Evaluation of the Effect of Chemical or Enzymatic Synthesis Methods on Biodegradability of Polyesters

This work compares the biodegradability of polyesters produced by an esterification reaction between glycerol and oleic di-acid (D 18:1) issued from green chemical pathways, via either classical thermo-chemical methods, or an enzymatic method using the immobilized lipase of Candida antartica B (Novozym 435). An elastomeric polymer synthesized by enzymatic catalysis is more biodegradable than an elastomeric thermo-chemical polyester synthesized by a standard chemical procedure. This difference lies in percentage of the dendritic motifs, in values of the degree of substitution, and certainly in cross-links inducing an hyper-branched structure less accessible to the lipolytic enzymes in a waste treatment plant. However, when the elastomeric polymer synthesized by enzymatic catalysis is processed at high temperature as required for certain industrial applications, it presents an identical rate of biodegradation than the chemical polyester. The advantages of the thermo-chemical methods are greater speed and lower cost. Enzymatic synthesis appears be suited to producing polyesters, devoid of metallic catalysts, which must be used without processing at high temperature to keep a high biodegradability.     

Comparative Biodegradation Studies of Non-poronized and Poronized LDPE Using Indigenous Microbial Consortium

Seventeen bacterial isolates were screened for the utilization of low density polyethylene (LDPE) as the sole carbon source, out of which five potential strains were selected for the development of a consortium. In vitro biodegradation efficiency of the consortium was studied for two differently textured forms of LDPE viz. non-poronized and poronized. Although, both the forms were acted-upon well by the consortium, but the degradation was found to be better in the poronized form. This was substantiated by λ-max shift, FTIR spectra and simultaneous TG-DTG-DTA. The analysis revealed the breakage and formation of chemical bonds in the polymer backbone, as a result of microbial activity. The biodegraded samples of non-poronized and poronized LDPE exhibited similar weight losses at 400 °C (24.12% and 24.48%, respectively) as compared to their controls (4% and 4.5% respectively), but the latter could achieve it with greater ease as reveled by its lower heat of reactions (ΔH values). The study signifies the influence of poronization of polyethylene on its rate of biodegradation.     

Enzymatic Degradation of Cellulose-Based Materials

The biodegradability of cellulose-based materials was compared in the standard Sturm test and by enzymatic hydrolysis. Trichoderma reesei culture filtrate, the purified enzymes endoglucanase I and II from T. reesei, and -glucosidase from Aspergillus niger were used in the experiments. The unpurified Trichoderma reesei culture filtrate was found to contain a mixture of enzymes suitable for cellulose degradation. However, when purified enzymes were used the right balance of the individual enzymes was necessary. The addition of -glucosidase enhanced the enzymatic hydrolysis of cellulose materials when both culture filtrate and purified enzymes were used. In the Sturm test the biodegradability of most of the cellulose materials exceeded 70% carbon dioxide generation, but, in contrast, the biodegradability of the highly substituted aminated cellulose and cellulose acetate was below 10%. The results concerning enzymatic hydrolysis and biodegradability were in good agreement for kraft paper, sausage casing, aminated cellulose, and cellulose acetate. However, diverging results were obtained with cotton fabric, probably as a result of its high crystallinity.     

Toxicological evaluation of the chemical oxidation methods for landfill stabilization

As the stabilization criteria for landfill sites, only chemical criteria for the leachate discharges from the landfill sites have been used in Japan and many other countries. Recently, chemical oxidation has been developed as a method for the early-stabilization of landfills. However, by-products that are difficult to detect by chemical analysis can be produced by this method. Therefore, toxicity tests are useful tools for detecting the changes of leachate quality after application of this method. The heat source in the A landfill was analyzed by organic position inquiry technology, and ozone-treated leachate was sprayed back to the heat source in the landfill. Toxicity changes of the leachate after the spray were monitored using Microtoxtrade mark, ToxScreen-II, and DaphTox tests. The hardly-degradable organic matter was efficiently removed and toxicities of the leachate in the heat source decreased after the application. These toxicity results were significantly related to chemical oxygen demand (COD) changes. Thus, it was concluded that the toxicity tests were effective for monitoring the leachate quality after applying the chemical oxidation method for landfill stabilization, and its incorporation to establish the criteria for early-stabilization of landfill sites needs to be considered.     

