Removal of Linear and Branched p-Alkylphenols from Aqueous Solution by Combined Use of melB Tyrosinase and Chitosan Beads

In this study, melB tyrosinase was applied for enzymatic removal of linear and branched p-alkylphenols from aqueous solutions. First, systematic studies were carried out to estimate the effects of the process parameters such as the temperature, pH value, and enzyme dose on quinone conversion of p-cresol as a model phenol compound. A variety of p-alkylphenols were removed from aqueous solutions through the tyrosinase-catalyzed quinone conversion and subsequent nonenzymatic adsorption of quinone derivatives on chitosan beads at pH 6.0 and 30 °C under the optimum conditions determined for p-cresol. The % removal values of 98–100 were obtained for p-n-alkylphenols. Branched p-alkylphenols with a weak estrogenic activity containing 4-tert-butylphenol and 4-tert-pentylphenol, which underwent no quinone conversion by commercially available mushroom tyrosinase in the absence of H₂O₂, were also effectively removed by further increasing either the melB tyrosinase concentration or the amount of added chitosan beads. The present technique is much effective in the fact that a series of reactions rapidly progress under mild conditions and the chitosan beads can be readily separated from the reaction medium after the enzymatic treatment.     

膜电解技术处理含氯及重金属的废酸

采用离子交换膜电解技术处理铜冶炼过程产生的含氯及重金属的废酸。考察了废酸处理工艺、电解温度、电解时间、电流密度和催化剂的添加等条件对处理效果的影响。实验结果表明：采用先沉淀重金属后脱氯的废酸处理工艺，氯离子和铜离子的去除效果均较好;当以钛盐为催化剂时，在电解温度为40 ℃、电解时间为2.0 h、电流密度为825 A/m²的最佳工艺条件下，处理后废酸中的氯离子质量浓度为0.22 g/L，氯离子去除率为98.59%，铜离子质量浓度为0.45 g/L，铜离子去除率为95.08%，其他重金属大部分也得到有效去除。净化后的废酸可回用至铜冶炼的生产过程中。     

A new strain for recovering precious metals from waste printed circuit boards

A new strain, Pseudomonas Chlororaphis (PC), was found for dissolving gold, silver, and copper from the metallic particles of crushed waste printed circuit boards (PCBs). The optimized conditions that greatly improved the ability of producing CN^? (for dissolving metals) were obtained. Dissolving experiments of pure gold, silver, and copper showed that the metals could be changed into Au⁺, Ag⁺, and Cu²⁺. PC cells and their secreta would adsorb metallic ions. Meanwhile, metallic ions destroyed the growth of PC. Dissolving experiments of metallic particles from crushed waste PCBs were performed by PC. The results indicated that 8.2% of the gold, 12.1% silver, and 52.3% copper were dissolved into solution. This paper contributed significance information to recovering precious metals from waste PCBs by bioleaching.     

Removal of copper,chromium, and arsenic from CCA-C treated wood by EDTA extraction

Ethylenediaminetetracetic acid (EDTA) is one of the most common chelators used to bind the metal ions in extremely stable complexes in heavy metal contaminated soils and thus to remediate such substrates. EDTA forms water soluble complexes with many metal ions and it is used to release the various metals. In this study, EDTA extraction of copper, chromium, and arsenic from chromated copper arsenate (CCA-C) treated wood was evaluated using batch leaching experiments. CCA-treated wood samples were extracted with eight different concentrations of EDTA for 4, 8, 18, and 24 h at room temperature. Exposing CCA-treated chips and sawdust to EDTA extraction enhanced removal of CCA components compared with extraction by deionized water. Grinding CCA-treated wood chips into 40-mesh sawdust provided greater access to and removal of CCA components. Extraction with 1% EDTA solution for 24 h removed 60% copper, 13% chromium, and 25% arsenic from treated chips. EDTA extraction of treated sawdust samples resulted in 93% copper, 36% chromium, and 38% arsenic removal. CCA leaching from treated wood blocks was also evaluated according to modified AWPA E11-99 standard test method of determining the leachability of wood preservatives. Leaching of CCA components from treated wood blocks with 1% EDTA solution for 14 days caused more copper leaching compared to leaching with deionized water. Leaching with 1% EDTA for 14 days removed 53% copper from the blocks whereas 14% copper was leached from the blocks with deionized water. The results suggest that EDTA extraction removes significant quantities of copper from CCA-treated wood. Thus, EDTA could be important in the remediation of wood waste treated with the newest formulations of organometalic copper compounds and other water-borne wood preservatives containing copper.     

