Potential of immobilized bitter gourd (Momordica charantia) peroxidases in the decolorization and removal of textile dyes from polluted wastewater and dyeing effluent

Immobilized peroxidases from Momordica charantia were highly effective in decolorizing reactive textile dyes compared to its soluble counterpart. Dye solutions, 50-200 mg/l, were treated with soluble and immobilized bitter gourd peroxidases (specific activity of 99.0 EU per mg protein). The decolorization of dyes with soluble and immobilized enzyme was maximum in the range of pH 3.0-4.0. The effect of different temperatures on the dye decolorization was monitored and it was observed that all the dyes were maximally decolorized at 40 degrees C. In order to examine the operational stability of the immobilized preparation, the enzyme was repeatedly exploited for the decolorization of the dyes from fresh batch of dye solutions. Even after 10 cycles in each case the immobilized preparation retained nearly 50% of the initial enzyme activity. The immobilized enzyme exhibited more than 90% of the original activity while the soluble enzyme lost 33% of the initial activity when stored for 40 d at room temperature. Mixtures of three, four and eight dyes were prepared and treated with soluble and immobilized bitter gourd peroxidase. Each mixture was decolorized by more than 80% when treated with immobilized enzyme. Dyeing effluent collected from local dyers was treated with both types of enzyme preparations. Immobilized enzyme was capable of removing remarkably high concentration of color from the effluent. TOC content of soluble and immobilized enzyme treated individual dyes, mixture of dyes and dyeing effluent was determined and it was observed that higher TOC was removed after treatment with immobilized enzyme.     

凹凸棒石粘土固定辣根过氧化物酶处理含酚废水

采用凹凸棒石粘土、可溶性淀粉和工业水玻璃作为制备凹凸棒石粘土基颗粒的材料,并将制备的凹凸棒石粘土基颗粒进行改性,得到了改性后的凹凸棒石基多孔材料,并将其作为固定辣根过氧化物酶的载体,再应用于含酚废水的处理研究,取得了良好的效果。实验结果表明,辣根过氧化物酶的最佳固定化条件为:单位酶活载体量1 mg、固定化时间1.5小时、固定pH值5。并且在固定化酶循环使用6次后,苯酚去除率仍能达到62.3%。     

Selective removal of some polyhydric phenols from aqueous solution by ferric antimonate

Ferric antimonate, a cation-exchanger, has been investigated as an adsorbent for the removal of phenol and polyhydric phenols from aqueous solution. It has been found that ferric antimonate in H+ form selectively adsorbs polyhydric phenols having hydroxyl groups on adjacent positions. While phenol, resorcinol, and quinol did not show any appreciable adsorption, catechol, pyrogallol, and gallic acid having hydroxyl groups on adjacent positions exhibited considerable adsorption on ferric antimonate. Batch equilibrium experiments were carried out to study the effect of contact time, initial concentration of phenolic compounds, and temperature on the adsorption of phenolic compounds on ferric antimonate. The equilibrium time was found to be 1.5 hours for gallic acid and pyrogallol and 2 hours for catechol and salicylic acid. The adsorption data of the phenols at temperatures of 30 degrees, 40 degrees, and 50 degrees C have been described by Langmuir and Freundlich isotherm models. The best fit was obtained with the Langmuir model in the whole range of concentrations studied at all temperatures, indicating a monolayer adsorption onto a homogeneous adsorption surface. On the basis of the Langmuir isotherm, the maximum adsorption capacity of ferric antimonate for gallic acid, pyrogallol, catechol, and salicylic acid was found to be 3.915, 3.734, 2.397, and 2.758 mg/g, respectively at 30 degrees C. The maximum sorption capacity of ferric antimonate for the phenolic compounds studied is in the following order: gallic acid > pyrogallol > salicylic acid > catechol. The adsorption of phenolic compounds was found to decrease with an increase in temperature. Thermodynamic parameters like free energy, enthalpy, and entropy changes were calculated and discussed. The adsorption of polyhydric phenols on ferric antimonate is exothermic and spontaneous in nature.     

Removal of phenols from water accompanied with synthesis of organobentonite in one-step process

A novel technology of wastewater treatment was proposed based on simultaneously synthesis of organobentonite and removal of organic pollutants such as phenols from water in one-step, which resulted that both surfactants and organic pollutants were removed from water by bentonite. The effects of contact time, pH and inorganic salt on the removal of phenols were investigated. Kinetic results showed that phenols and cetyltrimethylammonium bromide (CTMAB) could be removed by bentonite in 25 min. The removal efficiencies were achieved at 69%, 92% and 99%, respectively, for phenol, p-nitrophenol and beta-naphthol at the initial amount of CTMAB at about 120% cation exchange capacity of bentonite. Better dispersion property and more rapid bentonite sedimentation were observed in the process. The results indicated that the one-step process is an efficient, simple and low cost technology for removal of organic pollutants and cationic surfactants from water. The proposed technology made it possible that bentonite was applied as sorbent for wastewater treatment in industrial scale.     

