Degradation of Cellulosic Materials Under the Alkaline Conditions of a Cementitious Repository for Low- and Intermediate-Level Radioactive Waste. II. Degradation Kinetics

The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are - and -(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.     

Review of the kinetics of alkaline degradation of cellulose in view of its relevance for safety assessment of radioactive waste repositories

The degradation of cellulose (a substantial component of low- and intermediate-level radioactive waste) under alkaline conditions occurs via two main processes: a peeling-off reaction and a basecatalyzed cleavage of glycosidic bonds (hydrolysis). Both processes show pseudo-first-order kinetics. At ambient temperature, the peeling-off process is the dominant degradation mechanism, resulting in the formation of mainly isosaccharinic acid. The degradation depends strongly on the degree of polymerization (DP) and on the number of reducing end groups present in cellulose. Beyond pH 12.5, the OH^- concentration has only a minor effect on the degradation rate. It was estimated that under repository conditions (alkaline environment, pH 13.3-12.5) about 10% of the cellulosic materials (average DP = 1000-2000) will degrade in the first stage (up to 10⁵ years) by the peeling-off reaction and will cause an ingrowth of isosaccharinic acid in the interstitial cement pore water. In the second stage (10⁵-10⁶ years), alkaline hydrolysis will control the further degradation of the cellulose. The potential role of microorganisms in the degradation of cellulose under alkaline conditions could not be evaluated. Proper assessment of the effect of cellulose degradation on the mobilization of radionuclides basically requires knowing the concentration of isosaccharinic acid in the pore water. This concentration, however, depends on several factors such as the stability of ISA under alkaline conditions, sorption of ISA on cement, formation of sparingly soluble ISA-salts, etc. A discussion of all the relevant processes involved, however, is far beyond the scope of the presented overview.     

二氧化钛光催化降解甲醛反应动力学研究

以钛酸丁酯为前驱体，应用溶胶一凝胶法制备TiO2粉体和负载TiO2薄膜，考察了不同活化温度和活化时间对TiO2光催化降解甲醛性能的影响，并对TiO2薄膜光催化降解甲醛的反应动力学进行了研究。试验结果表明，在活化温度450℃、活化时间5h条件下，所得TiO2粉体及薄膜的光催化活性较好。不同初始浓度下甲醛光催化降解率与时间关系的动力学研究表明，一级反应动力学模型与试验数据拟合较好，方差R^2大于或等于0．99。     

Emission of Volatiles from Polymers — A New Approach for Understanding Polymer Degradation

Emission of low molar mass compounds from different polymeric materials was determined and the results from the volatile analysis were applied to predict the degree of degradation and long-term properties, to determine degradation rates and mechanisms, to differentiate between biotic and abiotic degradation and for quality control work. Solid-phase microextraction and solid-phase extraction together with GC-MS were applied to identify and quantify the low molar mass compounds. Volatiles were released and monitored at early stages of degradation before any matrix changes were observed by e.g. SEC, DSC and tensile testing. The analysis of volatiles can thus also be applied to detect small differences between polymeric materials and their susceptibility to degradation. The formation of certain degradation products correlated with the changes taking place in the polymer matrix, these indicator products could, thus, be analysed to rapidly predict the degree of degradation in the polymer matrix and further to predict the long-term properties and remaining lifetime of the product.     

糙皮侧耳降解碱木素的动力学研究

对糙皮侧耳B1(白腐真菌的一种)降解碱木素的动力学进行了研究.基于Logistic方程,建立了糙皮侧耳B1在纯培养条件和碱木素存在条件下的生长动力学模型.动力学模型参数分别为0.94d-1和0.90d-1.该模型能够较好地模拟体系中生物量的变化,平均相对误差分别为3.2％和3.4％.糙皮侧耳B1对低浓度碱木素的降解存在...     