Poly(Acrylic Acid) Grafted Sodium Alginate Di-Block Hydrogels as Efficient Biosorbents; Structure-Property Relevance

Naturally-based poly(acrylic acid) grafted sodium alginate di-block hydrogels were investigated as high efficiency biosorbents for copper(II) ion. The grafted di-block hydrogel was characterized using FTIR, TGA and SEM techniques. Blank and immobilized algal biosorbent beads formed via 2.0% (w/w) calcium ions were also investigated. Batch adsorption experiments revealed optimal pH dependence of copper(II) ion biosorption at pH 5.5 with high efficient copper(II) ion uptake of 98.5 mg/g. The dynamics studies showed that the high efficiency copper(II) ion biosorption followed pseudo-second order kinetics with significant contribution of intraparticle diffusion mechanism. The equilibrium data fitted to Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) adsorption isotherm models. Thermodynamics parameters for copper(II) biosorption on blank and immobilized algal beads depicted the spontaneous nature of the biosorption process. Such high efficiency, feasibility, simplicity, and low cost properties adapt the di-block biosorbent to be the next generation promising biosorbents for water decontamination and to help in the recovery of the missing ecologic harmony.     

A novel method for the preparation of silver/chitosan-O-methoxy polyethylene glycol core shell nanoparticles

Uniformly sized silver/chitosan-O-methoxy polyethylene glycol (chitosan-O-MPEG) core shell nanoparticles with different degree of substitution were synthesized. Thus, N-phthaloyl chitosan is reacted with polyethylene glycol monomethyl ether iodide in the presence of silver oxide by the following steps. At first, amino groups of chitosan are protected by fourfold excess of phthalic anhydride. Then N-phthaloyl chitosan is reacted with an appropriate amount of monomethyl ether iodide in the presence of silver oxide and lastly N-phthaloyl groups are removed to yield silver/chitosan-O-MPEG core shell nanoparticles. Structure of prepared silver/chitosan-O-MPEG core shell nanoparticles have been characterized by UV/Vis spectroscopy, transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), X-ray diffraction, and scan electron microscopy (SEM-EDX). Experimental results revealed that the prepared silver core particles had the size 18?±?2?nm. Core shell structure with chitosan-O-MPEG-coating had the size 40?±?2?nm.     

Chitosan Functionalization with Amino Acids Yields to Higher Copper Ions Adsorption Capacity

Chitosan (Chi) beads were conjugated with three different amino acids [namely, glutamic acid (GLU), methionine (MET), and taurine (TAU)] aiming to increase the divalent copper ions uptake in aqueous media. Scanning Electron Microscopy evidenced the development of a large porous structure after amino acid functionalization, associated with the increase in a number of amino groups in the polymer backbone. X-Ray Photoelectron Spectroscopy and Fourier-Transform Infrared Spectra analyses were also employed to assess the conjugation of these three different amino acids in chitosan backbone. Adsorption experiments were conducted in a batch process, at 298 K, and kinetic data indicated a slightly better fitting for the pseudo-first-order model when compared to pseudo-second order. Intraparticle diffusion model suggested a three-step mechanism for Cu(II) adsorption kinetics, limited by the third step, the intraparticle diffusion. The isotherm data fitting to the traditional Langmuir and Freundlich models indicated a better fit for the former case. The amino acid conjugation resulted in the increase of the maximum adsorption capacity for Cu(II) from 1.30 mmol g^?1 prior to amino acid conjugation to values as high as 2.31 mmol g^?1, 2.40 mmol g^?1 and 2.68 mmol g^?1 for Chi–TAU, Chi–GLU, and Chi–MET, respectively. These results are attributed to the introduction of additional amino groups and new carboxylate and amino acid residues into the chitosan backbone, which might also be explored for amino acid demanding applications.     

Study on the influence of various factors in the hydrometallurgical processing of waste printed circuit boards for copper and gold recovery

The present lab-scale experimental study presents the process of leaching waste printed circuit boards (WPCBs) in order to recover gold by thioureation. Preliminary tests have shown that copper adversely affects gold extraction; therefore an oxidative leaching pre-treatment was performed in order to remove base metals. The effects of sulfuric acid concentration, hydrogen peroxide volume and temperature on the metal extraction yield were studied by analysis of variance (ANOVA). The highest copper extraction yields were 76.12% for sample A and 18.29% for sample D, after leaching with 2 M H₂SO₄, 20 ml of 30% H₂O₂ at 30 °C for 3 h. In order to improve Cu removal, a second leaching was performed only on sample A, resulting in a Cu extraction yield of 90%. Other experiments have shown the negative effect of the stirring rate on copper dissolution. The conditions used for the process of gold extraction by thiourea were: 20 g/L thiourea, 6 g/L ferric ion, 10 g/L sulfuric acid, 600 rpm stirring rate. To study the influence of temperature and particle size, this process was tested on pins manually removed from computer central processing units (CPUs) and on waste CPU for 3½ h. A gold extraction yield of 69% was obtained after 75% of Cu was removed by a double oxidative leaching treatment of WPCBs with particle sizes smaller than 2 mm.     

