保水剂作为肥料养分缓释载体的应用

保水缓/控释肥料是具有吸水、保水及释水的新型缓/控释肥料,其对改善水肥效率具有良好的前景。保水缓/控释肥料的开发应用技术关键是研究开发可作为肥料载体材料的低成本新型保水剂材料。保水剂在性能上应具备吸水倍率高,吸水速率适宜,耐盐性好的优点;保水剂对肥料的吸附容量及其与肥料的化学结合性也是保水剂实际应用应考察的重要性能。不同类型的保水剂对肥料显示不同的吸附及化学结合特征,保水剂与肥料复合可以是物理、化学或物理化学的作用机制。保水剂可以通过物理包埋,物理、化学吸附、氢键、离子键及共价键结合、复合肥料养分。今后应加强新型廉价高效保水剂材料及其与肥料复合机制的研究。     

Ethylcellulose formulations for controlled release of the herbicide alachlor in a sandy soil

The development of controlled-release formulations of alachlor to diminish its leaching in sandy soils, avoiding groundwater contamination and maintaining its efficacy, was studied. For this purpose, ethylcellulose (EC) microencapsulated formulations (MEFs) of alachlor were prepared under different conditions and applied to soil columns to study their mobility. The results show that in all cases the release into water of alachlor from MEFs was retarded when compared with commercial formulation. Total leaching losses in soil columns were reduced to 59% from 98%. The mobility of alachlor from EC microspheres into soil columns has been greatly diminished in comparison with its current commercial formulation (CF), above all with increasing EC/herbicide ratios. Distribution of alachlor applied as MEFs at different depths in the soil was higher in the soil surface (66.3-81.3% of herbicide applied at the first 12 cm). In contrast, the residues from CF along the complete soil column were only 20.4%. From the results of bioassays, MEFs showed a higher efficacy than CF at 30 days after the treatment. The use of ME formulations could provide an advantage in minimizing the risk of groundwater contamination by alachlor and reducing the application rates, as a result of maintaining the desired concentration of the herbicide in the top soil layer, obtaining longer periods of weed control.     

Low molecular weight poly(lactic acid) microparticles for controlled release of the herbicide metazachlor: preparation, morphology, and release kinetics

The preemergence chloroacetamide herbicide metazachlor was encapsulated in biodegradable low molecular weight poly(lactic acid) micro- and submicroparticles, and its release to the water environment was investigated. Three series of particles, S, M, and L, varying in their size (from 0.6 to 8 μm) and with various initial amounts of the active agent (5%, 10%, 20%, 30% w/w) were prepared by the oil-in-water solvent evaporation technique with gelatin as biodegradable surfactant. The encapsulation efficiencies reached were about 60% and appeared to be lower for smaller particles. Generally, it was found that the rate of herbicide release decreased with increasing size of particles. After 30 days the portions of the herbicide released for its highest loading (30% w/w) were 92%, 56%, and 34% for about 0.6, 0.8, and 8 μm particles, respectively. The release rates were also lower for lower herbicide loadings. Metazachlor release from larger particles tended to be a diffusion-controlled process, while for smaller particles the kinetics was strongly influenced by an initial burst release.     

Influence of herbicide structure,clay acidity,and humic acid coating on acetanilide herbicide adsorption on homoionic clays

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite was studied by coupling batch equilibration and FT-IR analysis. Adsorption decreased in the order metolachlor > acetochlor > alachlor > propachlor on Ca(2+)- or Mg(2+)-saturated clays and in the order metolachlor > alachlor > acetachlor > propachlor on Al(3+)- or Fe(3+)-saturated clays. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in bonding. For the same herbicide, adsorption of alachlor, acetachlor, and metolachlor on clay followed the order Ca(2+) approximately Mg(2+) < Al(3+) < or = Fe(3+), which coincided with the increasing acidity of homoionic clays. Adsorption of propachlor, however, showed an opposite dependence, suggesting a different governing interaction. In clay and humic acid mixtures, herbicide adsorption was less than that expected from independent additive adsorption by the individual constituents, and the deviation was dependent on the clay-to-humic acid ratio, with the greatest deviation consistently occurring at a 60:40 clay-to-humic acid ratio.     