Effects of Temperature and Relative Humidity on Polylactic Acid Plastic Degradation

Three high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films from Chronopol (Ch-I) and Cargill Dow Polymers (GII and Ca-I) were analyzed for their degradation under various temperature and relative humidity (RH) conditions. Two sets of plastic films, each containing 11 samples, were randomly hung in a temperature/humidity-controlled chamber by means of plastic-coated paper clips. The tested conditions were 28, 40, and 55°C at 50 and 100% RH, respectively, and 55°C at 10% RH. The three tested PLA films started to lose their tensile properties when their weight-average molecular weight (M _w) was in the range of 50,000 to 75,000 g mol^–1. The average degradation rate of Ch-I, GII, and Ca-I was 28,931, 27,361, and 63,025 M _w/week, respectively. Hence, GII had a faster degradation rate than Ch-I and Ca-I under all tested conditions. The degradation rate of PLA plastics was enhanced by the increase in temperature and relative humidity. This trend was observed in all three PLA plastics (Ca-I, GII, and Ch-I). Of the three tested films, Ch-I was the first to lose its mechanical properties, whereas Ca-I demonstrated the slowest loss, with mechanical properties under all tested conditions.     

Cellulose acetate biodegradability upon exposure to simulated aerobic composting and anaerobic bioreactor environments

Cellulose acetate (CA) films with degree of substitution (d.s.) values of 1.7 and 2.5 were exposed to biologically active in-laboratory composting test vessels maintained at approximately 53 °C. The CA 1.7- and 2.5-d.s. films (thickness values of 0.5–1.0 and 2.0 mil, respectively) had completely disappeared by the end of 7- and 18-day exposure time periods in the biologically active bioreactors, respectively. The relatively small CA film weight loss observed in the poisoned control test vessels allows the conclusion that CA film erosion during the composting exposures resulted, at least in part, from biologically mediated processes. Under strictly anaerobic conditions, an active methanogenic inoculum was developed by acclimation of a sewage sludge to a synthetic municipal solid waste (SMSW) mixture at 42°C. The CA 1.7-d.s. film samples (0.5- to 1.0-mil thickness) were exposed in anaerobic serum bottles containing a 25% solids loading of SMSW in which methanogenic activity was rapidly established after introducing of the developed inoculum. For exposures of 30 days only small visually distinguishable fragments of the CA 1.7-d.s. films were recovered. In contrast, exposure of the CA 1.7-d.s. film to a poisoned control test vessel resulted in negligible weight loss. Therefore, degradation of the CA 1.7-d.s. films upon exposure to the anaerobic bioreactors was due, at least in part, to biologically mediated processes.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

不同光照度下活性艳红X-3B的光催化降解动力学研究

以活性艳红X-3B为模型化合物，以TiO2为光催化剂，研究了不同光照度下污染物的多相光催化降解动力学。结果表明，活性艳红X-3B的光催化降解动力学符合Langmiur—Hinshelwood动力学模型，其中的表观反应速率常数(k)随入射光照度的增加而增大，吸附平衡常数(KA)却随入射光照度的增加而减小，在实验的光照度范围内，k和KA^-1与光照度的平方根成比。     

Rheology of Lyocell Solutions from Different Cellulose Sources

Rheological measurements were used to characterize the behavior of lyocell solutions, i.e., cellulose dissolved in N-methymorpholine-N-oxide. Cellulose sources included dissolving pulp, kraft pulp, sugar cane fibers, and kenaf fibers. The dominance of viscous behavior, G values, over elastic behavior, G values, is affected by cellulose concentration and molecular weight. At lower concentrations and degrees of polymerization (DP), dissolving pulp solutions show viscous, inelastic behavior at low frequencies. At higher concentration and DP, dissolving pulp solutions are more elastic at higher frequencies. Solutions prepared with kenaf and sugar cane fibers show similar properties to those using pure dissolving pulp, and comparisons suggest the molecular weight and/or the presence of other substances such as lignin in the cellulose from these alternative sources affect the rheology.     

