Increased 3HV Concentration in the Bacterial Production of 3-Hydroxybutyrate (3HB) and 3-Hydroxyvalerate (3HV) Copolymer with Acid-Digested Rice Straw Waste

Bacterial synthesis of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) copolymer [P(3HB-co-3HV)] using the hydrolysate of rice straw waste as a carbon source was affected by the composition of the hydrolysate, which depends highly on the rice straw pretreatment condition. Acid digestion with 2 % sulfuric acid generated larger production of P(3HB-co-3HV) than 6 % sulfuric acid, but 3HV concentration in the copolymer produced with 2 % acid hydrolysate was only 8.8 % compared to 18.1 % with 6 % acid hydrolysate. To obtain a higher 3HV mole fraction for enhanced flexibility of the copolymer, an additional heating was conducted with the 2 % acid hydrolysate after removal of residual rice straw. As the additional heating time increased a higher concentration of levulinic acid was generated, and consequently, the mole fraction of 3HV in P(3HB-co-3HV) increased. Among the conditions tested (i.e., 20-, 40-, 60-min), 60-min additional heating following 2 % sulfuric acid digestion achieved the highest 3HV mole fraction of 22.9 %. However, a longer heating time decreased the P(3HB-co-3HV) productivity, probably due to the increased intermediates concentrations acting as inhibitors in the hydrolysates. Therefore, the use of additional heating needs to consider both the increase in the 3HV mole fraction and the decrease in the P(3HB-co-3HV) productivity.     

Microbial degradation of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in compost

The microbial degradation of tensile test pieces made of poly(3-hydroxybutyrate) [P(3HB)] or copolymers with 10% [P(3HB-co-10%3HV)] and 20% [P(3HB-co-20%3HV)] 3-hydroxyvaleric acid was studied in small household compost heaps. Degradation was measured through loss of weight (surface erosion) and changes in molecular weight and mechanical strength. It was concluded, on the basis of weight loss and loss of mechanical properties, that P(3HB) and P(3HB-co-3HV) plastics were degraded in compost by the action of microorganisms. No decrease inM _w could be detected during the degradation process. The P(3HB-co-20%3HV) copolymer was degraded much faster than the homopolymer and P(3HB-co-10%3HV). One hundred nine microbial strains capable of degrading the polymersin vitro were isolated from the samples used in the biodegradation studies, as well as from two other composts, and identified. They consisted of 61 Gram-negative bacteria (e.g.,Acidovorax facilis), 10 Gram-positive bacteria (mainlyBacillus megaterium), 35Streptomyces strains, and 3 molds.     

Effect of Lignosulfonate on the Thermal and Morphological Behavior of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

The effect of lignosulfonate on poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, was studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The PHBV/lignosulfonate samples were prepared by melt mixing in an internal mixer. SEM showed that PHBV/lignosulfonate samples present a cracked surface that is more intense in mixtures with high lignosulfonate proportions. According to DSC, melting and glass transition temperatures of the PHBV matrix decrease with lignosulfonate addition. The same effect was observed for melting enthalpies (ΔH_m), which indicates a decrease of crystallinity. TGA showed that thermal stability of PHBV/lignosulfonate samples was shifted to lower temperatures, which indicates the existence of an interaction between the thermal decomposition processes of PHBV and lignosulfonate.     

Degradation of Poly(3-hydroxybutyrate) and Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) by Some Soil Aspergillus spp.

Systematic screening of 45 soil fungi for degradation polyhydroxyalkanoic acids (PHAs) has led to the selection of 6 potent Aspergillus isolates belonging to A. flavus, A. oryzae, A. parasiticus, and A. racemosus. Degradation of PHAs as determined by tube assay method revealed that these Aspergillus spp. were more efficient in degrading poly(3-hydroxybutyrate) [P(3HB)] compared to copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid (P3HB-co-16% 3HV). Moreover, the extent of degradation in mineral base medium was much better than those in complex organic medium. For all the Aspergillus spp. tested, maximum degradation was recorded at a temperature of 37°C with significant inhibition of growth. The optimum pH range for degradation was 6.5–7.0 with degradation being maximum at pH 6.8. The extent of polymer degradation increased with increase in substrate concentration, the optimum concentration for most of the cultures being 0.4% and 0.2% (w/v) for P(3HB) and P(3HB-co-16%3HV) respectively. Supplementation of the degradation medium with additional carbon sources exerted significant inhibitory effect on both P(3HB) and P(3HB-co-16%3HV) degradation.     

