the short‐term rates of decay of Bt‐maize and non‐Bt‐maize, and to determine the rate at which the toxin in Bt‐maize leaves decomposes in soil. Intact soil, size fractions of soil, soluble fractions from soil and fractions of organic residues from a field where Bt‐maize had been cultivated for 4 years were analysed for the Btδ‐endotoxin. Traces of the δ‐endotoxin were detected in the whole (unfractionated) soil, the water‐soluble fractions, and some of the particle‐size fractions, but it was sufficiently concentrated only in the > 2000‐µm size fraction to be quantified. The δ‐endotoxin concentrations in this fraction ranged between 0.4 and 4.4 ng toxin g^?1 fraction, which equated to 70, 6 and 50 mg toxin m^?2 in the 0–15, 15–30 and 30–60 cm depths, respectively (or 126 mg toxin m^?2 over the 0–60 cm depth) in the field in June (early summer). The > 2000‐µm size fraction was a mixture of light‐ and dark‐coloured organic material and mineral material comprising sand grains and stable aggregates. For samples collected early in the growing season, most of the detected δ‐endotoxin was present in the light‐coloured organic material, which was comprised of primarily live roots. However, recognizable maize residues, probably from previous years' crops, also contained δ‐endotoxin. In a laboratory incubation study, Bt‐ and non‐Bt‐maize residues were added to soil and incubated for 43 days. There was no detectable difference in the decomposition of plant material from the two lines of maize, as determined by CO₂ production. The quantity of δ‐endotoxin in the decomposing plant material and soil mixtures declined rapidly with time during the incubation, with none being detectable after 14 days. The rapid disappearance of the δ‐endotoxin occurred at a rate similar to that of the water‐soluble components of the maize residues. The results suggested that much of the δ‐endotoxin in crop residues is highly labile and quickly decomposes in soil, but that a small fraction may be protected from decay in relatively recalcitrant residues.     

Effect of Soil Organic Matter on Adsorption and Insecticidal Activity of Toxins from Bacillus thuringiensis

With the large-scale cultivation of transgenic crops expressing Bacillus thuringiensis (Bt) insecticidal toxin in the world, the problem of environmental safety caused by these Bt crops has received extensive attention. The effects of soil organic matter (SOM) on the adsorption and insecticidal activity of Bt toxin in variable- and constant-charge soils (red and brown soils, respectively) were studied. Organic carbon in the soils was removed using hydrogen peroxide (H_2O_2). After H_2O_2 treatment, the SOM in the red and brown soils decreased by 71.26% and 82.82%, respectively. Mineral composition of the H_2O_2-treated soils showed no significant changes,but soil texture showed a slight change. After SOM removal, the cation exchange capacity (CEC) and pH decreased, while the specific surface area (SSA), point of zero charge (PZC), and zeta potential increased. The adsorption isotherm experiment showed that the Bt toxin adsorption on the natural and H_2O_2-treated soils fitted both the Langmuir model (R~2≥ 0.985 7) and the Freundlich model (R~2≥ 0.984 1), and the amount of toxin adsorbed on the H_2O_2-treated soils was higher than that on the natural soils. There was a high correlation between the maximum adsorption of Bt toxin and the PZC of soils (R~2= 0.935 7); thus, Bt toxin adsorption was not only influenced by SOM content, but also by soil texture, as well as the SSA, CEC, PZC, and zeta potential. The LC_(50) (lethal concentration required to kill 50% of the larvae) values for Bt toxin in the H_2O_2-treated soils were slightly lower than those in the natural soils, suggesting that the environmental risk from Bt toxin may increase if SOM decreases. As the measurement of insecticidal activity using insects is expensive and time consuming, a rapid and convenient in vitro method of enzyme-linked immunosorbent assays is recommended for evaluating Bt toxin degradation in soils in future studies.     

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.     