Nanosized silica modified with carboxylic acid as support for controlled release of herbicides

Hexagonal mesoporous silica modified with carboxylic acid (SiAc) has been obtained by reaction between chloroacetic acid and 3-aminopropyltrimethoxysilane, which was immobilized on porous material by a sol-gel process in the presence of an n-dodecylamine template. SiAc was characterized by TG, FT-IR, (29)Si NMR, (13)C NMR, SEM, surface charge density, surface area and porous diameter, which proved that the carboxylic group was chemically bonded to an inorganic structure, and the material presented a nanometric structure with spheres <50 nm and porous diameter of 10 nm. Herbicides 2,4-D and picloram were anchored on SiAc porous gel to produce the materials named SiD and SiPi, respectively. The controlled release of picloram from the SiAc was less than that of 2,4-D. After 26 days of releasing, 4.43 × 10(-5) mol L(-1) of picloram was delivered by SiPi, and 5.0 × 10(-5) L(-1) was released from the SiD in 30 days.     

Microparticle dispensers for the controlled release of insect pheromones

The potential utility of micrometer-sized particles as controlled-release devices for the volatilization of insect pheromones for mating disruption applications is evaluated in this study for two pheromone/model compound systems (codlemone/1-dodecanol and disparlure/1,2-epoxyoctadecane). To expedite the measurement of release rates from these particle devices, two techniques based on thermogravimetric analysis (TGA) have been exploited: isothermal TGA (I-TGA) at elevated temperatures (40-80 degrees C) with N(2) convection and volatilization temperature (VT) by dynamic TGA. A correlation between these two methods has been established. Samples that exhibit a higher VT provide a lower release rate from a particle substrate. Using these techniques, it has been demonstrated that chemical interactions between adsorbed liquids and particle surfaces may play a small role in defining release characteristics under conditions of low surface area, whereas parameters associated with total surface area and micropore structure appear to be much more significant in retarding evaporation for uncoated particles containing an adsorbed liquid. Additional regulation of release rates was achieved by coating the particle systems with water-soluble or water-dispersible polymers. By careful selection of particle porosity and coating composition, it is envisioned that the evaporation rate of pheromones can be tailored to specific insect control applications.     

Preparation and characterization of nanoparticles based on hydrophobic alginate derivative as carriers for sustained release of vitamin D3

Hydrophobic alginate derivative was prepared by modification of alginate by acid chloride reaction using oleoyl chloride without organic solvents. The conjugate of oleoyl alginate ester (OAE) was confirmed by FT-IR and (1)H NMR. The degree of substitution (DS) of OAE was determined by (1)H NMR, and it ranged from 0.84 to 3.85. In distilled water, OAE formed self-assembled nanoparticles at low concentrations in aqueous medium, and nanoparticles retained their structural integrity both in simulated gastric fluid (SGF) and simulated intestinal fluid (SIF). The loading and release characteristics of nanoparticles based on OAE were investigated using vitamin D(3) as a model nutraceutical. As the concentration of vitamin D(3) increased, the loading capacity (LC) increased, whereas the loading efficiency (LE) decreased. Nanoparticles could release vitamin D(3) at a sustained rate in gastrointestinal fluid. These results revealed the potential of OAE nanoparticles as oral carriers for sustained release of vitamin D(3).     

Herbicide solubilization in micelle-clay composites as a basis for controlled release sulfentrazone and metolachlor formulations

Sulfentrazone and metolachlor have been detected in groundwater due to extensive leaching. To reduce herbicide leaching and increase weed control, we have developed, designed, and tested controlled release formulations (CRFs) for both herbicides based on their solubilizion in cationic micelles and adsorption of the mixed micelles (surfactant and herbicide) on a clay mineral, montmorillonite. A better understanding of solubilizing anionic (sulfentrazone) and nonionic (metolachlor) organic molecules in cationic micelles was reached. The percent of active ingredient in the formulations was much higher than previously designed CRFs due to the enhanced solubilization of the herbicides in the micelles and due to their adsorption on the clay. Both CRFs demonstrated controlled release (compared to the commercial formulations) when applied to a thin soil layer. A bioassay in soil columns determined that the new sulfentrazone and metolachlor CRFs significantly improve weed control and reduce leaching (for the latter) in comparison with the commercial formulations.     

