Decolourization of Industrial Effluents – Available Methods and Emerging Technologies – A Review

Water pollution control is presently one of the major thrust areas of scientific research. While coloured organic compounds generally impart only a minor fraction of the organic load to wastewaters, their colour renders them aesthetically unacceptable. Stringent regulating measures are coaxing industries to treat their waste effluents to increasingly high standards. Colour removal, in particular, has recently become an area of major scientific interest as indicated by the multitude of related research reports. During the past two decades, several decolourization techniques have been reported, few of which have been accepted by some industries. There is a need to find alternative treatments that are effective in removing dyes and colourants from large volume of effluents, which are cost-effective, like the biological or integrated systems. This article reviews some of the widely used and most promising industrial wastewater decolourization methods. Data on decolourizing efficiencies of different causative agents, obtained by means of different physical, chemical and biological methods are discussed. Further a critical review is made on the various treatment methodologies and emerging technologies with a note on their advantages and disadvantages.     

Dye removal by immobilised fungi

Dyes are widely used within the food, pharmaceutical, cosmetic, printing, textile and leather industries. This has resulted in the discharge of highly coloured effluents that affect water transparency and gas solubility in water bodies. Furthermore, they pose a problem because of their carcinogenicity and toxicity. Therefore, removal of such dyes before discharging them into natural water streams is essential. For this, appropriate treatment technologies are required. The treatment of recalcitrant and toxic dyes with traditional technologies is not always effective or may not be environmentally friendly. This has impelled the search for alternative technologies such as biodegradation with fungi. In particular, ligninolytic fungi and their non-specific oxidative enzymes have been reported to be responsible for the decolouration of different synthetic dyes. Thus, the use of such fungi is becoming a promising alternative to replace or complement the current technologies for dye removal. Processes using immobilised growing cells seem to be more promising than those with free cells, since the immobilisation allows using the microbial cells repeatedly and continuously. This paper reviews the application of fungal immobilisation to dye removal.     

Advanced oxidation process and biological treatments for table olive processing wastewaters: constraints and a novel approach to integrated recycling process: a review

Table olive processing wastewaters constitute a dangerous environmental problem in the Mediterranean countries because of their large volumes, high organic matter and salt concentration. The quantity and the characteristics of wastewaters produced, and thus, their environmental impact, varied depending on the season, varieties, soil and process employed. Several chemicals, biological and combined technologies have proven effective at bringing down organic pollution and toxicity of these effluents. Advanced oxidation processes have recognized as highly efficient treatments for the degradation of organic matter. Nonetheless, complete mineralization is generally expensive without salt removal. Biological processes are the most environmentally compatible and least-expensive treatment methods, but these operations do not always provide satisfactory results. This article surveys the current available technologies and suggests an effective, cheaper alternative for the recycling and the valorization of green table olives wastewaters.     

Azo dyes degradation by microorganisms – An efficient and sustainable approach

Synthetic aromatic compounds consisting of various functional groups are known as dyes. These colored compounds are often discharged in effluents, and they are very dangerous to aquatic life. Basically, the dye industry started by using natural plant and insect sources, and then suddenly turned into artificial manufacturing. Natural equilibrium of our environment gets changed by the reduction in photosynthetic activity due to the dyes. In China 900,000 tons of all kinds of dyes are usually produced, which are used in many industries like food, textile, food, paper and leather. Untreated wastewater contaminates aquatic bodies by causing eutrophication, change in water color, oxygen depletion which affect aquatic organisms to a great extent. Dye wastewater is now the key environmental pollution form. In recent eras an extensive study line has been developed to explore the dye decolorization and biodegradation under both aerobic as well as anaerobic conditions. In this review, the chemistry, toxicity and microbial biodegradation/decolorization are presented. Some recent studies along with the new techniques and methodologies of remediating the dye pollution are also discussed to provide the bases of their handling. Overall, efficient and high biodegradation potential make microbes an impending foundation for green chemistry to eradicate toxic dyes from industrial wastewater.     

Decolorization of Synthetic Dyes by Aspergillus flavus

A problem of paramount importance that has attracted the attention of environmental biologists is the discharge of highly colored effluents into the environment by various industries, which use a wide range of synthetic dyes. The existing chemical methods for dye degradation are not only expensive but also contributes to secondary pollution due to high dose of the chemicals used. Hence an alternative is to exploit the potential of microorganisms to alleviate this problem. The current paper deals with the isolation, characterization, and sugar utilization for better growth of Aspergillus flavus, a marine fungus from the Bay of Bengal. The goal is to assess the bioremediation potential of a variety of synthetic, paper mill, and color photography dyes. A correlation between the amount of sugar used, biomass, and quality of protein produced was observed. This fungus is capable of reducing between 80% and 90% of synthetic dyes and 100% color photography effluents within 3 to 7 days, and 8 days, respectively. Significant effect of carbon sources was observed in the decolorization of the synthetic dye crystal violet, up to 90% in 3 to 7 days, by Aspergillus flavus. The organism showed better growth with fructose as the sole carbon source for the least sugar consumption. Therefore, this fungus can be used as an economical and eco-friendly tool to minimize the pollution by industries to a significant extent.     