超声光催化降解酸性粒子元青染料的研究

对超声波作用下的纳米TiO2光催化氧化法降角酸性粒子元青染料进行了研究。结果表明，超声波的引入提高了纳米TiO2光催化降解酸性粒子元青染料的降解率；降解率受反应时间、坡声波功率、空气流量的影响；添加少量的H2O2能够明显地提高酸性粒子元青染料的降解率。     

TiO2纳米管光电催化降解酸性橙染料

采用电化学阳极氧化法在金属钛表面制备锐钛矿型TiO2纳米管,并以TiO2纳米管薄膜为阳极,考察溶液pH、外加偏压以及NaC1浓度对酸性橙的光电催化降解反应的影响.实验结果表明:在溶液pH为3.0、外加偏压为2.5V、NaCl浓度为0.05 mol/L的最佳实验条件下反应30 min,酸性橙降解率可达99.99％;TiO2纳米管重复使用25次,酸性橙降解率仍可达94.57％.     

高频超声波降解4-氯酚的反应机理及试验研究

探讨了高频超声波（1.7MHz)降解4-氯酚的反应过程和反应机理，研究了高频超声波降解4-氯酚的效果及4-氯酚的初始浓度，高级氧化方法（AOPs)等因素对降解效果的影响。试验结果表明，高频超声波降解4-氯酚为一级反应，超声波空化效应在降解过程中起主导作用。超声波与其他氧化方法联用可大大提高降解效率。具有良好的工业应用前景。     

Effect of Degree of Substitution of Octenyl Succinate Starch on Enzymatic Degradation

Octenyl succinate starch of degree of substitution (ds) 0.03, 0.07, and 0.11 was synthesized in an aqueous medium. These compounds were then tested for the susceptibility to enzymatic degradation. The multiple-enzyme regime of -amylase, amyloglucosidase, and pullulanase was chosen for the evaluation. This combination of enzymes had been proven to degrade 99.5% of unmodified starch to glucose and hence was chosen for this study. It was found that even small amounts of subsituent caused a considerable decrease in the extent of degradation. The net extent of degradation decreased with increasing ds. Surprisingly, the amount of glucose from all three substituted substrates was quite similar, suggesting the effect small amounts of subtituent had on the enzymatic activity.     

Effect of Sequential Mixing and Compounding Conditions on Cellulose Acetate/Layered Silicate Nanocomposites

Injection molded nanocomposites have been successfully fabricated from cellulose acetate (CA), eco-friendly triethyl citrate (TEC) plasticizer, and organically modified clay with and without maleic anhydride grafted cellulose acetate butyrate (CAB-g-MA) as a compatibilizer. The effects of processing conditions such as mixing methods, pre-plasticizing times, extruder retention times (RT) and addition of compatibilizer on the performance of these nanocomposites have been evaluated. The cellulosic plastic with CA/TEC (80/20 wt%) was used as the polymer matrix for nanocomposite fabrication. The morphologies of these nanocomposites were evaluated through X-ray diffraction (XRD) and transmission electron microscopy (TEM) studies. The mechanical properties of the nanocomposites were measured and have been correlated with the XRD and TEM observations. From all of the sequential mixing methods used, powder–powder mixing leads to the most transparent nanocomposites. Cellulosic plastic-based nanocomposites obtained using increased pre-plasticizing times and RT showed better exfoliated structures. In the system containing compatibilizer, the minimum retention time required for obtaining almost completely exfoliated hybrid nanocomposites was shorter than in the system without compatibilizer.     

Preparation and Characterization of Cellulose/Polypropylene Composite Using an Oxidatively Degraded Polypropylene

In this work, an oxidatively degraded polypropylene (DgPP) was studied as a novel coupling agent for fibrous cellulose (FC)/polypropylene (PP) composite. An optimal preparation time of PP thermal oxidative degradation was 18 h at 130 °C, and the DgPP had functional groups such as γ-lactone and acid groups. The spherulite observation of the DgPP suggested miscibility for the undegraded PP. The addition of the DgPP presented the transparency improvement of FC/PP composite, and this behavior was found to be originated from the grafted DgPP, which was produced by the esterification reaction between the of FC and the DgPP. The scanning electron microscope (SEM) observation showed that the grafted DgPP coated the FC surface, and the tensile strength of the FC/PP composite increased by an appropriate amount of the DgPP addition. These results suggested that the DgPP was suitable for the coupling agent of FC/PP composite.     