Temperature activated degradation (mineralization) of 4-chloro-3-methyl phenol by Fenton's reagent

With the aim to evaluate the effect of temperature, 4-chloro-3-methyl phenol (CMP) degradation by Fenton's reagent was investigated at 25 and 70 degrees C under the following initial conditions: [CMP]0 = 10 mM, [Fe2+]0 = 0.5 mM; ([H2O2]0/[CMP]0) = 80, pH0 = 3. The results indicated that CMP degradation was strongly influenced by temperature. In fact, the maximum TOC removal, achieved after ca. 24h, was by far greater at 70 degrees C (85%) than at 25 degrees C (36%). The same happened for organic chlorine (TOX) conversion into inorganic chloride, i.e. 100%, after 3 h at 70 degrees C, and 87%, after 27 h at 25 degrees C. As the recorded trends of CMP removal and chloride formation were basically the same, hydroxy substitution (ipso-substitution) was hypothesised as one likely mechanism of CMP degradation. The higher level of mineralization recorded at 70 degrees C was ascribed to: (i) a greater *OH concentration; (ii) a consequently greater extent of CMP oxidation to organic acids; (iii) a higher decarboxylation rate of such acids. An interesting consequence of such extended organic acids decarboxylation was a pH increase up to 8 that, in turn, caused, in the treated mixture, the decomposition of excess H2O2 as well as the precipitation of iron ions. These two latter outcomes are technologically important considering that usually, before discharging Fenton treated wastewater, specific polishing steps are required just to remove iron ions, decompose excess hydrogen peroxide and neutralise the pH.     

Synergetic integration of laccase and versatile peroxidase with magnetic silica microspheres towards remediation of biorefinery wastewater

In this study, a tailor-made biocatalyst consisting of a co-immobilized lignolytic enzyme cascade on multi-functionalized magnetic silica microspheres (MSMS) was developed. Physical adsorption was the most promising strategy for the synthesis of individual immobilized laccase (IL), immobilized versatile peroxidase (IP), as well as co-immobilized laccase (Lac) and versatile peroxidase (VP) with an enzyme activity recovery of about 79, 93, 27, and 27.5%, respectively. Similarly, the biocatalytic load of 116, 183, 23.6, and 31 U/g was obtained for IL, IP, and co-immobilized Lac and VP, respectively. The co-immobilized enzyme system exhibited better pH stability than the free and individual immobilized system by retaining more than 100% residual activity at pH 7.0 after a 150-h incubation; whereas, the thermal stability and kinetics of the co-immobilized biocatalyst were not much improved. IL and IP could be recycled for 10 cycles after which they retained 31 and 44% of their initial activities. Co-immobilized Lac and VP were reused for ten consecutive cycles at the end of which Lac activity was depleted, and 37% of VP activity was left. Free enzymes, IL, IP, co-immobilized Lac, and VP were applied to biorefinery wastewater (BRW) in a batch study to investigate the transformation of phenolic contaminants over a period of 5 days. The major classes of phenolic constituents in terms of their order of removal in a Lac-VP system was phenol >2-chlorophenol > trichlorophenol > dichlorophenol > cresols > dimethylphenol >2 methyl- 4, 6-dinitrophenol > 4-nitrophenol > tetrachlorophenols > pentachlorophenol. The free enzymes and individually immobilized enzymes resulted in 80% dephenolization in 5 days. By contrast, the co-immobilized biocatalyst provided rapid dephenolization yielding the same 80% removal within 24 h and 96% removal of phenols in 60 h after which the system stabilized, which is the major advantage of the co-immobilized biocatalyst.

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Comparison of commercial peroxidases for removing phenol from water solutions

This paper describes a comparison between horseradish peroxidase (HRP) and soybean peroxidase (SBP), the two most widely used commercial peroxidases for the removal of phenol from wastewater. Both enzymes achieve maximal removal efficiency in a neutral pH medium although they are still quite active in a pH range of between 6.0 and 8.0. The fact that both enzymes show similar phenol elimination levels at any temperature between 25 and 40 degrees C is also of interest. Studies were carried out in the absence and presence of different concentrations of a stabilisation additive, polyethylene glycol (PEG), in an attempt to optimise the phenol elimination procedure. The final choice of peroxidase will depend on the characteristics of the effluent, operational requirements and on economic considerations. Our findings show that HRP acts faster than SBP but is more susceptible to inactivation, although it is better protected by PEG. In consequence HRP will be the most suitable choice but the addition of a sufficient amount of PEG is critical.     