Toxicity assessment and microbial degradation of azo dyes

Toxic effluents containing azo dyes are discharged from various industries and they adversely affect water resources, soil fertility, aquatic organisms and ecosystem integrity. They pose toxicity (lethal effect, genotoxicity, mutagenicity and carcinogenicity) to aquatic organisms (fish, algae, bacteria, etc.) as well as animals. They are not readily degradable under natural conditions and are typically not removed from waste water by conventional waste water treatment systems. Benzidine based dyes have long been recognized as a human urinary bladder carcinogen and tumorigenic in a variety of laboratory animals. Several microorganisms have been found to decolourize, transform and even to completely mineralize azo dyes. A mixed culture of two Pseudomonas strains efficiently degraded mixture of 3-chlorobenzoate (3-CBA) and phenol/cresols. Azoreductases of different microorganisms are useful for the development of biodegradation systems as they catalyze reductive cleavage of azo groups (-N=N-) under mild conditions. In this review, toxic impacts of dyeing factory effluents on plants, fishes, and environment, and plausible bioremediation strategies for removal of azo dyes have been discussed.     

Integrated treatment of farm effluents in New Zealand’s dairy operations

Maintaining growth through intensification in the New Zealand dairy industry is a challenge for various reasons, in particular sustainably managing the large volumes of effluent. Dairy farm effluents have traditionally been treated using two-pond systems that are effective in the removal of carbon and suspended solids, however limited in their ability to remove nutrients. In the past these nutrient-rich two-pond treated effluents were disposed of in surface waters. Current environmental concerns associated with the direct discharge of these effluents to surface waters has prompted in developing technologies to either minimise the nutrient content of the effluent or apply effluents to land. Here, we discuss various approaches and methods of treatment that enable producers to sustainably manage farm effluents, including advanced pond treatment systems, stripping techniques to reduce nutrient concentration, land application strategies involving nutrient budgeting models to minimise environmental degradation and enhance fodder quality. We also discuss alternative uses of farm effluents to produce energy and animal feed.     

Reduction of azo dyes by anaerobic bacteria: microbiological and biochemical aspects

Azo dyes are recalcitrant pollutants commonly found in several industrial wastewaters, such as those originated from textile factories, which generally persist to biological transformation. Discharge of these effluents in open water bodies not only represents an aesthetic problem, but also may limit photosynthesis in aquatic plants. Furthermore, many azo dyes and products derived from their partial transformation in the environment (e.g. aromatic amines) may be toxic or carcinogenic. Biological wastewater treatment processes have emerged as promising technologies to remove azo dyes from industrial effluents and intensive research has been conducted during the last two decades in order to elucidate the mechanisms involved in the reductive decolourisation of azo dyes. The present work describes the main biochemical and microbiological aspects involved in the reductive decolourisation of azo dyes by anaerobic bacteria.     

Peroxidase mediated decolorization and remediation of wastewater containing industrial dyes: a review

In this article an effort has been made to review literature based on the role of peroxidases in the treatment and decolorization of a wide spectrum aromatic dyes from polluted water. Peroxidases can catalyze degradation/transformation of aromatic dyes either by precipitation or by opening the aromatic ring structure. Peroxidases from plant sources; horseradish, turnip, tomato, soybean, bitter gourd, white radish and Saccharum uvarum and microbial sources; lignin peroxidases, manganese peroxidases, vanadium haloperoxidases, versatile peroxidases, dye decolorizing peroxidases have been employed for the remediation of commercial dyes. Soluble and immobilized peroxidases have been successfully exploited in batch as well as in continuous processes for the treatment of synthetic dyes with complex aromatic molecular structures present in industrial effluents at large scale. However, recalcitrant dyes were also decolorized by the action of peroxidases in the presence of redox mediators.     