Biosynthesis and Characterization of Poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) from Bacillus cereus S10

The biodegradable and biocompatible copolymer poly-(3-hydroxybutyrate-co-5 mol% 3-hydroxyvalerate), poly-(3HB-co-5 mol% 3HV), was synthesized by Bacillus cereus S10 and the highest yield was determined as 69.91 % at pH 7 and 30 °C after 48 h of incubation using a glucose as the sole carbon source. Poly-(3HB-co-5 mol% 3HV) was purified from bacterial biomass using chloroform. FTIR analysis showed absorption bands at 1,723, 1,274, 1,373, 1,453, 2,932 cm^?1 corresponding to C=O, C–O stretching, CH₃, –CH₂ and –CH groups, respectively. ¹H-NMR and ¹³C-NMR analysis confirmed that the copolymer was composed of 95 mol% of 3-hydroxybutrate and 5 mol% of 3-HV monomeric units. Poly-(3-HB-co-5 mol% 3HV) was used for nanoparticles preparation. The diameter of nanoparticles was 202 nm.     

Production of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) from various carbon sources by batch-fed cultures ofAlcaligenes eutrophus

Copolyesters of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) were produced at 30°C from various carbon sources byAlcaligenes eutrophus under batch-fed growth conditions. The production of P(3HB-co-3HV) from butyric and pentanoic acids was effective under nitrogenlimited conditions, and the conversion of carbon sources into copolyester was as high as 56 wt% at a C/N molar ratio of 40. In contrast, under excess-nitrogen conditions (C/N<10), cell growth was good, while P(3HB-co-3HV) production was partially inhibited. The production of P(3HB-co-3HV) from fructose and propionic acid was almost completely inhibited under excess-nitrogen conditions.     

WO_3/Ag_3VO_4复合光催化剂的制备及其可见光催化性能

采用超声辅助沉淀法—浸渍法制备了WO3/Ag3VO4复合光催化剂,对其进行了表征,考察了其在可见光条件下对罗丹明B的催化降解性能,并对催化机理进行了探讨。表征结果显示:WO3紧密包覆在Ag3VO4颗粒的表面,并未改变Ag3VO4的晶体结构;与Ag3VO4和WO3相比,WO3/Ag3VO4的吸收带边发生了红移。实验结果表明:w(WO3)为3.5%时,WO3/Ag3VO4对罗丹明B的可见光催化降解效果最好;在光催化剂加入量0.8 g/L、初始罗丹明B质量浓度10 mg/L的条件下,于室温下光照180 min时的罗丹明B去除率达95.76%,TOC去除率达96.5%;WO3与Ag3VO4在能带间的耦合作用下形成异质结结构,很好地抑制了光生电子-空穴对的复合。     

Microscopic Visualization of the Enzymatic Degradation of Poly(3HB-co-3HV) and Poly(3HV) Single Crystals by PHA Depolymerases From Pseudomonas lemoignei

As a complement to previous studies of the enzymatic degradation of folded chain lamellar single crystals of polyhydroxyalkanoates, single crystals of a number of polyhydroxyalkanoates were partially degraded with depolymerases from Pseudomonas lemoignei and examined by transmission electron microscopy. Single crystals of bacterial poly(3-hydroxybutyrate-co-3-hydroxyvalerate), bacterial poly(3-hydroxyvalerate), and synthetic poly(3-hydroxybutyrate) with 88% isotactic diads were degraded using purified extracellular PHA-depolymerases from P. lemoignei: PHB-depolymerase A, PHB-depolymerase B, and depolymerases from recombinant E. coli: PHB-depolymerase PhaZ4 (PHB-depolymerase E), PHB-depolymerase PhaZl (PHB-depolymerase C), and PHB-depolymerase PhaZ5 (PHB-depolymerase A). In contrast to previous results with single crystals of bacterial PHB, the predominant effect observed with all crystals was a significant narrowing of the lamellae. This suggests an edge attack mechanism which because of lateral disorder of the crystals leads to a narrowing of the crystalline lamellae as opposed to the splintering effect previously observed. The model suggested for the degradation of single crystals of bacterial PHB by PHB-depolymerases is refined to include the effects of lateral disorder caused by the introduction of valerate or repeat units of opposite stereochemistry into the single crystal.     