Enzymatic processing of municipal solid waste

The focus of this work was to investigate an enzymatic liquefaction of MSW organics, paper and cardboard. Liquefaction trials were conducted in different trial volumes: 50 g lab-scale trials and 50 kg vessel-tests and evaluated based on particle size and viscosity. The viscosity results showed that Celluclast 1.5 L had the singular significant effect on liquefaction of model MSW. No effect of α-amylase, protease and interaction in between and with cellulases on viscosity and particle size distribution was found in this study. Degradable material with a particle size above 1 mm after treatment was evaluated using SEM microscopy. These results showed that paper particles were the main obstacles needing additional treatment in order to become fully liquefied. In a pilot scale test treating authentic MSW; more than 90% of initial organic and paper dry matter (DM) was recovered as liquid slurry after sieving through a 5-mm sieve. These tests were performed at up to 35% DM, showing that this process can easily manage high DM loadings. MSW enzymatic liquefaction promotes the separation of organics and paper from solids, which facilitate the use of these degradable fractions, with minimal loss, capable to enter a biogas plant through existing pipes.     

酶法合成生物柴油的研究进展

生物柴油是一种清洁可再生的生物能源,是石油燃料的理想替代物。酶法合成生物柴油具有提取简单、反应条件温和、醇用量小、甘油易回收和无废物产生等优点。综述了脂肪酶与固定化脂肪酶、全细胞生物催化剂在生物柴油生产中应用的新进展,并对我国生物柴油产业的发展提出了建议。     

Self-Bonding Boards From Plantain Fiber Bundles After Enzymatic Treatment: Adhesion Improvement of Lignocellulosic Products by Enzymatic Pre-Treatment

Self-bonding boards were manufactured with treated fibers at different concentrations of a laccase enzyme. This enzyme induced the generation of phenoxy radicals in the fiber lignin which can generate covalent bonds and cross-linked by radical–radical coupling. The effect of laccase concentration on the properties of obtained fiberboards was evaluated. The formation of free radicals and changes in the lignin macromolecule was measured using scavenging activity test, infrared spectroscopy, electron paramagnetic resonance and scanning electron microscopy. Thermal and mechanical properties of the resulting fiberboards were determined by differential scanning calorimetry, thermo gravimetric analysis and flexion tests. Increased thermal stability, modulus of elasticity and modulus of rupture and also, a reduction in thickness swelling and water absorption, were observed at higher concentrations of laccase. These results are ascribed to the effect of the free radicals that were generated during the enzymatic treatment.     

Development of Urea Uptake and Release Studies Using N,N-Dimethylacrylamide/Maleic Acid/Citric Acid Based Macrogel

Journal of Polymers and the Environment - Recently, the use of polymers in agricultural and horticultural applications has been seen as a solution to reduce water consumption and excess fertilizer...     

Enzymatic pretreatment of lignocellulosic wastes to improve biogas production

The effect of enzymatic pretreatment of sugar beet pulp and spent hops prior to methane fermentation was determined in this study. These industrial residues were subjected to enzymatic digestion before anaerobic fermentation because of high fiber content (of 85.1% dry matter (DM) and 57.7% DM in sugar beet pulp and spent hops, respectively). Their 24h hydrolysis with a mix of enzymatic preparations Celustar XL and Agropect pomace (3:1, v/v), with endoglucanase, xylanase and pectinase activities, was most effective. Reducing sugars concentrations in hydrolysates of sugar beet pulp and spent hops were by 88.9% and 59.4% higher compared to undigested materials. The highest yield of biogas was obtained from the enzymatic hydrolysate of sugar beet pulp (183.39 mL/d from 1g COD at fermenter loading with organic matter of 5.43 g COD/L × d). Fermentation of sugar beet pulp gave 19% less biogas. Methane fermentation of spent hops hydrolysate yielded 121.47 mL/d biogas from 1g COD (at 6.02 g COD/L × d, 13% more than from spent hops). These results provide evidence that suitable enzymatic pretreatment of lignocellulosic wastes improve biogas yield from anaerobic fermentation.     

Adsorption of Cationic Dye Using A newly Synthesized CaNiFe2O4/Chitosan Magnetic Nanocomposite: Kinetic and Isotherm Studies

Journal of Polymers and the Environment - Chitosan biopolymer was extracted from chitin and utilized for the synthesis of CaNiFe2O4/Chitosan as a new magnetic nanocomposite. The structural and...     