Improvement of Physico-Mechanical Properties of Photo-Cured Chitosan Films with Ethylene Glycol Dimethacrylate and (2-Hydroxyethyl) Methacrylate

Chitosan, a natural polymer, was prepared by deacetylation of chitin which was obtained from dried prawn shell and was characterized. Thin chitosan film of chitosan was prepared by casting method from 0.2 % chitosan in 2 % acetic acid solution. Five formulations were developed with ethylene glycol dimethacrylate and (2-hydroxyethyl) methacrylate along with photo-initiator, Darocur-1664 (4 %). The chitosan film was soaked in the formulations at different soaking times and irradiated under UV-radiation at different intensities for the improvement of its physical and mechanical properties. The cured chitosan films were then subjected to various mechano-chemical tests like tensile strength, elongation at break, polymer loading, water absorption and gel content. The formulation containing 30 % ethylene glycol dimethacrylate and 66 % (2-hydroxyethyl) methacrylate showed the best performance at the 30th UV pass of UV-radiation for 3 min soaking time.     

Improvement of Physico-mechanical Properties of Chitosan Films by Photocuring with Acrylic Monomers

Natural polymer, chitosan was obtained from dried prawn shell waste through the preparation of chitin and was characterized. Thin film of chitosan was prepared by casting method from its 2% chitosan solution. Mechanical properties like tensile strength (TS), elongation at break (Eb) of chitosan film were studied. Five formulations were developed with 2-ethyl-2-hydroxy methyl-1,3-propandiol trimethacrylate (EHMPTMA), a trifunctional monomer and 2-ethylhexyl acrylate (EHA), a monofunctional monomer in the presence of photoinitiator Darocur-1664 (2%). The film was soaked in those monomer formulations in dissimilar soaking times and irradiated under UV-radiation at different radiation intensities for the improvement of the properties of chitosan film. The cured films were then subjected to various characterization tests like TS, Eb, polymer loading (PL), water absorbency, gel content etc. The formulation, containing 25% EHMPTMA and 73% EHA showed the best performance at 10th UV passes of UV radiation for 4 min soaking time.     

壳聚糖吸附重金属离子的研究进展

综述了,我国近几年来壳聚糖处理含重金属离子废水的研究进展。壳聚糖及其改性产品的吸附性能主要体现在对各种金属离子的吸附上,为了有选择性地吸附某种或某些金属离子,人们通过修饰、交联、接枝等方法对壳聚糖进行了各种改性研究。     

Synthesis of Polymeric Matrices for Adsorption and Purification of Endoglucanase

Chitosan (CHS), chitosan–Eudragit® EPO (CHS–EPO) and chitosan beads partially cross-linked with glutaraldehyde (CHS–GLUT) were obtained in order to improve the adsorption selectivity of endoglucanase from a fungal culture obtained under SSF by Aspergillus niger using soybean harvest residues as support. The matrices synthetized were characterized in terms of physical and chemical changes. Fourier-transformed infrared spectroscopy with attenuated total reflectance device (FTIR-ATR) was employed to verify the chemical changes on the CHS matrix after the synthesis of CHS–GLUT and CHS–EPO. Scanning electron microscopy (SEM) was performed to compare the surface morphology of the polymeric beads. Two variables, purification factor and yield percentage of the adsorption process, were analyzed using a bifactorial ANOVA considering the matrix–time first order interaction. SEM results exhibited greater surface roughness in the CHS–GLUT and CHS–EPO matrices which may enhance endoglucanase adsorption. FTIR-ATR results confirmed an effective chemical modification of the CHS matrix after crosslinking with GLUT and corroborated the efficiency of the synthesis of the CHS–EPO matrix by the presence of chemical groups of the EPO polymer. An endoglucanase purification factor close to 9 was achieved with the CHS–GLUT matrix and a yield percentage of 60% was obtained with the CHS–EPO matrix. Bifactorial ANOVA results showed the matrix–time interaction to be significant for both variables. The CHS–GLUT matrix with low crosslinking times and the novel CHS–EPO matrix could be included in the bioseparation stage of endoglucanase using a simple and a low-cost method such as batch adsorption.     