Controlled release of the herbicide norflurazon into water from ethylcellulose formulations

The herbicide norflurazon was encapsulated in ethylcellulose (EC(40)) microspheres by the solvent evaporation technique to obtain controlled release formulations. The kinetics of release of the active ingredient into the aqueous solution from different preparations was determined. It was found that the percentage release of the incorporated herbicide was a function of the composition and formation conditions of the formulations (amount of emulsifying agent, EC(40)/herbicide ratio, stirring speed, and percentage of pore-forming agent). The percentage of the herbicide release was related to the properties of the different microspheres obtained, such as particle size distribution, herbicide loading, or surface morphology. The release percentage depended inversely on the particle size of the microspheres and directly on the content of active ingredient and emulsifying and pore-forming agents. An empirical equation was used to fit the herbicide release data, indicating that the release of norflurazon from the various formulations is controlled by a diffusion mechanism. The time taken for 50% of the active ingredient to be released into water (T(50)) was calculated, showing a wide variation among the different preparations (0.95-16.4 days).     

Inorganic and organic pollutant measurements at the Kuwait Waterfront Project

The present paper presents the spatial distribution and monthly variations of Pb, Hg, PO₄, polycyclic aromatic hydrocarbons (PAH), and total organic carbon (TOC) collected from ten different sites along the Kuwait Waterfront Project during construction from October 1984 to September 1985. The data suggest that concentrations of the pollutants were not affected by the Waterfront Project construction, but were mainly related to activities on or near the Kuwait shore prior to construction.     

Amylose-lipid complexes as controlled lipid release agents during starch gelatinization and pasting

The effect of amylose-lipid (AM-L) complexes consisting of amylose populations with different peak degrees of polymerization (DP) and complexed with glyceryl monostearate (GMS) or docosanoic acid (C22) on the pasting properties of wheat and rice starches was evaluated with a rapid visco analyzer (RVA). AM-L complexes were formed by both (i) addition of lipids to amylose fractions with peak DP 20, 60, 400, or 950 at 60 degrees C or (ii) potato phosphorylase-catalyzed amylose synthesis in the presence of lipids. All AM-L complexes affected pasting properties in line with their dissociation characteristics. AM-L complexes therefore have potential as "controlled lipid release agents" with effects markedly different from those observable with emulsifier addition in starch pasting. More in particular, short chain AM-L complexes resulted in a starch pasting behavior comparable to that of cross-linked starch, as evidenced by reduced granule swelling, good viscosity stability in conditions of high temperature and shear, and a stable cold paste viscosity.     

Effects of organic amendment and herbicide treatment on soil microbial biomass

 The interactive effects of vermi-compost from sewage sludge and either the sulfonylurea herbicide, rimsulfuron, or the imidazolinone herbicide, imazethapyr, on some soil biochemical and microbiological properties were investigated. The herbicides were applied at field and 10-fold field rates. Both herbicides exerted a detrimental effect on soil microbial biomass and its biochemical properties. Even though the effect of both herbicides on soil microbial biomass was not detectable at the field rate, some significant influences on acid and alkaline phosphatase were observed. The higher rate of herbicide application impaired the observed microbial parameters to a greater degree. The detrimental effects seemed to be reduced by organic amendments. Among the studied microbial characteristics, the specific respiration quotient was particularly reliable and sensitive in determining the influence of herbicides on the soil microbial biomass. In this paper a new synthetic index, specific hydrolytic activity (qFDA), for assessing microbial activity in reply to xenobiotic treatments is proposed. Received: 31 May 1999     

Inorganic and organic mercury uptake and loss by the crayfish orconectes propinquus