Characterization of Chemically Modified Potato Starch Films Through Enzymatic Degradation

The present investigation was undertaken to characterize the biodegradation pattern of chemically modified starch films. Chemically modified starch films obtained by esterification of the hydroxyl groups of the polysaccharide have shown lower water sorption than native starch films, being therefore more attractive for a number of processing applications. However, no systematic study characterizing their biodegradation behavior and comparing it with the degradation pattern of native starch films has still been published. In the current contribution we characterized the enzymatic degradation pattern of three derivatized starch films by use of a commercial α-amylase from Bacillus licheniformis. Optimum degradation conditions were chosen upon assaying the effect of enzyme load and temperature on the reaction course of native starch films. Under the conditions selected, comparison of different derivatization procedures revealed that the starch film modified with octanoyl chloride was enzymatically hydrolyzed at a much higher rate than native starch film. Maleated starch films also showed higher susceptibility to α-amylolytic hydrolysis than native starch, whereas acetylated starch showed a hydrolysis pattern similar to that of native starch. Differences in degradation rates of chemically modified films were explained in terms of their amylose content which promotes dense networks that hinder the access of starch-degrading enzymes.     

Enzymatic hydrolysis of organic waste materials in a solid-liquid system

In the current climate of increasing emphasis on environmental protection and efficient waste management, regional management bodies and environmental agencies are striving to achieve an economical and environmentally acceptable system for the recycling of biodegradable organic wastes. Composting would appear to be a cost effective solution to this problem, but in its entirety, composting is an inherently lengthy and variable process and is restrictive in terms of the demand on resources and space in composting plants. The aim of this study was to compare a biological composting process of solid residues with an enzymatic hydrolysis process of residues. The length of time required to naturally compost three organic materials, spent mushroom compost (SMC), farmyard manure (FYM) and dairy wastewater sludge (DWS) under optimal conditions was 42 days, 98 days and 84 days, respectively. In an attempt to accelerate this process, commercial enzymes were added to the waste products in a heterogeneous solid-liquid system. The enzymes utilised included a range of proteases, cellulases, ligninases, lipases and pectinases, which are responsible for the hydrolysis of protein, cellulose, lignin, lipids and carbohydrates, respectively. Preliminary results indicate that all of the organic materials were stabilised within 9h and that the enzymes used would, therefore, improve the efficiency of a waste management plant, if such a system were employed. Spent mushroom compost has a mean N/P/K ratio of 20:10:10 recorded for composted SMC, while a similar ratio of 20:10:20 was obtained for hydrolysed SMC. In contrast, composted farmyard manure has a N/P/K ratio of 30:0:30 and a ratio of 10:1:10 for hydrolysed FYM. Finally, composted DWS has a N/P/K ratio of 20:1:30 while DWS hydrolysate has a N/P/K ratio of 40:1:20, with the decrease in nitrogen in the composted DWS attributed to the addition of wood chippings and sawdust as a bulking agent. While all three materials have a considerable supply of plant nutrients, the variability in nutrients could be overlooked when employed as a soil amendment.     

Influence of Short Central PEO Segment on Hydrolytic and Enzymatic Degradation of Triblock PCL Copolymers

Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (M _n 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by ¹H NMR, quantitative ¹³C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (<?2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss, while FTIR analysis detected changes in crystallinity indexes and GPC measurements revealed bulk degradation. Enzymatic degradation tested by cell-free extracts containing Pseudomonas aeruginosa PAO1 confirmed high enzyme activity throughout the surface causing morphological changes detected by optical microscopy and AFM analysis. The changes in roughness of polymer films revealed surface erosion mechanism of enzymatic degradation. Copolymer with the highest content of PEO segment and the lowest molecular weight showed better degradation ability compared to PCL and other copolymers. Furthermore, composting of polymer films in a model compost system at 37 °C resulted in significant degradation of the all synthesized block copolymers.     