Effect of aeration modes on the characteristics of composting emissions and the NH3 removal efficiency by using biotrickling filter

A pilot biotrickling filter (BTF) packed with ZX02 fibrous balls as packing material was tested for the treatment of ammonia (NH₃) released from a composting plant of dairy manure. In order to investigate the effects of three compost aeration modes (mode Co-I, Co-II and In-II) on the NH₃ removal efficiency, a field experiment was continuously carried out for more than eight months. The results demonstrated that under the intermittent aeration mode (In-II), the NH₃ removal efficiency reached 99.2 ± 0.1% when the inlet NH₃ concentration was 7.5-32.3 mg m⁻³ (9.8-42.5 ppmv). The maximum and critical elimination capacity of the biotrickling filter was 22.6 and 4.9 g NH₃ m⁻³ h⁻¹, respectively. The effluent concentration of NH₃ was lower than 1.0 mg m⁻³, which meets the first class discharge standards of GB14554-93. When the concentration of free ammonia in the trickling liquid was varied from 0.1 to 0.4 mg L⁻¹, the nitrification yield was between 47.9% and 103.8%. In addition, the optimum liquid tricking velocity (LTV) of the biotrickling filter was 0.5 m³ m⁻² h⁻¹ for low inlet concentrations and 2.2 m³ m⁻² h⁻¹ for high inlet concentrations. Therefore, the use of the biotrickling filter for the compost under the third aeration mode (In-II) yielded an effective optimum NH₃ removal and reduced the nitrogen loss in the compost.     

Utilization of Broken Rice for the Production of Poly(3-hydroxybutyrate)

The feasibility of utilizing non edible rice (broken rice) for production of fine materials such as poly(3-hydroxybutyrate) (PHB) was considered as one of the alternative ways of keeping the environment clean for sustainable development. Thus, production of PHB from broken rice by simultaneous saccharification and fermentation (SSF) was investigated. During the SSF process, the rice (15% w/v) material was hydrolyzed to glucose, which was utilized by Cupriavidus necator for growth and production of PHB. The PHB content reached 38% at 58 h fermentation. The PHB had weight average molar mass (Mw) and polydipersity index of 3.82 × 10⁵ (g/mol) and 4.15, respectively. Differential calorimetric scan of the PHB showed a melting temperature (Tm) of 176 °C. Given that the PHB was a homopolymer (which consisted of (R)-3-hydroxybutyric acid monomers), it was thought that broken rice could be a raw material for production of both PHB and (R)-3-hydroxybutyric acid. This SSF process would not only help in the utilization of broken rice or non edible rice, but would also serve as a model for utilization of other raw materials that contain starch for production of PHB.     

Assessment of the Viability of NIH3T3 Fibroblast Cells Cultured in Polymer Matrices with rhGH

Developing a biomaterial that functions as a scaffold (osteoconductor), combined with a growth factor (osteoinductor), is of great interest for clinical application in oral and maxillofacial surgery. Growth hormone (GH) is a good candidate, as it is a major regulator of postnatal bone growth and remodeling. Pure PLGA and 70/30 PLGA/PCL matrices were prepared by the solvent evaporation method, combined or not with GH, and tested for toxicity and cell viability using an MTT assay with NIH3T3 mouse cells (ATCC). Cell toxicity was assessed at 24, 48, 72 h, and 7 days of biomaterial exposure to culture medium. All polymers had high cell viability rates. However, from 48 h onwards, the groups with GH-polymer combinations had better results than the polymer groups without association with GH when compared to the control group. At 7 days of culture, only the pure PLGA matrix showed a significant difference from the control group. These results may suggest a preference of cells for the presence of GH in the biomaterial in culture medium, especially in the PLGA matrix. GH appeared to contribute to the increase in cell viability observed at some assessment time points, especially when combined with PLGA as compared to pure PLGA.     

