Urea-montmorillonite-extruded nanocomposites: a novel slow-release material

The present study describes the preparation and characterization of a novel urea slow-release nanocomposite, based on urea intercalation into montmorillonite clay by an extrusion process at room temperature. Nanocomposites with urea contents ranging from 50 to 80 wt % were successfully produced and characterized. Analyses by XRD, DTA, and SEM-EDX confirmed the effectiveness of this simple process to exfoliate the clay lamellae into the urea matrix, forming a product that can be classified as a nanocomposite, due to the exfoliation degree attained. Diametral compression tests showed that the samples were very deformable, and the release rate of active components in water showed that the nanocomposite showed a slow release behavior for urea dissolution, even in low montmorillonite amounts (20% in weight).     

Benzalkonium Chloride Surface Adsorption and Release by Two Montmorillonites and Their Modified Organomontmorillonites

Benzalkonium chloride (BAC) loaded to montmorillonites (Mt) or organomontmorillonites (OMt) generates a functional material that can be incorporated to several systems (polymers, paints, etc) as a controlled release bactericide. Understanding the BAC adsorption sites on these adsorbents is of high importance to clarify their adsorption/desorption characteristics in aqueous media or other solvents. In this work, a thorough study about the adsorption/desorption properties of Mt and OMt with regards to BAC is presented, in order to evaluate further BAC release with the consequent aquatic environment contamination. In this work, the BAC adsorption on two different sites is demonstrated: the interlayer space and the external surface. Depending on BAC concentration in water, sorption of BAC at Mt occurred in two steps. At adsorbed amount <0.5 mmol g^?1, there was an Mt interlayer expansion of 0.49 nm with no change of the external charge. At adsorbed amount >0.5 mmol g^?1, there was a new interlayer expansion attaining 0.75 nm and the external charge shifted to positive value. In the case of OMt, the introduction of BAC produced changes in the interlayer structure and in the external surface charge. BAC desorption was strongly dependent on the type of Mt or OMt and extraction solvent, knowledge of which will allow its safe use in environmental friendly technological applications.     

The nature and stability of aluminum hydroxide precipitated on wyoming montmorillonite

A freeze—fracture technique was used to prepare replicas of interlayer surfaces of a hydroxy-aluminum montmorillonite (OH-Al-SWy-1), synthesized by titrating an Al-clay with NaOH. Aqueous suspensions containing 0.01 M NaClO₄ and 4% OH-Al-SWy-1 were frozen rapidly with Freon 22 to vitrify the solution phase and stored in liquid N₂. The frozen samples were fractured at 10^?6 Torr and 158K and C-Pt replicas were made of the exposed surface. Transmission electron microscopy (TEM) of the replicas showed a randomly distributed surface precipitate. The precipitate was flat and angular, resembling gibbsite morphologically. Gibbsite crystals were observed outside the interlayer when the suspension was air-dried on microscope grids, underscoring the value of the freeze—fracture technique in minimizing alteration of the OH-Al-SWy-1 complex. Using the mass of Al(OH)₃ fixed by the clay and the average particle perimeter observed by TEM (49.3 nm), we estimated the maximum Al(OH)₃ surface charge density and site density available for phosphate adsorption. The range of surface charge density for the Al(OH)₃, estimated from crystallographic data, was very close to the range of surface charge density for montmorillonite, suggesting that the latter may influence the maximum particle size of the precipitate. The total charge and edge [-Al(OH)(H₂O)] site density were less than the observed CEC reduction on SWy-1 and maximum phosphate retention on OH-Al-SWy-1 at pH 5.3, respectively. Interlayer Al(OH)₃ is known to be unstable with respect to gibbsite and it is possible that a relatively high specific surface area was responsible for the high solubility.     