Comparison of the removal of 2,4-dichlorophenol and phenol from polluted water, by peroxidases from tomato hairy roots, and protective effect of polyethylene glycol

Multiple efforts have been directed towards optimized processes in which enzymes, like peroxidases, are used to remove phenolic compounds from polluted wastewater. Here we describe the use of peroxidase isoenzymes from tomato hairy roots, which were able to oxidise 2,4-dichlorophenol (2,4-DCP) and phenol from aqueous solutions. This could be an interesting alternative for the removal of these compounds from contaminated sites. We used different enzyme fractions: total peroxidases (TP), ionically bound to cell wall peroxidases (IBP), basic (BP) and acidic peroxidases (AP). We analyzed the optimum conditions of removal, the effect of Polyethyleneglycol (PEG-3350) on the process and on the enzyme activities, to obtain the maximum efficiency. The optimal H2O2 concentrations for 2,4-DCP and phenol removal were 1 and 0.1mM, respectively. TP, IBP and BP showed better removal efficiencies than AP, for both contaminants. The addition of different concentrations (10-100mg l(-1)) of PEG-3350 to solutions containing 2,4-DCP showed no effect on the removal efficiencies of the isoenzymes. However, PEG (100mg l(-1)) increased the removal efficiency of phenol by BP and IBP fractions. On the other hand, peroxidase activities from BP and IBP fractions were 3 and 13 times higher, respectively, than those detected for the same fractions in phenol treated solutions without PEG. The protective effect of PEG, which depends on the contaminant as well as of the enzyme fraction used, would be important to improve the removal efficiency of phenol by some peroxidase isoenzymes.     

含酚废水的无害化处理技术进展

概述了含酚废水的无害化处理技术现状及其进展。着重介绍了传统生物处理工艺的改良、高效菌种的选育、酶及固定化细胞等技术在含酚废水生物处理中的研究与应用 ,分析了先进氧化技术与焚烧技术的特点和存在的主要问题及应用前景 ,并探讨了含酚废水无害化处理技术的发展趋势     

Treatment of phenolic wastewater by horseradish peroxidase immobilized by bioaffinity layering

Horseradish peroxidase was immobilized by bioaffinity layering and used for the treatment of wastewater containing p-chlorophenol. For this purpose, lectin Concanavalin A was bound to Sephadex beads. The glycoenzyme peroxidase was layered upon this Con A layer. Subsequently, alternate layers of the enzyme and Con A were applied. The most efficient design consisted of three layers of Con A and peroxidase each. This immobilized enzyme preparation retained 80% of the activity of the free peroxidase used for immobilization. PEG at the concentration of 0.1 mg ml(-1) was found to prevent enzyme inactivation by the products, although it increased the process time. Thus 60 U ml(-1) of enzyme completely converted the p-chlorophenol (into products) in 4 min in the absence of PEG. On the other hand, only 0.05 U ml(-1) of enzyme was required for this purpose in the presence of PEG but the process required 60 min. Peroxidase converts phenol molecules into free radicals. These free radicals then polymerize and get precipitated. As a further means of minimizing exposure of the enzyme to free radicals and enhancing the reusability, it was decided to remove the enzyme from reaction medium after 10 min. With this strategy, the bioaffinity layered peroxidase preparation could be reused five times without any loss of activity.     

铁炭微电解-Fenton氧化-A/A/O生化等联合工艺处理酚类、硝基苯类废水的探讨

采用酸化沉淀-超滤-铁炭微电解-Fenton氧化-混凝沉淀-A/A/O生化处理等联合工艺处理酚类、硝基苯类废水。设计处理水量:物化预处理2 m^3/h、生化处理3 m^3/h。运行结果表明,该工艺处理效果良好,出水pH6~9,COD≤500 mg/L,SS≤400 mg/L,NH3-N≤50 mg/L,TP≤2 mg/L,酚类≤0.5 mg/L,硝基苯类≤2,盐分≤5000 mg/L,出水水质优于设计指标要求。     

Degradation of fenamiphos in soils collected from different geographical regions: the influence of soil properties and climatic conditions