Inorganic and organic Hg accumulation from food by the crayfish Orconectes propinquus was studied in the laboratory. Animals were fed pellets of dried cat food dosed in 1 jig g^?1 dw with ²⁰³Hg labeled HgCl₂ and CH₃HgCl over a two-week period. This was followed by a three-week depuration period which crayfish were fed uncontaminated food. At the end of each of these periods body tissues were analyzed for labeled Hg. ²⁰³Hg uptake from HgCl₂ followed the ranking: hepatopancreas > gills > exoskeleton > muscle. In all tissues there was evidence of Hg uptake from water via leaching from food although uptake was principally from food. Mercury uptake from CH₃HgCl followed the ranking: gills > muscle > hepatopancreas > exoskeleton. Only Hg accumulated from HgCl₂ by the hepatopancreas failed to depurate over the next three weeks. Mercury uptake by the hepatopancreas from CH₃HgCl was negligible. Results suggest a more rapid turnover of Hg in crayfish than in finfish.     

Efficacy of food proteins as carriers for flavonoids

Enrichment of flavonoids in food is often limited by their off-tastes, which might be counteracted by the use of food proteins as carriers of flavonoids. Various milk proteins, egg proteins, and gelatin hydrolysates were compared for their binding characteristics to two flavan-3-ols. Among the proteins tested for their affinities toward epigallocatechin gallate (EGCG), β-casein and gelatin hydrolysates, in particular fish gelatin, were found to be the most promising carriers with an affinity on the order of 10(4) M(-1). A flexible open structure of proteins, as present in random coil proteins, was found to be important. The saturation of binding observed at high flavonoid/protein ratios was used to estimate the maximal binding capacity of each protein. To reach a daily intake of EGCG that has been associated with positive health effects, only 519 mg of gelatin B and 787 mg of β-casein were required to complex EGCG on the basis of their maximal binding capacity. When the absence of turbidity is taken into account, β-casein prevails as carrier. Three selected proteins were further investigated for their binding potential of representative flavonoids differing in their C-ring structure. An increase in hydrophobicity of flavonoids was related to a higher affinity for proteins, and the presence of a gallic acid ester on the C-ring showed an overall higher affinity.     

包膜控释肥养分释放特性评价方法的研究进展

控释肥已成为国内外肥料研究的热点 ,但是评价控释肥养分释放特性的方法研究相对滞后 ,至今没有较为完善的方法和统一的测试标准。本文综述了包膜控释肥养分释放特性的现有评价方法 :水中 (或溶液 )溶出率法、土壤溶出率法、扩散率法、渗透率法、电超滤法和同位素示踪法等 ;评述了各种方法的优缺点及改进途径 ;并展望了今后评价方法的研究方向     

Controlled release of herbicide acetochlor from clay/carboxylmethylcellulose gel formulations

Controlled-release formulations of the herbicide acetochlor were prepared by using carboxylmethylcellulose (CMC) gel and different types of clay, which were obtained by acid activation, pillared with metal hydroxides, or saturated with organic cations. The effect of formulation parameters (amount and type of clay used, cross-linking time, and drying of the hydrogel formulations) on the acetochlor release rate from different formulations was evaluated by water-release studies. The time taken for 50% of acetochlor to be released, t 50, showed a wide variation (151-522 h) for dried gel formulations, the largest value corresponding to the formulation incorporating aluminum hydroxide pillared clay into CMC gels. The release rate of acetochlor from clay/CMC hydrogel formulations decreased with the increase of the hydrogels' cross-linking time (t50 values ranged from 2.18 to 14.0 h for cross-linking times ranging from 2.0 to 120 min). The performance of inorganic clays in dried gel formulations on slowing the release of acetochlor is related to their sorption capacities, but the addition of organic clay did not lead to the slowest release despite its highest sorption capacity. According to the parameters of an empirical equation used to fit herbicide-release data, the release of acetochlor from clay/CMC gel formulations is controlled by diffusion mechanism.     

Potential contributions of smectite clays and organic matter to pesticide retention in soils.