胡敏酸对铵钾在粘土矿物上交互作用的影响

Interaction of ammonium (NH+4) and potassium (K+) is typical in field soils. However, the effects of organic matter on interaction of NH+4 and K+have not been thoroughly investigated. In this study, we examined the changes in major physicochemical properties of three clay minerals (kaolinite, illite, and montmorillonite) after humic acid (HA) coating and evaluated the influences of these changes on the interaction of NH+4 and K+on clay minerals using batch experiments. After HA coating, the cation exchange capacity (CEC) and specific surface area (SSA) of montmorillonite decreased significantly, while little decrease in CEC and SSA occurred in illite and only a slight increase in CEC was found in kaolinite. Humic acid coating significantly increased cation adsorption and preference for NH+4, and this effect was more obvious on clay minerals with a lower CEC. Results of Fourier transform infrared spectrometry analysis showed that HA coating promoted the formation of H-bonds between the adsorbed NH+4 and the organo-mineral complexes. HA coating increased cation fixation capacity on montmorillonite and kaolinite, but the opposite occurred on illite. In addition, HA coating increased the competitiveness of NH+4 on fixation sites. These results showed that HA coating affected both the nature of clay mineral surfaces and the reactions of NH+4 and K+with clay minerals, which might influence the availability of nutrient cations to plants in field soils amended with organic matter.     

Adsorption of the Bacillus thuringiensis toxin (Cry1Ab) on Na‐montmorillonite and on the clay fractions of different soils

The adsorption of the toxin from Bacillus thuringiensis (Bt‐toxin), which is synthesized in genetically modified maize, on sterilized Na‐montmorillonite and on H₂O₂‐treated and untreated clay fractions of three soils from different sites were studied. All adsorption isotherms can be described by a linear isotherm. Although all clay fractions from the different soils show nearly the same mineralogical composition, we found different affinities ranging from k = 47.7 to k = 366.7 of the adsorbates for the Bt‐toxin. The H₂O₂‐treated clay fractions show no correlation between the adsorption affinity and the amount of soil organic matter. On the other hand, there is a correlation between the content of organic carbon and the adsorption affinity of the untreated clay fractions. This can be explained by the fact that due to the coatings of soil organic matter on aggregates, the Bt‐toxin polymers are not able to adsorb within the clay aggregates.     

Phosphate-induced aggregation kinetics of hematite and goethite nanoparticles

Purpose

The purpose of the present study is to examine the effect of phosphate on the aggregation kinetics of hematite and goethite nanoparticles.

Materials and methods

The dynamic light scattering method was used to study the aggregation kinetics of hematite and goethite nanoparticles.

Results and discussion

Specific adsorption of phosphates could promote aggregation through charge neutralization at low P concentrations, stabilize the nanoparticle suspensions at medium P concentrations, and induce aggregation through charge screening by accompanying cations at high P concentrations. Two critical coagulation concentration (CCC) values were obtained in each system. In NaH₂PO₄, the goethite CCC at low phosphate concentrations was smaller than hematite and vice versa at high phosphate concentrations. Stronger phosphate adsorption by goethite rapidly changed the zeta potential from positive to negative at low phosphate concentrations, and the zeta potential became more negative at high phosphate concentrations. The clusters of hematite nanoparticles induced by phosphate adsorption had an open and looser structure. Solution pH and the phosphate adsorption mechanisms in NaH₂PO₄, KH₂PO₄, and Na₃PO₄ solutions affected zeta potential values and controlled the stability of hematite suspensions during aggregation. High pH and preference for non-protonated inner-sphere complexes in Na₃PO₄ solution decreased the zeta potential of positively charged hematite and promoted aggregation. Activation energies followed the order NaH₂PO₄ > KH₂PO₄ > Na₃PO₄ at low P concentrations. K⁺ was more effective than Na⁺ in promoting hematite aggregation due to the non-classical polarization of cations.

Conclusions

Phosphate can enhance or inhibit the aggregation of hematite and goethite nanoparticles in suspensions by changing surface charge due to specific adsorption onto the particles. The phosphate-induced aggregation of the nanoparticles mainly depended on the initial concentration of phosphate.