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

Adsorption of malachite green on groundnut shell waste based powdered activated carbon

In the present technologically fast changing situation related to waste management practices, it is desirable that disposal of plant waste should be done in a scientific manner by keeping in view economic and pollution considerations. This is only possible when the plant waste has the potential to be used as raw material for some useful product. In the present study, groundnut shell, an agricultural waste, was used for the preparation of an adsorbent by chemical activation using ZnCl2 under optimized conditions and its comparative characterisation was conducted with commercially available powdered activated carbon (CPAC) for its physical, chemical and adsorption properties. The groundnut shell based powdered activated carbon (GSPAC) has a higher surface area, iodine and methylene blue number compared to CPAC. Both of the carbons were used for the removal of malachite green dye from aqueous solution and the effect of various operating variables, viz. adsorbent dose (0.1-1 g l(-1)), contact time (5-120 min) and adsorbate concentrations (100-200 mg l(-1)) on the removal of dye, has been studied. The experimental results indicate that at a dose of 0.5 g l(-1) and initial concentration of 100 mg l(-1), GSPAC showed 94.5% removal of the dye in 30 min equilibrium time, while CPAC removed 96% of the dye in 15 min. The experimental isotherm data were analyzed using the linearized forms of Freundlich, Langmuir and BET equations to determine maximum adsorptive capacities. The equilibrium data fit well to the Freundlich isotherm, although the BET isotherm also showed higher correlation for both of the carbons. The results of comparative adsorption capacity of both carbons indicate that groundnut shell can be used as a low-cost alternative to commercial powdered activated carbon in aqueous solution for dye removal.     

Improving the two-step remediation process for CCA-treated wood: Part II. Evaluating bacterial nutrient sources

Remediation processes for recovery and reuse of chromated-copper-arsenate- (CCA) treated wood are not gaining wide acceptance because they are more expensive than landfill disposal. One reason is the high cost of the nutrient medium used to culture the metal-tolerant bacterium, Bacillus licheniformis, which removes 70-100% of the copper, chromium, and arsenic from CCA-treated southern yellow pine (CCA-SYP) in a two-step process involving oxalic acid extraction and bacterial culture. To reduce this cost, the nutrient concentration in the culture medium and the ratio of wood to nutrient medium were optimized. Maximum metal removal occurred when B. licheniformis was cultured in 1.0% nutrient medium and at a wood to nutrient medium ratio of 1:10. Also, malted barley, an abundant by-product of brewing, was evaluated as an alternative nutrient medium. Tests were done to determine absorption of metals by barley, and the results indicate that the barley acted as a biosorbent, removing heavy metals from the liquid culture after their release from CCA to SYP. For comparison, tests were also performed with no nutrient medium. Following bacterial remediation, 17% copper and 15% arsenic were removed from an aqueous slurry of CCA-SYP (no medium). When oxalic acid extraction preceded the aqueous bacterial culture, 21% copper, 54% chromium, and 63% arsenic were removed. The two-step process (oxalic acid extraction and bacterial culture with nutrient medium) appears to be an effective, yet costly, way to remove metals.     

The storage of sewage sludge: influence of liming on the evolution of copper chemical fractions

Sewage sludge re-used in agriculture has to be stabilized and is often stored for several months before land spreading. Stabilization treatment may affect the behaviour of heavy metals such as Cu, which is an element potentially toxic to the environment. In the present study, the chemical forms of copper have been investigated in heaps of limed and unlimed sludge coming from the wastewater treatment plant of Roselies (Belgium). These limed and unlimed aerobically digested sludges were stored during 4 mo in controlled conditions close to field ones. The sequential extraction procedure developed by Tessier was used to determine the copper chemical forms of representative samples taken in the outer shell and in the depth of the heaps. The physico-chemical properties (pH, organic matter, dry matter and temperature) of these samples were also monitored. This study shows that liming transforms part of organically-bound copper into both exchangeable and residual copper. These changes mainly occur during the first 2 wk of storage. After several months of storage, copper passes from the residual fraction to the exchangeable and oxide fractions. During the whole experiment, changes occur faster in the outer shell than in the depth of the heaps. Thus, we demonstrate that the distribution of the copper forms depends on the storage time and it is different in the outer shell from that in the depth of the heaps.     