Enzymatic Degradation and Aminolysis of Microbial Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Single Crystals

Solution-grown single crystals of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] were hydrolyzed by polyhydroxybutyrate (PHB) depolymerase from Ralstonia pickettii T1. Enzymatic degradation proceeded from the edges of lamellar crystals, yielding serrated contour and small crystal fragments. Gel permeation chromatography analysis revealed that the molecular weights of the crystals decreased during enzymatic degradation, suggesting that the enzymatic hydrolysis of chain-folding regions at the crystal surfaces occurred in addition to the enzymatic degradation at crystal laterals or edges. After P(3HB-co-4HB) single crystals were aminolysed in 20% aqueous methylamine solution to remove the folded-chain regions and enzymatic degradation by lipase from Rhizopus oryzae to remove 4HB components at crystal surfaces of single crystal aminolyzed, it was found that a small amount (up to ca. 2 mol%) of 4HB component can be incorporated into the P(3HB) mother crystal lattice irrespective of the 4HB content.     

Composites Produced from Natural Rubber and Chrome-Tanned Leather Wastes: Evaluation of their In Vitro Toxicological Effects for Application in Footwear and Textile Industries

A new composite has been developed from natural rubber and chrome-tanned leather waste for use in footwear and textile industries. The contribution of this material to environmental quality and sustained development should be highligh because chrome tanned leather wastes, a major environmental problem, can be recycled. However, the safety of this new material for human use is questionable, as it is already well reported in the literature that chromium, particularly in its hexavalent oxidation state, can be genotoxic and carcinogenic to living beings. Thus, the aim of this study was to evaluate in vitro biocompatibility of this composite material for possible use in the footwear and textile industries, through cytotoxicity, cell adhesion, and genotoxicity tests. Inductively coupled plasma optical emission spectrometry (ICP-OES) was used to measure both concentrations of total and hexavalent chromium. Based on the findings, it was concluded that the composite exhibits low levels of cytotoxicity and genotoxicity, and possesses favorable properties for initial cell adhesion. Furthermore, it was verified that the composites released low concentrations of chromium and that the predominant species released would be trivalent chromium. The results of the present study open the possibility of the incorporation of solid residues of tanned leather into chromium without necessarily the chromium contained in these residues influences the toxicity and genotoxicity of this new material.     

Enzymatic Degradation of Poly(l-Lactic Acid): Effects of UV Irradiation

Amorphous and crystallized poly(l-lactic acid) (PLLA-A and PLLA-C, respectively) films were prepared, and the proteinase K-catalyzed enzymatic degradation of UV-irradiated and non-irradiated PLLA-A and PLLA-C films was investigated for periods up to 10 h (PLLA-A) and 60 h (PLLA-C). The molecular weights of both the PLLA-A and PLLA-C films can be manipulated by altering the UV irradiation time. The enzymatic weight loss values of the UV-irradiated PLLA films were higher than or similar to those of the non-irradiated PLLA film, when compared with the specimens of same crystallinities. UV irradiation is expected to cause the PLLA films to undergo chain cleavage (a decrease in molecular weight) and the formation of C=C double bonds. It seems that the acceleration effects from decreased molecular weight on enzymatic degradation were higher than or balanced with the disturbance effects caused by the formation of C=C double bonds. After enzymatic degradation, a fibrous structure appeared on the spherulites of the UV-irradiated PLLA-C film. This structure may have arisen from chains containing or neighboring on the C=C double bonds, which were enzymatically undegraded and assembled on the film surface during enzymatic degradation. The results of this study strongly suggest that UV irradiation will significantly affect the biodegradation behavior of PLLA materials in the environment.     

Renewable Resources and Enzymatic Processes to Create Functional Polymers: Adapting Materials and Reactions from Food Processing

We are exploiting materials and concepts from food science to create functionalized, environmentally friendly derivatives of the biopolymer chitosan, a byproduct of seafood processing. Functional groups are grafted onto chitosan using tyrosinase, the enzyme responsible for food browning. The functionalizing groups studied include low-molecular-weight phenols derived from natural sources and high-molecular-weight proteins. The approach of using low-molecular-weight phenols to functionalize chitosan is illustrated with arbutin, a natural phenol found in pears. Results demonstrate that tyrosinase initiates reactions that lead to the conversion of arbutin–chitosan solutions into gels. These gels can be rapidly broken by treatment with the chitosan-hydrolyzing enzyme chitosanase, demonstrating that the chitosan derivatives remain biodegradable. We briefly review other studies in which low-molecular-weight natural phenols are enzymatically grafted onto chitosan to confer functional properties. The creation of co-polymers is illustrated by results in which tyrosinase is used to couple gelatin onto chitosan. Gelatin is a proteinaceous byproduct of meat production. The tyrosinase-generated gelatin–chitosan conjugates have been observed to offer interesting rheological and thermal properties. These results demonstrate the potential for using renewable resources and enzymatic processing to create environmentally friendly polymers with useful functional properties.     