Assessment of urea coated with pomegranate fruit powder as N slow-release fertilizer in maize

It has been hypothesized that plant polyphenol plus lignin, cellulose, and hemicelluloses can immobilize/remineralize inorganic fertilizers, such as urea, better than polyphenol alone. To test this hypothesis, urea was coated with pomegranate (Punica granatum L.) fruit powder (containing polyphenol+lignin+cellulose) at rates of 0%, 30%, 70%, and 100% (w/w) of fertilizer urea. Fertilizer nitrogen was applied at 100 and 200 mg kg^?1 soil in a clay loam soil. This natural coating material, particularly at the rate of 100% (w/w), improved the distribution of mineral nitrogen (N) and available phosphorus (P) in soil during both early and advanced growth stages of maize and significantly increased total crop N and P uptake at both rates of fertilizer nitrogen compared to urea alone. The results suggest that urea coated with the powder of pomegranate fruit could potentially be an N slow-release fertilizer for use in better synchronizing crop N demand with soil N supply.     

Vermiculite in Some Japanese Soils

Since Gruner's pioneer work in 1934¹⁾, vermiculite has been attracting the attention of mineralogists and soil scientists with much interest, probably because of its unique behaviour on cation exchange and of a component common in most soils derived from various parent rocks. A number of papers thereafter dealt with the mineral, revealing its properties, diagenesis, and distribution in soils. However, as information has been accumulated on vermiculite, especially on clay vermiculite, it became evident that the difference between vermiculite and montmorillonite is due simply to the difference in layer charge and that the division is essentially an arbitrary one²⁾. Walker suggested that the Mg plus glycerol test would be the only one which appeared to be universaIlY valid in the identification of vermiculite, and that although the K test was still of value as an aid in the differentiation, it could no longer be reo commended as of universal validity. In recent years, several workers^4-12) indicated that interlayer materials, especially Al-hydroxyls, prevented vermiculite from contracting to 10 Å in the K test and prevented montmorillonite from expanding to 18 Å in the Mg-glycerol test. This suggests that in the light of new evidences the 14 Å mineral hitherto believed as vermiculite, chlorite, or montmorillonite by the classical test should be reexamined after removal of interlayer materials.     

Assessment of Salinity Variations in TBT Adsorption onto Kaolinite and Montmorillonite at Different pH Levels

Adsorption onto solid phases is an important process in controlling the distribution of toxic tributyltin (TBT) compounds in aqueous systems. In the present study, the TBT adsorption onto two types of clay, kaolinite (KGa) and montmorillonite (SWy), as a function of salinity (0, 8, 16, 24, 32‰) was investigated using the conventional batch technique. Experiments were carried out under different pHs (4, 6 and 8). For the different clay types examined, the highest TBT adsorption was found at a salinity of 0‰ and pH 6. In general, the TBT adsorptiondecreased with increasing salinity due to the growing competition with metallic cations to the surface sites of the clay minerals. Only at pH 4, the TBT adsorption onto kaolinite did not show any effect by changing the salinity. This was attributed to the pH_ZPC of 4.9 determined for the kaolinite sample. The results clearly demonstrated the importanceof identifying and characterizing the sorbents and determining the environmental conditions, in order to predict TBT distribution in natural systems or to compare partitioning coefficients of TBT ontosediment phases from different locations.     

Bioavailability of an organophosphorus pesticide,fenamiphos, sorbed on an organo clay

Hydrolysis of an insecticide/nematicide, fenamiphos [ethyl-3-methyl-4-(methylthio)phenyl-(1-methylethyl)phosphoramidate], immobilized through sorption by cetyltrimethylammonium-exchanged montmorillonite (CTMA-clay) by a soil bacterium, Brevibacterium sp., was examined. X-ray diffraction analysis, infrared spectra, and a negative electrophoretic mobility strongly indicated that fenamiphos was intercalated within the bacterially inaccessible interlayer spaces of CTMA-clay. The bacterium hydrolyzed, within 24 h, 82% of the fenamiphos sorbed by the CTMA-clay complex. There was a concomitant accumulation of hydrolysis product, fenamiphos phenol, in nearly stoichiometric amounts. During the same period, in abiotic (uninoculated) controls, 4.6% of the sorbed insecticide was released into the aqueous phase as compared to 6.0% of the sorbed fenamiphos in another abiotic control where activated carbon, a sink for desorbed fenamiphos, was present. Thus, within 24 h, the bacterium hydrolyzed 77% more fenamiphos sorbed by organo clay than the amounts desorbed in abiotic controls. Such rapid degradation of an intercalated pesticide by a bacterium has not been reported before. Evidence indicated that extracellular enzymes produced by the bacterium rapidly hydrolyzed the nondesorbable fenamiphos, even when the enzyme itself was sorbed. Fenamiphos strongly sorbed to an organo clay appears to be readily available for exceptionally rapid degradation by the bacterium.     