     

Verhalten von Dünger-NH4 in Böden unterschiedlicher tonmineralischer Zusammensetzung im Inkubationsversuch

Fate of fertilizer ammonium in soils with different composition of clay minerals in an incubation experiment In an incubation experiment with three different soils (gray brown podsolic soil from loess, alluvial gley, and brown earth, derived from basalt) the specific adsorption (fixation) and release of fertilizer NH₄⁺ was investigated. In one treatment 120 mg NH₄–N/kg soil was added, while the other treatment (control) received no nitrogen. Soils samples were taken every ten days and analyzed for nonexchangeable and exchangeable NH₄⁺ and NO₃^?. The experimental results are showing that the specific adsorption of applied NH₄⁺ was related to the type of clay minerals. While the loess soil, rich in illite, and the alluvial soil, rich in expansible clay minerals, bound about 40% of the added NH₄⁺ specifically, the soil derived from basalt with mainly kaolinite bound only about 10 %. From the recently “fixed” fertilizer NH₄⁺ about a half was nitrified during the incubation period of about 9 weeks. In the control there was no significant release of specifically bound NH₄⁺. Obviously this NH₄⁺ is located more deeply in the interlayers of the clay minerals and not available to microorganisms.     

Iron oxides serve as natural anti-acidification agents in highly weathered soils

Purpose

The effect of Fe oxides on the natural acidification of highly weathered soils was investigated to explore the natural acidification process in variable charge soils

Materials and methods

A variety of highly weathered soils with different Fe oxide contents were collected from the tropical and subtropical regions of southern China to investigate the soil acidity status. Electrodialysis experiments were conducted to simulate natural acidification process and promote accelerated acidification in a variety of systems such as relatively less weathered soils, mixtures of goethite with montmorillonite or kaolinite, an Alfisol, a limed Ultisol, and Fe oxides coated montmorillonite. The objective was to gather evidence for the occurrence of Fe oxide inhibited natural acidification in highly weathered soils.

Results and discussion

Highly weathered soils with free Fe₂O₃?<?100?g/kg (17 soils) had an average pH?=?4.64?±?0.06, while the soils with free Fe₂O₃?>?100?g/kg (49 soils) had an average pH?=?5.25?±?0.04. A significant linear relationship was found between the soil pH and Fe oxide content of these soils. Similar results were obtained in electrodialysis experiments, i.e., in soils that underwent accelerated acidification. A negative correlation was found between the Fe oxide content and exchangeable acidity or effective cation exchange capacity, respectively. In another set of experiments, goethite slowed down acidification in experiments conducted with this Fe oxide and montmorillonite, or kaolinite, or an Alfisol, or a limed Ultisol. The overlapping of the electrical double layers on the positively charged Fe oxide particles and negatively charged minerals may have caused the release and subsequent leaching of the base cations, but inhibited the production of exchangeable acidity cations. In addition, when montmorillonite or Fe oxide-coated montmorillonite were electrodialyzed in another set of experiments, exchangeable acidity of the former was much greater than that of the latter, suggesting that the positively charged Fe oxide coatings on montmorillonite have partially neutralized the permanent negative charge on montmorillonite surfaces, decreasing exchangeable acidity.

Conclusions

Fe oxides may function as natural ??anti-acidification?? agents through electric double-layer overlapping and coating of phylliosilicates in highly weathered soils.     