Electro and Baromembrane Methods of Petrochemical Enterprises' Wastewater Treatment

The paper focuses on the development of production methods for new ion‐exchange membranes on the basis of ED‐20 industrial epoxide resin, resorcinol diglycidyl ether (RDGE), vinyl ether of monoethanolamine (VEMEA), and different di‐ and polyamines (polyethylenepolyamine (PEPA), polyethyleneimine (PEI), and hexamethylenediamine (HMDA)) in the presence of polyvinyl chloride (PVC) as a thermoplastic polymer binder. With the purpose to establish optimum conditions for synthesis of interpolymer membranes, the influence of reactants' concentration, of the temperature, of the nature and the quantity of the solvent, and of the process duration, was studied. It was found that when the VEMEA content in the reaction mixture is increased, the static exchange capacity (SEC) of the membrane increases in the presence of: PEI in the range of 1.2 to 4.7 mEq/L; PEPA: 1.0 to 4.0 mEq/L; and, HMDA: 1.4 to 5.2 mEq/L. It was shown that the optimum synthesis conditions are heating the reaction mixture to 60 °C to 70 °C for six to seven hours with constant stirring. For increasing the basicity of membranes, N‐alkylation was carried out using known alkylating agents (methyl iodide, dimethyl sulfate, and epichlorohydrin (ECH)). The primary electrochemical and physic‐mechanic properties of the obtained membranes were studied on pilot electrodialysis cells. The process flow diagram of the electrodialysis plant, as well as the engineering design documentation thereof were developed, and a pilot electrodialysis plant was constructed. The maximum production capacity of the pilot plant was 600 L/hr with a 30 percent desalinization rate. To increase the desalinization rate up to 75 percent, circulation of the solution and a decrease of production capacity was suggested. For meeting the treated water requirements in terms of salt content, a partial recirculation mode was introduced. In the course of the studies conducted, a process flow diagram was developed, and an experimental installation and a pilot reverse osmosis plant were fabricated for phenol and ammonium nitrogen purification. The pilot plant was tested using process condensate from the Pavlodar Petrochemical Plant. It was found that prior oxidation of the condensate with ozone in alkali medium resulted in phenol purification up to 85 percent and ammonium nitrogen up to 93 percent. ©2015 Wiley Periodicals, Inc.     

High-Solid Loading Enzymatic Hydrolysis of Waste Office Paper for poly-3-hydroxybutyrate Production Through Simultaneous Saccharification and Fermentation

Journal of Polymers and the Environment - Waste paper holds great potential as a substrate for the microbial production of bioplastic (Poly-3-hydroxybutyrate (PHB)). This study aimed to produce PHB...     

Atmospheric Metal Pollutants-Archives, Methods, and History

Pollution of the atmosphere with cadmium (Cd), mercury (Hg), and lead (Pb) is a consequence of human activities. Natural archives are necessary to reconstruct the long-term history of metal deposition because accurate measurement of atmospheric deposition is a recent accomplishment. Reconstructions require: (1) accurate determination of concentrations of elements and isotopes, (2) accurate chronology of archives, and (3) archives that faithfully record atmosphere deposition. The most useful long-term archives are accumulations of ice and snow, peat, and lake sediment. Quantification of Cd deposition is uncommon because of its low concentration and substantial chemical mobility. Nonetheless, trends in peat and lake sediment are similar to those of Hg and Pb since ca. 1800 a.d. Both Hg and Pb are relatively chemically immobile and thus the peat and lake archives are believed to record historic trends of atmospheric deposition. Isotopic and concentration studies of Pb indicate a history of northern hemisphere atmospheric pollution extending back prior to 0 a.d. Although measurements of Hg concentration are now routine, isotopic measurements are in their infancy. Some Hg pollution sources have unique isotopic ratios, thereby contributing unique signals to the total Hg. Maximum accumulation rates of Hg and Pb occur up to 10 years later than for Cd (1970s versus 1960s in eastern North America, perhaps slightly later in Europe). By 2004, deposition of Cd, Hg, and Pb had declined from peak values in eastern North America more than 75, 75, and 90%, respectively.