新型尿素缓释剂对作物产量的影响

尿素缓释剂不使用HQ(氢醌),而是采用多种化合物复配成的具有复合抑制功能的新型脲酶抑制剂。培养试验结果表明,尿素缓释剂对土壤脲酶活性有一定的抑制作用,可提高尿素肥效,使土壤中有效氮贮存量提高20 4%。田间试验结果表明,使用尿素缓释剂添加到尿素中,比普通尿素有明显的增产作用,粮食作物可增产14 5%,蔬菜可增产19 5%,且可省掉追肥的工序。     

尿素与缓释尿素配施添加DMPP对砂姜黑土氮素转化的影响

研究尿素与缓释尿素配施添加硝化抑制剂3,4-二甲基吡唑磷酸（DMPP）对砂姜黑土氮素转化的影响，为田间速效与缓释氮的合理配施提供理论依据。采用室内恒温、恒湿培养试验方法，试验设不施肥（CK）、单施尿素（N）、单施缓释尿素（S）、60%尿素+40%缓释尿素（NS）、尿素+DMPP（ND）、缓释尿素+DMPP（SD）、60%尿素+40%缓释尿素+DMPP（NSD）共七个处理，通过测定不同处理土壤中不同形态氮素含量，探究添加DMPP在单施尿素、单施缓释尿素及尿素与缓释尿素配施上对土壤氮素转化的不同影响。ND处理在培养第1~35 d内铵态氮含量均显著高于N处理（P<0.05），并有效延缓了铵态氮向硝态氮转化的时间。SD处理较之S处理在显著提高土壤中铵态氮含量的同时（P<0.05），也能有效抑制硝化作用，其硝化抑制有效作用时间在49 d左右，并且在此期间内能降低表观硝化率，提高硝化抑制率。与NS处理相比，NSD处理不仅能够显著提高土壤铵态氮含量（P<0.05），使铵态氮半衰期延长至18.6 d，硝化抑制率显著提高（P<0.05），表观硝化作用有效抑制时间延长了32 d左右。综合分析表明，尿素与缓释尿素配施添加DMPP在抑制氨氧化作用中效果明显，显著提高硝化抑制率（P<0.05），降低表观硝化率，有效延长了铵态氮在土壤中停留的时间，该措施为有效阻控农田氮素损失提供了科学依据。     

Interactions between montmorillonite and fulvic acid

The isotherms at 20°C for the adsorption of ¹⁴C-labelled fulvic acid from aqueous solutions by montmorillonite containing different exchangeable cations, have been determined. Below a concentration of 0.45 mg/ml and at near neutral pH, all samples give linear isotherms, the slope of which increases in the order Ba²⁺ < Ca²⁺ < Zn²⁺ < La³⁺ < Al³⁺ <Cu²⁺ < Fe³⁺. In the absence of interlayer expansion, the shape of the isotherms is interpreted in terms of solute entry into intercrystalline pores within a clay domain. The affinity of fulvic acid for the clay surface is related to the ionic potential or polarising power of the exchangeable cation. It is inferred that fulvic acid adsorbs by hydrogen bonding between an anionic group of the acid and a water molecule in the primary hydration shell of the saturating cation. Comparison of the data with those for the humic acid extracted from the same organic matter source, indicates that secondary interactions between adsorbed molecules or directly with the montmorillonite surface, contribute to the overall affinity. With samples saturated with Al³⁺, Fe³⁺, and Cu²⁺ ions, part of the adsorbed fulvic acid may also be attached to the clay by a complexation reaction involving the metals as such, or when they exist as polyhydroxy compounds at the mineral surface.     