Ammonium fluoride extraction for determining inorganic sulphur in acid forest soils

Current methods for determining inorganic sulphur (S) in aerated mineral soil horizons often result in underestimates. To overcome this defect we developed a new method combining a batch extraction with 0.5 m NH₄F solution at a soil:solution ratio of 1:5 with a subsequent analysis of the mobilized SO₄^2– by ion chromatography. The ammonium fluoride extraction enables us to characterize inorganic sulphate in non‐calcareous forest soils. It is more efficient than conventional procedures in which inorganic S is extracted with phosphate or bicarbonate solution. In contrast to the extraction with strongly alkaline reagents (NaOH, KOH, LiOH), the NH₄⁺–NH₃ buffer system in NH₄F prevents the pH of the suspension from exceeding 9.0 and thus the undesired conversion of organic S into SO₄^2– by auto‐oxidation and hydrolysis of ester sulphate. In a comparison we demonstrated that the inorganic S in six German forest soils is underestimated by up to 50% or 200 kg S ha^?1 in the uppermost 60 cm, if it is assessed by extraction with 0.016 m KH₂PO₄ or 0.5 m NaHCO₃ instead of 0.5 m NH₄F. Conversely, the pool of ester sulphate is overestimated almost threefold.     

Estimating soil ammonium adsorption using pedotransfer functions in an irrigation district of the North China Plain

Extensive use of chemical fertilizers in agriculture can induce high concentration of ammonium nitrogen(NH4⁺_-N) in soil. Desorption and leaching of NH4⁺_-N has led to pollution of natural waters. The adsorption of NH4⁺_-N in soil plays an important role in the fate of the NH4⁺_-N. Understanding the adsorption characteristics of NH4⁺_-N is necessary to ascertain and predict its fate in the soil-water environment, and pedotransfer functions(PTFs) could be a convenient method for quantification of the adsorption parameters. Ammonium nitrogen adsorption capacity, isotherms, and their influencing factors were investigated for various soils in an irrigation district of the North China Plain. Fourteen agricultural soils with three types of texture(silt, silty loam, and sandy loam) were collected from topsoil to perform batch experiments. Silt and silty loam soils had higher NH4⁺_-N adsorption capacity than sandy loam soils.Clay and silt contents significantly affected the adsorption capacity of NH4⁺_-N in the different soils. The adsorption isotherms of NH4⁺_-N in the 14 soils fit well using the Freundlich, Langmuir, and Temkin models. The models’ adsorption parameters were significantly related to soil properties including clay,silt, and organic carbon contents and Fe²⁺ and Fe³⁺ ion concentrations in the groundwater. The PTFs that relate soil and groundwater properties to soil NH4⁺_-N adsorption isotherms were derived using multiple regressions where the coefficients were predicted using the Bayesian method. The PTFs of the three adsorption isotherm models were successfully verified and could be useful tools to help predict NH4⁺_-N adsorption at a regional scale in irrigation districts.     

不同热解温度茶渣生物质炭对茶园土壤吸附解吸NH4-N的影响

生物质炭对铵根的吸附解吸影响着土壤的固氮效果,为探讨茶渣生物质炭对茶园土吸附—解吸NH_4~+—N性能的影响,减少土壤中氮素的淋失,提高氮素利用效率,通过模拟培养试验,采用平衡吸附法及HCL解吸法,研究了不同热解温度下制备的茶渣生物质炭在不同添加比例(0.35%,0.70%,1.40%,2.80%)下,茶园土对NH_4~+—N吸附解吸的特性。结果表明:施用生物质炭能有效增强茶园土对NH_4~+—N的吸附,并随生物质炭添加量的增加而增强。同一生物质炭添加量下,4种生物质炭处理下茶园土对NH_4~+—N的吸附量大小表现为BC400BC300BC500BC600。生物质炭的CEC含量是影响土壤吸附NH_4~+—N能力的主要因素。土壤对NH_4~+—N的吸附过程均以Langmuir方程拟合达到显著水平(0.953 7R~20.995 5),以单层吸附为主。施用生物质炭后,土壤产生了解吸滞后,有效降低了茶园土对NH_4~+—N的解吸率,BC400的解吸率最低。茶渣生物质炭能够增强土壤对NH_4~+—N的吸附,降低对NH_4~+—N的解吸,有利于提高土壤对氮素的吸持能力,其中BC400,2.80%处理下效果最佳。     