Large-scale production of poly(3-hydroxyvaleric acid) by fermentation ofChromobacterium violaceum,processing, and characterization of the homopolyester

A fed-batch process was developed, which allowed biotechnological production of the homopolyester poly(3-hydroxyvaleric acid) [poly(3HV)], in a mineral salts medium containing valeric acid as carbon source and complex nutrients as supplements byChromobacterium violaceum at a 10- and 300-L fermentation scale. This process yielded up to 40 g dry cell matter per L fermentation broth, and the cells contained up to 70% (w/w) poly(3HV). Poly(3HV), which was extracted from the cells with chloroform and was precipitated from this solvent with ethanol, was processed to test bars by injection molding or by press processing and to fibers by melt spinning. The unprocessed and processed poly(3HV) material was characterized with respect to the molecular weight and with respect to thermal, rheological, and mechanical properties. It was shown that it is possible to process biodegradable poly(3HV) thermoplastically and to obtain a polymer suitable for applications with low strength requirements.     

Thermal Properties and Biodegradability Studies of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

For investigating the relationship between thermal properties and biodegradability of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), several films of PHBV containing different polyhydroxyvalerate (HV) fractions were subjected to degradation in different conditions for up to 49 days. Differential scanning calorimetry (DSC), thermogravimetry (TG), specimen weight loss and scanning electron microscopy (SEM) were performed to characterize the thermal properties and enzymatic biodegradability of PHBV. The experimental results suggest that the degradation rates of PHBV films increase with decreasing crystallinity; the degradability of PHBV occurring from the surface is very significant under enzymatic hydrolysis; the crystallinity of PHBV decreased with the increase of HV fraction in PHBV; and no decrease in molecular weight was observed in the partially-degraded polymer.     

O3氧化法和O3-H2O2氧化法去除水中聚丙烯酰胺

采用O3氧化法和O3-H2O2氧化法去除水中的聚丙烯酰胺（PAM），分别考察了反应时间、O3质量浓度、n（H2O2）∶n（O3）和溶液pH对PAM去除效果的影响。实验结果表明：O3氧化的最佳操作条件为反应时间30 min、O3质量浓度22.6 mg/L、溶液pH 8.5，O3-H2O2氧化的最佳操作条件为反应时间10 min、O3质量浓度22.6 mg/L、n（H2O2）∶n（O3）=0.1、溶液pH 8.5;在最佳操作条件下，O3氧化和O3-H2O2氧化均可有效降低PAM溶液的黏度和PAM质量浓度，但对COD的去除效果不佳，黏度可降至和蒸馏水相近，PAM的去除率可达80%以上，而COD的去除率分别约为15%和28%;O3-H2O2氧化后的PAM比O3氧化后的PAM更容易被微生物利用，两种氧化预处理方法均有利于后续的生化处理。     

Fe3O4-PTFE电极制备条件和双阴极电-Fenton反应条件的优化

制备了Fe₃O₄-聚四氟乙烯（PTFE）电极,优化了原料配比和焙烧温度。对比了Fe₃O₄-PTFE单阴极和Fe₃O₄-PTFE与乙炔碳黑-PTFE电极并联双阴极体系对模拟Rhb染料废水的处理效果。实验结果表明：在m（Fe₃O₄）∶m（PTFE）=3.0∶2.5、焙烧温度为300 ℃的条件下制备Fe₃O₄-PTFE电极,采用阴极电-Fenton法降解模拟Rhb废水的效果最佳,电解反应120 min时Rhb降解率达86.91%;Fe₃O₄-PTFE电极与乙炔碳黑-PTFE电极并联作为双阴极电解Rhb废水时,最佳电压为6 V,最佳初始废水pH为3,在此条件下电解反应120 min时Rhb降解率达91.65%。     

羟基磷灰石去除废水中的Fe3+

以天然磷矿粉制备的羟基磷灰石(HAP)作为吸附剂，处理模拟含Fe3+废水。实验结果表明，在HAP加入量为1.0g/L、初始模拟废水pH为3.00、反应温度为室温的最佳条件下，处理初始Fe3+质量浓度为150mg/L的模拟废水，反应90min后Fe3+去除率为99.89%，处理后模拟废水中Fe3+质量浓度为0.15mg/L，低于0.30mg/L，达到GB5749—2006《生活饮用水卫生标准》的要求。     

Report: anaerobic digestion of a sulphate-rich high-strength landfill leachate: the effect of differential dosing with FeCl3.