Efficacy of starter N fertilizer and rhizobia inoculant in dry pea (Pisum sativum Linn.) production in a semi-arid temperate environment

ABSTRACT

Uncertainties exist about the importance of rhizobia inoculant and starter nitrogen (N) application in dry pea (Pisum sativum L.) production. Three field experiments were conducted to evaluate how rhizobia inoculant and starter N fertilizer affect pea seed yield and protein concentration in a semi-arid environment in central Montana. Commercial rhizobia inoculant was mixed with seed prior to planting at the manufacturer’s recommended rate. Starter N fertilizers were applied into the same furrow as seed at 0, 22, 44 and 88 kg ha^?1 as urea, slow-release polymer-coated N fertilizer (ESN), and a combination of both. The application of rhizobia inoculant had no or a very small beneficial effect on pea yield in lands with a previous history of peas. In a land without pea history, application of rhizobia increased pea seed yield by 16%. The positive effect of starter N was only pronounced when initial soil N was low (≤ 10 kg ha^?1 nitrate-nitrogen), which increased net return by up to US$ 42 ha^?1. In this condition, application of slow-release N outperformed urea. However, application of starter N (especially with urea) had a negative effect on pea establishment, vigor and seed yield when soil initial N was high (≥ 44 kg ha^?1 NO₃-N). The results indicate that the rate, placement and form of the starter N must be optimized to benefit pea yield and protein without detrimental effects on germination and nodulation. Moreover, application of starter N must be guided by the soil nitrate content.     

缓释尿素在双季稻上的养分供应特征

采用双季早晚稻的田间试验,研究了养分释放期为60 d和90 d的两种不同缓释尿素对整个生育期内水稻养分吸收的影响。结果表明:60 d型缓释尿素一次性施用在早、晚稻上均达到了普通尿素分次施肥时的产量水平,而90 d型缓释尿素一次性施用在早稻上效果好晚稻上效果欠佳。60 d和90 d型缓释尿素一次性施用的优势在于能使水稻有较高的有效穗数及穗粒数,整个生育期地上植株氮(灌浆期不含籽粒)含量也显著高于普通尿素分次施肥、普通尿素一次施用及不施氮处理,而灌浆过程中籽粒、剑叶、倒二位及倒三位叶的氮含量及剑叶SPAD值(叶绿素相对含量)也均高于其他3个处理。两种缓释尿素均使水稻出现了不同程度的贪青状况,其中以90 d型缓释尿素贪青最为严重,60 d型缓释尿素的养分释放期对水稻较为适中而90天型缓释尿素较长。     

Influence of potassium chloride on desorption of cadmium sorbed on hydroxyaluminosilicate-montmorillonite complex

Cadmium adsorption and desorption on a synthetic hydroxyaluminosilicate-montmorillonite (HAS-Mt) complex were investigated in comparison with a montmorillonite (Mt) and hydroxyaluminum-montmorillonite (HyA-Mt) complex.

Kinetics studies of Cd adsorption on Mt, HyA-Mt and HAS-Mt complexes were conducted at pH 5.0, using a 10^-7 M Cd(NO₃)₂ solution in a solid to solution ratio of 100 mg to 100 mL. After 240 min reaction, 94, 88, 32% of the added Cd were removed from the solutions of the Mt, HyA-Mt, and HAS-Mt systems, respectively. Considering the magnitude of the cation exchange capacity of the clay and complexes, affinity of Cd ions was highest for the HAS-Mt complex.

Desorption experiment was conducted using 1 M KC1, 1 M KNO₃, and water. The desorption rate of Cd sorbed on the Mt was the highest, 90 and 59%, using KC1 and KNO₃, respectively, while, that on the HyA-Mt and HAS-Mt was around 30% and much lower than in the case of Mt, using both chemical reagents. Water could not desorb the adsorbed Cd at all. The difference in the desorption rate between KC1 and KNO₃ was due to the complex ion formation of Cd with the anionic species.