Evaluation of Extracted Chitosan from Portunus Pelagicus for the Preparation of Chitosan Alginate Blend Scaffolds

In recent years there is a growing need in generating a biocompatible and cost effective porous scaffold for tissue engineering purposes. Therefore, this study focused on conversion of the shell waste of locally available crab variety P.pelagicus (Blue swimming crab) into the chitosan scaffold. As the poor mechanical strength of chitosan limits its usage in tissue engineering, it was blended with alginate. The scaffolds were prepared by the freeze gelation method which requires less time and minimum energy, with fewer residual solvent and easier to scale up. To the best of our knowledge there are no reports on scaffold preparation from the extracted chitosan, blended with alginate by freeze gelation method. The biological properties of chitosan-alginate scaffolds (Cts–Alg) were evaluated and compared with those of chitosan scaffolds. The prepared scaffolds were characterized by SEM, swelling property, in vitro enzymatic degradation, and hemo, biocompatibility properties. Chitosan-alginate scaffolds had an average pore size of 40 μm and tensile strength of 0.564 ± 0.0.018 % MPa. Its swelling ratio was 27.5 ± 0.28 %, with mass loss percentage of 10 ± 0.33 % after 4 weeks of degradation. It has exhibited good hemocompatible properties too. Mouse fibroblast 3T3 cells were able to adhere and proliferate well in the blended scaffold. All these results indicated that chitosan-alginate scaffold is a suitable alternative substitute for tissue engineering.     

Enhanced bioleaching efficiency of copper from waste printed circuit boards (PCBs) by dissolved oxygen-shifted strategy in <Emphasis Type="Italic">Acidithiobacillus ferrooxidans</Emphasis>

Acidithiobacillus ferrooxidans, as chemolithotrophic aerobic bacterium, can obtain energy by oxidation of ferrous ions (Fe²⁺) to ferric ions (Fe³⁺) and use molecular oxygen (O₂) as terminal electron acceptor. In this study, the effects of dissolved oxygen (DO) levels in culture medium on cell growth and copper extraction from waste printed circuit boards (PCBs) were investigated in A. ferrooxidans. The whole culture period was divided into two stages of cell growth and copper extraction. At the former stage, relatively lower DO level was adopted to satisfy bacterial growth while avoiding excessive Fe²⁺ oxidation. At the later stage, higher DO was used to promote copper extraction. Moreover, shift time of DO from lower to higher level was determined via simulating Gauss function. By controlling DO at 10 % for initial 64 h and switching to 20 % afterwards and with 18 g/l PCBs addition at 64 h, final copper recovery reached 94.1 %, increased by 37.6 and 48.3 % compared to constant DO of 10 and 20 % operations. More importantly, copper leaching periods were shortened from 108 to 60 h. It was suggested that application of DO-shifted strategy to enhancing copper extraction from PCBs with reduced leaching periods is being feasible.     

Enhancement of Sedimentation Velocity of Heavy Metals Loaded Hydroxyapatite Using Chitosan Extracted from Shrimp Waste

In this study, synthesize hydroxyapatite (HA) suspensions sedimentation was used after usual terms as support for adsorption of heavy metals ions. Thus, the effectiveness of chitosan, produced from shrimp waste, in the flocculation of turbid suspensions resulting from the treatment of water contaminated with heavy metals was studied by adsorption on HA. Different particles sizes of HA were mainly controlled in this work (an average of granule size ranging from 1.6 to 63 μm). The results of Cu²⁺ and Zn²⁺ adsorption on HA showed relatively fast kinetics, with removal extent of 88–95 % by varying the initial total metal concentration. High removal rates were obtained for Cu²⁺. Chitosan was found to be able to eliminate by flocculation more than 98 % of turbid suspensions generated by metals adsorption on HA after only 30 min of sedimentation. Effects of pH and dose of chitosan on the coagulation–flocculation process were also studied. The optimal dose of chitosan was found between 0.2 and 2 mg/L which corresponds to an optimal pH ranging from 6 to 7.     

壳聚糖复合吸附剂对油的吸附性能

以天然可生物降解的壳聚糖和硬脂酸为原料,通过壳聚糖2位氨基与硬脂酸的羧基相互作用,引入疏水烷基链,制备了疏水的壳聚糖-硬脂酸复合吸附剂(简称复合吸附剂),采用傅立叶红外光谱、X射线衍射对复合吸附剂的结构进行表征,并考察了复合吸附剂对油的回收性能.实验结果表明:壳聚糖和硬脂酸以离子形式结合得到复合吸附剂;当硬脂酸与壳聚糖质量比为0.7时,硬脂酸的结合量最大;复合吸附剂对油的吸附量、保油率、脱附率的顺序分别为花生油(14.93 g/g)>甲基硅油(10.71 g/g)>液体石蜡(9.37 g/g),花生油(94.51%)>液体石蜡(90.74%)>甲基硅油(78.69%),花生油(95.62%)>液体石蜡(93.27%)>甲基硅油(90.73%).