The effect of different dose concentrations of FeCl3 on the performance of a mesophilic anaerobic digester treating a highly alkaline, high-strength and sulphate-rich landfill leachate was tested. The results indicated that sulphate reduction was the predominant reaction and methanogenic processes were entirely inhibited in the reactor without FeCl3 addition. Adding FeCl3 into the reactor restored some methanogenic activity and also improved the rates of sulphate reduction. A combination of sulphate reduction and methanogenic activity resulted in up to 75% chemical oxygen demand (COD) removal and 85% sulphate removal. Sulphate reduction remained the principle mechanism by which COD removal took place with a methane yield of only between 0.14 and 0.18 m3 CH4 kg(-1) COD removed being achieved. The process was, however, stable and offered advantages for the further treatment or conveyance of the anaerobically treated leachate.     

Contribution of 3-D time-lapse ERT to the study of leachate recirculation in a landfill

Leachate recirculation is a key process in the operation of municipal waste landfills as bioreactors. It aims at increasing the moisture content to optimise the biodegradation. Because waste is a very heterogeneous and anisotropic porous media, the geometry of the leachate plume recirculation is difficult to delineate from the surface at the scale of the bioreactor site. In this study, 3-D time-lapse electrical resistivity tomography (ERT) was used to obtain useful information for understanding leachate recirculation hydrodynamics. The ERT inversion methodology and the electrode arrays were optimised using numerical modelling simulating a 3-D leachate injection scenario. Time-lapse ERT was subsequently applied at the field scale during an experimental injection. We compared ERT images with injected volumes to evaluate the sensitivity of time-lapse ERT to delineate the plume migration. The results show that time-lapse ERT can accomplish the following: (i) accurately locate the injection plume, delineating its depth and lateral extension; (ii) be used to estimate some hydraulic properties of waste.     

Quantifying dry NH3 deposition to an ombrotrophic bog from an automated NH3 field release system

Providing an accurate estimate of the dry component of N deposition to low N background, semi-natural habitats, such as bogs and upland moors dominated by Calluna vulgaris is difficult, but essential to relate nitrogen deposition to effects in these communities. To quantify the effects of NH₃ inputs to moorland vegetation growing on a bog at a field scale, a field release NH₃ fumigation system was established at Whim Moss (Scottish Borders) in 2002. Gaseous NH₃ from a line source was released along of a 60 m transect, when meteorological conditions (wind speed >2.5 m s^?1 and wind direction in the sector 180–215°) were met, thereby providing a profile of decreasing NH₃ concentration with distance from the source. In a complementary study, using a NH₃ flux chamber system, the relationships between NH₃ concentrations and cuticular resistances were quantified for a range of NH₃ concentrations and micrometeorological conditions for moorland vegetation. Cuticular resistances increased with NH₃ concentration from 11 s m^?1 at 3.0 μg m^?3 to 30 s m^?1 at 30 μg m^?3. The NH₃ concentration data and the concentration-dependent canopy resistance are used to calculate NH₃ deposition taking into account leaf surface wetness. The implications of using an NH₃ concentration-dependent cuticular resistance and the importance for refining critical loads are discussed.     

γ-Al2O3负载多金属复合催化剂选择性催化还原烟气脱硝

以γ-Al₂O₃作为载体，先后负载CeO₂，MnC₂O₄，Fe（NO₃）₃，CrO₃，Ni（NO₃）₂，NH₄VO₃等多种金属组分制备γ-Al₂O₃负载多金属复合催化剂，并用于模拟烟气的选择性催化还原脱硝。通过SEM和XRD技术对催化剂进行了表征。表征结果显示：Fe，Mn，Cr的添加能增加催化剂的低温催化活性、提高催化剂的N₂选择性;γ-Al₂O₃对活性金属氧化物的负载效果良好。实验结果表明：各金属化合物的最佳加入量为 w（MnC₂O₄·2H₂O）=20%，w（Fe（NO₃）₃·9H₂O）=15%，w（CrO₃）=10%，w（Ni（NO₃）₂·6H₂O）=5%，w（NH₄VO₃）=10%，w（CeO₂）=5%，w（γ-Al₂O₃）=35%;以在最佳正交实验条件下制得的γ-Al₂O₃负载多金属复合物为催化剂，在脱硝反应温度为205 ℃的条件下，NO转化率为96.7%;γ-Al₂O₃负载多金属复合催化剂经5次重复使用，NO转化率仍可稳定在94%左右。