The persistence of fenamiphos (nematicide) in five soils collected from different geographical regions such as Australia, Ecuador and India under three temperature regimes (18, 25 and 37 degrees C) simulating typical environmental conditions was studied. The effect of soil properties (soil pH, temperature and microbial biomass) on the degradation of fenamiphos was determined. The rate of degradation increased with increase in temperature. Fenamiphos degradation was higher at 37 degrees C than at 25 and 18 degrees C (except under alkaline pH). The degradation pathway differed in different soils. Fenamiphos sulfoxide (FSO) was identified as the major degradation product in all the soils. Fenamiphos sulfone (FSO2), and the corresponding phenols: fenamiphos phenol (FP), fenamiphos sulfoxide phenol (FSOP) and fenamiphos sulfone phenol (FSO2P) were also detected. The degradation of fenamiphos was faster in the alkaline soils, followed by neutral and acidic soils. Under sterile conditions, the dissipation of the pesticide was slower than in the non-sterile soils suggesting microbial role in the pesticide degradation. The generation of new knowledge on fenamiphos degradation patterns under different environmental conditions is important to achieve better pesticide risk management.     

Application of pier waste sludge for catalytic activation of proxy-monosulfate and phenol elimination from a petrochemical wastewater

This investigation aimed to remove phenol from real wastewater (taken from a petrochemical company) by activating peroxy-monosulfate (PMS) using catalysts extracted from pier waste sludge. The physical and chemical properties of the catalyst were evaluated by FE-SEM/EDS, XRD, FTIR, and TGA/DTG tests. The functional groups of O–H, C–H, CO₃^2?, C–H, C–O, N–H, and C–N were identified on the catalyst surface. Also, the crystallinity of the catalyst before and after reaction with petrochemical wastewater was 103.4 nm and 55.8 nm, respectively. Operational parameters of pH (3–9), catalyst dose (0–100 mg/L), phenol concentration (50–250 mg/L), and PMS concentration (0–250 mg/L) were tested to remove phenol. The highest phenol removal rate (94%) was obtained at pH=3, catalyst dose of 80 mg/L, phenol concentration of 50 mg/L, PMS concentration of 150 mg/L, and contact time of 150 min. Phenol decomposition in petrochemical wastewater followed the first-order kinetics (k> 0.008 min^?1, R²> 0.94). Changes in pH factor were very effective on phenol removal efficiency, and maximum efficiency (≈83%) was achieved in pH 3. The catalyst stability test was performed for up to five cycles, and phenol removal in the fifth cycle was reduced to 42%. Also, the energy consumption in this study was 77.69 kW h/m³. According to the results, the pier waste sludge catalyst/PMS system is a critical process for eliminating phenol from petrochemical wastewater.

     

Dephenolization and detoxification of olive-mill wastewater (OMW) by purified biotic and abiotic oxidative catalysts

The capability of two oxidative catalysts, a laccase from Rhus vernicifera and birnessite, a manganese oxide, in the dephenolization and detoxification of two olive-mill wastewater (OMW) samples, C1 and C2, differing for complexity and composition, was evaluated. OMW phenolic extracts (EC1 and EC2) and mono-substrate solutions of phenols mostly present in OMW samples were also tested. Birnessite was more effective than laccase in removing the phenolic content from mono-substrate solutions (more than 70% of each initial phenolic concentration) and of either OMW samples or EC1 and EC2 extracts. For instance, 60% of the total phenolic content of EC1 was removed after 48-h treatment with 5 mg mL(-1) birnessite and the efficiency was lower as greater was the complexity of the OMW sample (only 17% removal from EC2 over the same time span). Phytotoxicity tests with Lepidium sativum and Lycopersicon esculentum seeds and antibacterial toxicity tests with Bacillus megaterium were performed on crude OMW samples and their extract and exhausted fractions before and after the catalytic treatment. Results demonstrated that (a) monomeric phenols were certainly but not exclusively responsible of OMW phytotoxicity, whereas their removal led to a quite complete elimination of the toxicity toward bacterial growth; (b) other components not removable by the oxidative catalysts very likely contribute to OMW phytotoxicity; and (c) the choice of the vegetal species to use in toxicity tests might be crucial for correct and easily interpretable results. Overall the results provided useful information on the possible use of oxidative catalysts for the efficient treatment of complex aqueous wastes such as those deriving from olive industry.     

Adsorption of phenolic compounds by activated carbon--a critical review

Adsorption of phenol and its derivatives on activated carbons is considered based on numerous papers related to this issue. Special attention is paid to the effects of carbon surface functionalities, pH of solution and heterogeneity effects that accompany adsorption of phenolic compounds. Moreover, in this paper the most important aspects are overviewed referring to irreversible adsorption of phenols and impact of different substituents of phenolic compounds on their uptake by activated carbons is considered. Finally, some remarks pertaining to applications of novel adsorbents for phenol adsorption are discussed and illustrated by means of a few examples.     