Synthesis of a Novel Ambipolar Resin Membrane for Ion Adsorption

ABSTRACT

We have synthesized a novel composite ambipolar resin membrane with a high water absorption capacity (150?200%) and superior ion adsorption properties. The ambipolar membrane was capable of adsorbing nitrate, ammonium, potassium and phosphorus simultaneously from aqueous solutions. The adsorption capacity of the membrane varied with ionic concentration and composition. Thus, from a mixed solution of 30 mmol…L^{? 1}NH₄ ⁺ and 10 mmol…L^{? 1} each of NO₃ ^?, K⁺, and H₂PO₄ ^?, the synthetic membrane was able to take up 0.241 mmol NH₄ ⁺, 0.151 mmol NO₃ ^?, 0.120 mmol K⁺, and 0.046 mmol H₂PO₄ ^? per g membrane. A large proportion (73.9?92.5%) of the adsorbed ions could be desorbed with dilute (5%) HCl. The rate of desorption is inversely related to the cross-linking density of the membrane. The competition between NO₃ ^?and H₂PO₄ ^? as well as between K⁺ and NH₄ ⁺ was also investigated.     

Interaction of naphthalene derivatives with soil: an experimental and theoretical case study

This study provides insight into the relevance of the chemical functional groups of soil organic matter (aromatic, paraffinic, O‐alkyl, carboxyl and carbonyl carbon), as determined by CPMAS ¹³C NMR, on adsorption processes. Batch adsorption experiments with eight naphthalene derivatives were conducted with soils from a long‐term field experiment and model sorbents. Although the adsorption of some derivatives was mainly affected by the paraffinic organic carbon content in soil, the relation between the C‐distribution and adsorption was complex. This casts doubt on the use of such NMR data to estimate sorption behaviour. Additionally, sorption experiments were performed with six model sorbents representing typical soil components. Considerable adsorption of naphthalene derivatives was observed for montmorillonite and lignin; the smallest values were for kaolinite and cellulose. A quantum chemical approach was used to calculate a local polarity parameter as a molecular property of the naphthalene derivatives. This parameter was correlated with the logarithm of the adsorption coefficients, logK_d. Here, clear trends were observed for three of the model sorbents (kaolinite, montmorillonite and lignin).     

Interactions between Inorganic Nitrogen Nutrition and Root Development

Root development responds not only to the quantity of inorganic nitrogen in the rhizosphere, but to its form, NH₄⁺ or NO₃^?. Root growth of tomato showed a hyperbolic response to soil levels of inorganic nitrogen: very few roots were found in soil blocks depleted in inorganic nitrogen, roots proliferated as soils increased to 2 μg NH₄⁺-N g^?1 soil or 6 μg NO₃^?-N g^?1 soil, and root growth declined in soils with the higher levels of inorganic nitrogen. High NH₄⁺ concentrations inhibited root growth, but low concentrations promoted the development of an extensive, fine root system. Supply with NO₃^? as the sole nitrogen source led to a more compact root system. These differences in root morphology under NH₄⁺ and NO₃^? nutrition may be mediated through pH. Rice and maize roots absorbed NH₄⁺ most rapidly right at the apex and appeared to assimilate this NH₄⁺ in the zone of elongation. During NH₄⁺ assimilation, root cells must release protons, and the resulting acidification around the walls of cells in this region should stimulate root extension. By contrast, NO₃^? absorption reached a maximum in the maturation zone of rice and maize roots, and this NO₃^? was probably assimilated in more basal regions. Absorption of NO₃^? requires proton efflux, whereas NO₃^? assimilation requires proton influx. The net result under NO₃^? nutrition was only subtle shifts in rhizosphere pH that probably would not influence root elongation. The signal through which roots detect changes in rhizosphere NH₄⁺ and NO₃^? levels is still obscure. It is proposed that a product of nitrogen metabolism such as nitric oxide serves as a signal.     