The adsorption of Cd by Mt varied with the nature of intercalated materials, namely, HyA and HAS. The extent of the desorption of Cd decreased due to intercalation of HAS and HyA. In the soil environment, Mt is commonly intercalated with HyA and/or HAS. Our data indicated that the formation of HyA- and HyA-Mt complexes should lead to Cd accumulation in soil environments. In addition, the application of potash (KC1) fertilizer would enhance the desorption of the Cd accumulated in soils.     

Effects of Clay Surfaces on the Adsorption and Biological Decomposition of Proteinaceous Components of Fulvic Acid

Shaking of an aqueous fulvic acid (FA) solution with montmorillonite at pH 2.5 at room temperature, removed about 43 % of the FA fraction containing proteinaceous components. About 65 % of this fraction was adsorbed reversibly in interlayers, 20 % on external surfaces and 15 % was adsorbed irreversibly. The relative molar distribution of the amino acids (after hot acid hydrolysis) in the original FA, the FA fraction adsorbed in clay interlayers and in the FA fraction not adsorbed by montmorillonite was relatively uniform, indicating that clay interlayers were relatively inefficient for separating proteinaceous constituents from main structural FA components. External clay surfaces, however, appeared to adsorb peptides and/or proteins that differed qualitatively from those adsorbed on internal clay surfaces. Five successive treatments with fresh clay showed that only 61 % of the FA fraction containing proteinaceous components could be adsorbed. The original FA and all fractions separated from it by montmorillonite were able to support microbial growth without the addition of an external N source. The rate of biodegradation decreased when the FA was complexed with montmorillonite.     

Slow-release formulations of sulfometuron incorporated in micelles adsorbed on montmorillonite

The design and tests of slow-release formulations of sulfometuron (SFM), an anionic sulfonylurea herbicide, are described. The formulations are based on incorporation of the herbicide in octadecyltrimethylammonium (ODTMA) micelles, which adsorb on a clay mineral, montmorillonite. An optimization of herbicide/micelle clay ratios yielded high adsorption of SFM (95%), and at a 1% (w/w) water suspension only 0.5% of the adsorbed SFM was released at times varying from hours to 9 days. An analytical test in Seville soil showed that under excessive irrigation (400 mm) 100% of the commercial formulation leached, whereas the micelle-clay formulations showed only 50-65% elution. A plant bioassay in Rehovot soil showed that the commercial dispersible granule formulation (Oust, 75% ai sulfometuron methyl) yielded only 23% root elongation inhibition at the top 5 cm of the soil, whereas complete inhibition was achieved with the micelle-clay formulation. The detected concentration of SFM for the micelle-clay formulation at a depth of 15-20 cm was half of that detected for the commercial one, indicating a reduction in leaching when applying the micelle-clay formulation. A 10-fold reduction in the applied dose of SFM in the micelle-clay formulations resulted in good herbicidal activity of 60-87% inhibition. These characteristics make the new formulation promising from the environmental and economic points of view.     

Effect of pH on Zinc Adsorption and Solubility in Suspensions of Different Clays and Soils

Zinc solubility in clay and soil suspensions was controlled by chemisorption at pH 4.5 – 7.0. The solubility in clay mineral suspensions was in the order palygorskite < montmorillonite « kaolinite and reflected the high affinity of zinc to palygorskite and the high CEC of montmorillonite. The solubility in soil suspensions was in the order Haplustoll < Torrifluvents and reflected the effect of high CEC and organic matter content of the first. The slopes of the pH-pZn curves, calculated zinc potential and sequential desorption data suggested that Zn⁺⁺ ? Zn(OH)₂ aqueous controlled the solubility of zinc in soil and clay mineral suspensions at pH 7.5 – 9.0. The slopes of the pH–pZn curves of two soils were, however, modified by the possible peptization of organic matter and Zn(OH)₂.     