球形纤维素吸附剂对Cr3+吸附和解吸的研究

用静态法和动态法研究了球形纤维素吸附剂对水中 Cr3+的吸附和解吸 ,包括静态等温吸附以及各种因素对吸附的影响等 ,并探讨了吸附机理。 Cr3+的吸附容量为 2 8mg/ g,采用浓度为 1.2 mol/ L 的 HCl溶液作解吸液回收 Cr3+的综合效果较好。静态法和动态法的吸附率均达 90 %左右 ,解吸率均达 85 %以上 ,且静态法的吸附率和解吸率分别略高于动态法的吸附率和解吸率 ,但动态法耗时短 ,更符合工业化要求。     

Mechanism of Microbial Degradation of Slow-Release Fertilizers

Methyleneureas are condensation products of urea and formaldehyde of different molecular mass and solubility; they are used in large amounts both as resins, binders, and insulating materials for industrial applications, as well as a slow-release nitrogen fertilizer for greens, lawns, or in bioremediation processes. In the present study, the microbial breakdown of these products was investigated. The nitrogen was released as ammonia and urea, and the formaldehyde released immediately oxidized via formiate to carbon dioxide. The enzymatic mechanism of metabolization of methyleneureas was studied in microorganisms isolated from soil, which were able to use these compounds as the sole source of nitrogen for growth. A strain of the Gram-negative bacterium Ralstonia paucula (formerly Alcaligenes sp. CDC group IVc-2) completely degraded methylenediurea and dimethylenetriurea to urea, ammonia, formaldehyde, and carbon dioxide. The enzyme initiating this degradation (methylenediurease) was purified and turned out to be different from the previously described enzyme from Ochrobactrum anthropi with regard to its regulation of expression and physicobiochemical properties. Fungal degradation of methyleneureas may occur via the formation of organic acids, thus leading to a nonenzymatic degradation of methyleneureas, which are unstable under acidic conditions.     

电解法降解有机污染物机理及动力学的研究

对阳极电解催化降解有机污染物的机理进行了研究。结果表明 ,在电解过程中能够产生氧化能力极强的羟基自由基 (HO· ) ,使有机污染物以间接氧化的方式降解。用非线性最小二乘法对试验数据的分析表明 ,降解过程基本符合两步一级模型 ,并得到了水杨酸降解过程中的两步速率常数和 2 ,3-二羟基苯甲酸在 5 10 nm处的摩尔吸光系数     

微生物降解重油的初步研究

丛石油污染的土壤中筛选出一株假单胞菌,考察了其对重油的降解效果。降解18d,重油的降解率达到42．8％,饱和烃、芳香烃、胶质、沥青质的降解率分别为42．95％,43．85％,44．5％,5．55％;质量浓度2．5g／L的表面活性剂Tween-80可使重油的18d降解率达到51．0％;弱碱性条件有利于重油的生物降解;生物泥浆法处理重油污染的土壤,1kg土壤中重油质量100g,降解45d,重油的降解率达到38．85％。     

Evaluation of the Biodegradation of Starch and Cellulose Under Controlled Composting Conditions

In order to verify the response of the controlled composting test method (i.e., the ISO/DIS 14855:1997, the ASTM D 5338-92, or the CEN counterpart) to starch at different concentrations, the maximum amount prescribed by the test method (100 g) and lower amounts (60 and 30 g), as if starch were a coingredient in a blend, were tested. After 44 days of incubation (at a constant temperature of 58°C) the biodegradation curves were in a plateau phase, displaying the following final values (referred to a nominal starch initial amount of 100 g): starch 100 g, 97.5%; starch 60 g, 63.7%; and starch 30 g, 32.5%. The data show a CO₂ evolution roughly equal, in each case, to the theoretical maximum, indicating a complete starch mineralization. We cannot discern whether the deviations found at lower concentrations are caused by a priming effect. In any case, the extent of the deviations is not high and is acceptable in biodegradation studies. The average biodegradation of cellulose, obtained gathering four independent experiments with 11 biodegradation curves, turned out to be 96.8 ± 6.7% (SD) after 47 ± 1 days. The data indicate that the controlled composting is a reliable test method also for starch and cellulose and, consequently, for starch-based and cellulose-based materials.