Adsorption of DNA on clay minerals and various colloidal particles from an Alfisol

Adsorption and desorption of salmon sperm DNA on four different colloidal fractions from Brown Soil and clay minerals were studied. The adsorption isotherms of DNA on the examined soil colloids and minerals conformed to the Langmuir equation. The amount of DNA adsorbed followed the order: montmorillonite?fine inorganic clay>fine organic clay>kaolinite>coarse inorganic clay>coarse organic clay. A marked decrease in the adsorption of DNA on organic clays and montmorillonite was observed with the increase of pH from 2.0 to 5.0. Negligible DNA was adsorbed by organic clays above pH 5.0. As for inorganic clays and kaolinite, a slow decrease in DNA adsorption was found with increasing pH from 2.0 to 9.0. The results implied that electrostatic interactions played a more important role in DNA adsorption on organic clays and montmorillonite. Magnesium ion was more efficient than sodium ion in promoting DNA adsorption on soil colloids and minerals. DNA molecules on soil colloids and minerals were desorbed by sequential washing with 10 mM Tris, 100 mM NaCl and 100 mM phosphate at pH 7.0. A percentage of 53.7-64.4% of adsorbed DNA on organic clays and montmorillonite was released, while only 10.7-15.2% of DNA on inorganic clays and kaolinite was desorbed by Tris and NaCl. The percent desorption of DNA from inorganic clays, organic clays, montmorillonite and kaolinite by phosphate was 39.7-42.2, 23.6-28.8, 29.7 and 11.4%, respectively. Data from this work indicated that fine clays dominate the amount of DNA adsorption and coarse clays play a more important role in the binding affinity of DNA in soil. Organic matter may not favor DNA adsorption in permanent-charge soil. The information obtained is of fundamental significance for the understanding of the ultimate fate of extracellular DNA in soil.     

Hydrolysis of cellobiose by β-glucosidase in the presence of soil minerals - Interactions at solid-liquid interfaces and effects on enzyme activity levels

Extracellular enzymatic activities in soils are essential for the cycling of organic matter. These activities take place in multiphase environments where solid phases profoundly affect biocatalytic activities. Aspergillus niger is ubiquitous in soils; its β-glucosidase plays an important role in the degradation of cellulose, and therefore in the global carbon cycle and in the turnover of soil organic matter. However, the information on the interactions of this protein with soil minerals is very limited, and even less is known about their consequences for the hydrolysis of the natural substrate cellobiose. We therefore characterised the sorptive interactions of this enzyme with the soil minerals montmorillonite, kaolinite and goethite and quantified the resulting changes in the hydrolysis rate of cellobiose. Fractions of adsorbed protein, and the resulting catalytic activity loss, were lower for montmorillonite than for kaolinite and goethite at given experimental conditions; adsorption was 9.7 ± 7.3% for montmorillonite, 70.3 ± 3.1% for kaolinite and 71.4 ± 1.8% for goethite, respectively. Adsorption of the protein to the minerals caused a total decrease in the catalytic activity of 18.8 ± 3.4% for kaolinite and 17.9 ± 4.7% for goethite whereas it was not significant for montmorillonite. The average catalytic activity lost by the pool of adsorbed molecules was 26.8% for kaolinite and 25.0% for goethite. Both the amount of adsorbed protein and the resulting loss of catalytic activity were found to be independent of the specific surface areas yet were influenced by the electrical properties of the mineral surfaces. Under the experimental conditions, montmorillonite and kaolinite are negatively charged whereas goethite is positively charged. However, because of the adsorption of phosphate anions from the buffer, a charge reversal took place at the surface of goethite. This was confirmed by zeta (ζ)-potential measurements in phosphate buffer, revealing negative values for all the tested minerals. Indeed goethite interacted with the enzyme as a negatively charged surface: the amount of adsorbed protein and the resulting catalytic activity loss were very similar to those of kaolinite. Our results show that, even if an important fraction of β-glucosidase is adsorbed to the minerals, the catalytic activity is largely retained. We suggest that this strong activity retention in presence of soil minerals results from a selective pressure on A. niger, which benefits from the activity of the adsorbed, and thus stabilized, enzyme pool.     