Adsorption mechanisms of thiazafluron in mineral soil clay components

The adsorption of the herbicide thiazafluron, 1,3-dimethyl-1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)urea, by three smectites, illite, kaolinite, ferrihydrite and the clay fraction of an illitic soil (54.9% illite, 17.0% montmorillonite and 24.9% kaolinite) and a montmorillonitic soil (33.9% illite, 55.0% montmorillonite and 11.1% kaolinite) has been determined. Thiazafluron adsorbed on neither kaolinite nor iron oxide. The adsorption isotherms on smectites and illite conformed to the Freundlich equation. Values of K_f-obtained for smectites were larger than for the illite and increased as the layer charge of the smectite decreased. Desorption of thiazafluron on smectites was shown to be highly irreversible. Adsorption isotherms of thiazafluron on different homoionic montmorillonite samples suggest an important role of the exchangeable cations in the adsorption. Infrared spectra and X-ray diffraction analysis of the complexes of thiazafluron with homoionic montmorillonites indicated that thiazafluron adsorbs in the interlamellar space of the smectites, mainly by substitution of water molecules associated with the exchangeable cations through the carbonyl-amide group and formation of H-bonds or waterbridge between the NH group of the amide and the basal oxygens of the montmorillonite. The illitic soil clay adsorbed more of the herbicide than the montmorillonitic one did, suggesting that illite and montmorillonite may be present in soils in altered forms giving rise to different adsorption capacities from those of the pure minerals.     

Computer simulation of the structure and dynamics of phenol in sodium montmorillonite hydrates

Monte Carlo and molecular dynamics computer simulations have been used to study the structure and dynamics of phenol‐water solutions in the bulk and confined within the interlayer pores of sodium montmorillonite clays, as a function of pressure and temperature. Conditions have been chosen to mimic those encountered at burial depths of up to 6 km, thereby enabling us to shed light on subsurface processes including groundwater contamination and oil and gas migration. The structural data show that the phenol molecules are able to form a donor hydrogen bond to the clay surface. In addition, the phenolic –OH group is solvated by approximately three water molecules, and is also able to coordinate directly to an interlayer sodium cation. The phenolic aromatic ring is surrounded by approximately 25 water molecules in the bulk, compared to 18 in the compacted clay. Interlayer diffusion increases by an order of magnitude as temperature is increased from 275 K to 460 K. However, diffusion decreases by a factor of 2–4 as we move from the bulk into a clay hydrate of layer spacing ∼17 Å. For example, at 275 K the diffusion coefficient of phenol is 8.3 × 10⁻¹⁰ m² s⁻¹ in bulk solution, compared to 2.5 × 10⁻¹⁰ m² s⁻¹ in the clay.     

太白山北坡土壤的粘土矿物

太白山位于陕西省西部,绝顶海拔近4000米,是秦岭山脉的主峰,属于我国西北中部地区最高名山之一。地理位置约为北纬33.9-34.15度,东经107.4-108.0度。由于秦岭的屏障使潮湿的海洋气团不易深入西北,同时也阻挡了北方的寒潮不致长驱南下,所以秦岭已成为自然地理上划分我国东部南北的重要界线。太白山的气候具有南温带的温和气候和北亚热带的温暖气候特点,属于温带和亚热带过渡性地带。     

Interactions between H-bentonite and aluminous chlorite-like complexes

In synthetic chlorite-like complexes, amounts of amorphous and/or crystalline hydrous aluminum oxide were determined through use of H-bentonite that converts into Albentonite by reaction with Al-gel or gibbsite. In Al(OH)_x-complexes with less than 1,000 mequiv. of Al per 100 g of clay, hydrous aluminum oxide gel remains held on clay surfaces without crystallizing for a long time. The neutralization reaction between a one-symmetry-concentration of H-bentonite and chlorite-like complexes at 10°C is initially very fast and seems to affect exclusively the hydrous oxide in suspension or adsorbed on the external surfaces and edges of clay particles. After a few hours, the interlayer Al-gel begins to be neutralized and the reaction rate decreases according to first-order kinetics. In complexes of equal ages, more time is required to neutralize the hydrous oxide precipitated in the presence of clay than added to the clay, because of a different interlayering.The kinetics of reactions between complexes characterized by amorphous and crystalline aluminum hydroxide (more than 1,000 mequiv. aluminum per 100 g of clay) and H-bentonites were studied. H-bentonite reacts with gibbsite much more slowly than it does with amorphous forms, always according to first order kinetics.