Soil organic matter (SOM) is often considered the dominant sorptive phase for organic contaminants and pesticides in soil-water systems. This is evidenced by the widespread use of organic-matter-normalized sorption coefficients (K(OM)) to predict soil-water distribution of pesticides, an approach that ignores the potential contribution of soil minerals to sorption. To gain additional perspective on the potential contributions of clays and SOM to pesticide retention in soils, we measured sorption of seven pesticides by a K-saturated reference smectite clay (SWy-2) and SOM (represented by a muck soil). In addition, we measured the adsorption of atrazine by five different K-saturated smectites and Ca-saturated SWy-2. On a unit mass basis, the K-SWy-2 clay was a more effective sorbent than SOM for 4,6-dinitro-o-cresol (DNOC), dichlobenil, and carbaryl of the seven pesticides evaluated, of which, DNOC was sorbed to the greatest extent. Atrazine was sorbed to a similar extent by K-SWy-2 and SOM. Parathion, diuron, and biphenyl were sorbed to a greater extent by SOM than by K-SWy-2. Atrazine was adsorbed by Ca-SWy-2 to a much lesser extent than by K-SWy-2. This appears to be related to the larger hydration sphere of Ca(2+) (compared to that of K(+)) which shrinks the effective size of the adsorption domains between exchangeable cations, and which expands the clay layers beyond the apparently optimal spacing of approximately 12.2 A for sorption of aromatic pesticide structures. Although a simple relation between atrazine adsorption by different K-smectites and charge properties of clay was not observed, the highest charge clay was the least effective sorbent; a higher charge density would result in a loss of adsorption domains. These results indicate that for certain pesticides, expandable soil clays have the potential to be an equal or dominant sorptive phase when compared to SOM for pesticide retention in soil.     

聚合物/膨润土复合控释材料的应用研究

用聚合物/膨润土复合材料与肥料混合制备混合型缓/控释肥和用复合材料包裹尿素制备包膜型缓/控释肥进行盆栽试验。结果表明,聚合物和膨润土都具有控释作用,二者复合具有更好的控释效果。几种混合型缓/控释肥处理的玉米生物量均较对照有显著提高,以添加含膨润土0.5倍(相对于聚合物质量)的复合材料配制的缓/控释肥效果最好。几种包膜型缓/控释肥处理的玉米生物量较对照有所提高,差异达显著水平,以含膨润土2倍的复合材料制备的缓/控释肥效果最好。     

Complex coacervates for thermally sensitive controlled release of flavor compounds

To improve the appeal of frozen baked foods upon heating, we have encapsulated flavor oil in complex coacervate microcapsules using gelatin and gum Arabic. Variation of polyion concentrations and homogenization rate affected particle morphology, size distribution, and oil release upon heating. Release of the oil from formulations was determined by a simple spectroscopic method based on separation of oil labeled with a lipophilic dye from unaffected particles. When heated to 100 degrees C or higher, univesicular microcapsules (prepared with a lower homogenization rate) released almost all of the encapsulated oil, while multivesicular microcapsules (produced by high homogenization rates) resulted had lesser degrees of release. The oil remained encapsulated during 4 weeks of storage at 4 and -20 degrees C (freezing and thawing) but was released by exposure to 100 mM NaCl at room temperature. When particles were cooled after releasing their oil content, the oil was re-encapsulated.     

膜材料及其构成对调节控释肥料养分释放特性的影响

试验采用水溶出率实测法研究了自行研制的控释肥料养分释放的特性。以养分释放速率和释放期为主要指标评价了膜材料及其构成对调节控释肥养分释放特性的影响。结果表明,膜材料M2的控释性能优于膜材料M1;用膜材料M1包膜肥料的养分累积释放曲线呈对数曲线,而用膜材料M2包膜肥料的养分累积释放曲线呈直线型。在膜的比面重(单位肥料面积上所含膜材料的重量)为20～80g/m2范围内,随着比面重的增加,包膜肥的初期溶出率降低,释放期延长;通过调节膜材料组成与比面重可以研制出释放期不同的控释肥料。