Uptake Kinetics of Different Nitrogen Forms by Chinese Kale

In this paper, the uptake kinetics of various nitrogens (nitrate (NO₃^?), ammonium (NH₄⁺), urea, amino acid) by Chinese kale (Brassica oleracea L. var. Bailey) were studied under hydroponic condition. The results indicated that the uptake kinetics of organic and inorganic nitrogen (N) by Chinese kale conform to the Michaelis–Menten equation, and the maximum uptake rate (Vmax) and affinity index (1/Km) showed nitrate (NO₃^—N) > ammonium (NH₄⁺-N) > urea-N > Gly-N, with significant differences between treatments (p < 0.05). Adding different types of N to NO₃^? nutrient solution had little impact on its affinity, but significantly decreased the NO₃^? Vmax, which showed NO₃^–N > NO₃^? + NH₄⁺ > NO₃^? + urea > NO₃^? + Gly. Chinese kale preferred inorganic N to organic N, with NO₃^? preceding NH₄⁺. Adding organic and NH₄⁺ N to nutrient solution reduced the NO₃^? uptake capacity by the plant.     

Adsorption and Desorption of Cry1Ab Proteins on Differently Textured Paddy Soils

In recent years, selected cry genes from Bacillus thuringiensis (Bt) encoding the production of Cry proteins (Bt toxins) have been engineered into crop plants (Bt-crops). Through the cultivation of Bt crops and the application of Bt pesticides, Cry proteins could be introduced into arable soils. The interaction between the proteins and soils was analyzed in this study to investigate the affinity of Cry proteins in paddy soil ecosystems. Four Paddy soils were selected to represent different soil textures. Cry proteins were spiked in soils, and the amount of protein adsorbed was measured over 24 h. Desorption of Cry1Ab proteins from paddy soils was performed by washing with sterile Milli-Q water (H₂O_MQ), and subsequently extracted with an extraction buffer. The paddy soils had a strong affinity for Cry1Ab proteins. Most of the Cry1Ab proteins added (> 98%) were rapidly adsorbed on the paddy soils tested. More Cry1Ab proteins were adsorbed on non-sterile soils than on sterile soils. Less than 2% of the adsorbed Cry1Ab proteins were desorbed using H₂O_MQ, while a considerable proportion of the adsorbed proteins could be desorbed with the buffer, ranging from 20% to 40%. The amount of proteins desorbed increased with the increases in the initial amount of Cry1Ab proteins added to the paddy soils. The concentration of Cry1Ab proteins desorbed from the paddy soils was higher for sterile soils than non-sterile ones. Our results indicate that Bt toxins released via the cultivation of Bt crops, the application of Bt pesticides can be adsorbed on paddy soils, and soil texture could impose an impact on the adsorption capability.     

Clinoptilolite Zeolite Influence on Nitrogen in a Manure-Amended Sandy Agricultural Soil

Zeolite minerals may improve nitrogen availability to plants in soil and reduce losses to the environment. A study was conducted to determine the influence of clinoptilolite (CL) on nitrogen (N) mineralization from solid dairy manure (224 kg N ha^?1) in a sandy soil. Clinoptilolite was added to soil at six rates (0 to 44.8 Mg CL ha^?1), each sampled during 11 sampling dates over a year. Over time, nitrate (NO₃)-N increased, ammonium (NH₄)-N decreased, but total inorganic N increased. Clinoptilolite did not influence the nitrification rates of initial manure NH₄-N or mineralization of organic N (ON) over time. It is possible that adsorption of manure-derived potassium (K) outcompeted the NH₄-N for CL exchange sites. The ON concentration was constant up to 84 days and then decreased by approximately 18% over the remaining time of the study across all treatments. Clinoptilolite use in this sandy soil did not alter mineralization of N from dairy manure.