沸石负载Fe_3O_4光催化氧化去除水中苯酚

为了对水中苯酚的去除进行研究,通过离子交换法及液相沉积法在天然沸石上负载Fe3O4制备出一种具有较高反应活性的复合催化剂,采用X-射线衍射仪(XRD)、扫描电镜(SEM)等仪器对其结构和形貌进行表征,并利用复合催化剂进行非均相UV/Fenton反应处理模拟苯酚废水,考察不同因素对苯酚降解效果的影响。实验结果表明,在催化剂投加量为0.4 g/L,H2O2投加量为二分之一理论投加量,pH为3~10且室温的条件下,处理100 mg/L的模拟苯酚废水,60 min之内苯酚去除率可达90%以上。通过对催化剂的稳定性研究,发现经5次循环使用后,苯酚去除率均可保持在90%以上,具有良好的循环使用性能。     

Formation of chlorinated phenols, dibenzo-p-dioxins, dibenzofurans, benzenes, benzoquinnones and perchloroethylenes from phenols in oxidative and copper (II) chloride-catalyzed thermal process

Formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and chlorinated phenols on CuCl(2) from unsubstituted phenol and three monochlorophenols was studied in a flow reactor over a temperature range of 100-425 degrees C. Heated nitrogen gas streams containing 8.0% oxygen were used as carrier gas. The 0.00024mol of unsubstituted phenol and 0.00039mol of each monochlorophenol were passed through a 1g and 1cm SiO(2) particle containing 0.5% (Cu by mass) CuCl(2). Chlorination preferentially occurred on ortho-(2, 6) and para-(4) positions. Chlorination increased up to 200 degrees C, and thereafter decreased as temperature increased. Chlorination of phenols plays an important role in the formation of the more chlorinated PCDD/Fs. Chlorinated benzenes are formed possibly from both chlorination of benzene and chlorodehydroxylation of phenols. Chlorinated phenols with ortho chlorine formed PCDD products, and major PCDD products were produced via loss of one chlorine. For PCDF formation, at least one unchlorinated ortho carbon was required.     

Metal-mediated chlorinated dibenzo-p-dioxin (CDD) and dibenzofuran (CDF) formation from phenols

Heterogeneous formation of chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) on CuCl2 from three phenols without ortho chlorine and one phenol with two ortho chlorines was studied in a flow reactor over a temperature range of 325-450 degrees C. Heated nitrogen gas streams containing 8% oxygen, 1.5% benzene vapor, and equal amounts of phenol, 3-chlorophenol, 3,4-dichlorophenol and 2,4,6-trichlorophenol vapor (700 ppmv, each) were passed through a 1 g particle bed of silica and 0.5% (Cu mass) CuCl2. Maximum product yields of greater than 1.4% phenol conversion to CDD and 5.7% phenol conversion to CDF were observed between 400 and 450 degrees C. CDDs formed with loss of one chlorine atom were favored. While total CDD/F yield varied with temperature, CDD/F homologue and isomer distributions did not vary significantly with temperature. Based on the results of experiments with single phenol precursors, phenol precursors could be assigned to all PCDD/F products. Of the chlorinated phenols without ortho chlorine that were studied, 3,4-dichlorophenol was found to have the greatest propensity to form CDFs.     

Treatment of coking wastewater by an advanced Fenton oxidation process using iron powder and hydrogen peroxide

In this study the treatment of coking wastewater was investigated by an advanced Fenton oxidation process using iron powder and hydrogen peroxide. Particular attention was paid to the effect of initial pH, dosage of H₂O₂ and to improvement in biodegradation. The results showed that higher COD and total phenol removal rates were achieved with a decrease in initial pH and an increase in H₂O₂ dosage. At an initial pH of less than 6.5 and H₂O₂ concentration of 0.3 M, COD removal reached 44-50% and approximately 95% of total phenol removal was achieved at a reaction time of 1 h. The oxygen uptake rate of the effluent measured at a reaction time of 1 h increased by approximately 65% compared to that of the raw coking wastewater. This indicated that biodegradation of the coking wastewater was significantly improved. Several organic compounds, including bifuran, quinoline, resorcinol and benzofuranol were removed completely as determined by GC-MS analysis. The advanced Fenton oxidation process is an effective pretreatment method for the removal of organic pollutants from coking wastewater. This process increases biodegradation, and may be combined with a classical biological process to achieve effluent of high quality.