Chromium removal from a real tanning effluent by autochthonous and allochthonous fungi

Heavy metals represent an important ecological and health hazard due to their toxic effects and their accumulation throughout the food chain. Conventional techniques commonly applied to recover chromium from tanning wastewaters have several disadvantages whereas biosorption has good metal removal performance from large volume of effluents. To date most studies about chromium biosorption have been performed on simulated effluents bypassing the problems due to organic or inorganic ligands present in real industrial wastewaters that may sequestrate the Cr(III) ions. In the present study a tanning effluent was characterized from a mycological point of view and different fungal biomasses were tested for the removal of Cr(III) from the same tanning effluent in which, after the conventional treatments, Cr(III) amount was very low but not enough to guarantee the good quality of the receptor water river. The experiments gave rise to promising results with a percentage of removed Cr(III) up to 40%. Moreover, to elucidate the mechanisms involved in biosorption process, the same biomasses were tested for Cr(III) removal from synthetic aqueous solutions at different Cr(III) concentrations.     

Significance of exploiting non-living biomaterials for the biosorption of wastewater pollutants

Industrial effluents from various sectors have become a matter of major environmental concern. The treatment of wastewater in recent year plays a significant role in order to remove the pollutants and to safeguard the water resource. The conventional wastewater treatment is considered costlier and associated with problem of sludge generation. Biosorption methods are considered as the potential solution due to their economical efficiency, good adsorption capacity and eco-friendliness. In this review, an extensive list of biosorbents from algae, bacteria, fungi and agricultural byproducts have been compiled. The suitability of biosorbents towards the eradication of heavy metals, textile dyes and phenolic compounds were highlighted. It is evident from the literature survey of recently published research articles that the biosorbents have demonstrated outstanding removal potential towards the wastewater pollutants. Therefore, biosorbents from the source of dead microbial and agricultural byproduct can be viable alternatives to activated carbon for the wastewater treatment.     

Removal of Heavy Metals from the Environment by Biosorption

The pollution of the environment with toxic metals is a result of many human activities, such as mining and metallurgy, and the effects of these metals on the ecosystems are of large economic and public‐healthsignificance. This paper presents the features and advantages of the unconventional removal method of heavy metals – biosorption – as a part of bioremediation. Bioremediation consists of a group of applications, which involvethe detoxification of hazardous substances instead of transferring them from one medium to another, by means of microbes and plants. This process is characterized as less disruptive and can be often carried out on site, eliminating the need to transport the toxic materials to treatment sites. The biosorption (sorption of metallic ions from solutions by live or dried biomass) offers an alternative to the remediation of industrial effluents as well as the recovery of metals contained in other media. Biosorbents are prepared from naturally abundant and/or waste biomass. Due to the high uptake capacity and very cost‐effective source of the raw material, biosorption is a progression towards a perspective method. The mechanism by which microorganisms take up metals is relatively unclear, but it has been demonstrated that both living and non‐living biomass may be utilized in biosorptive processes, as they often exhibit a marked tolerance towards metals and other adverse conditions. One of their major advantages is the treatment of large volumes of effluents with low concentrations of pollutants. Models developed were presented to determine both the number of adsorption sites required to bind each metal ion and the rate of adsorption, using a batch reactor mass balance and the Langmuir theory of adsorption to surfaces or continuous dynamic systems. Two main categories of bioreactors used in bioremediation – suspended growth and fixed film bioreactors – are discussed. Reactors with varying configurations to meet the different requirements for biosorption are analyzed considering two major groups of reactors – batch reactors and continuous reactors. Biosorption is treated as an emerging technology effective in removing even very low levels of heavy metal.     

Potential applications of the oxidoreductive enzymes in the decolorization and detoxification of textile and other synthetic dyes from polluted water: a review

Recently, the enzymatic approach has attracted much interest in the decolorization/degradation of textile and other industrially important dyes from wastewater as an alternative strategy to conventional chemical, physical and biological treatments, which pose serious limitations. Enzymatic treatment is very useful due to the action of enzymes on pollutants even when they are present in very dilute solutions and recalcitrant to the action of various microbes participating in the degradation of dyes. The potential of the enzymes (peroxidases, manganese peroxidases, lignin peroxidases, laccases, microperoxidase-11, polyphenol oxidases, and azoreductases) has been exploited in the decolorization and degradation of dyes. Some of the recalcitrant dyes were not degraded/decolorized in the presence of such enzymes. The addition of certain redox mediators enhanced the range of substrates and efficiency of degradation of the recalcitrant compounds. Several redox mediators have been reported in the literature, but very few of them are frequently used (e.g., 1-hydroxybenzotriazole, veratryl alcohol, violuric acid, 2-methoxy-phenothiazone). Soluble enzymes cannot be exploited at the large scale due to limitations such as stability and reusability. Therefore, the use of immobilized enzymes has significant advantages over soluble enzymes. In the near future, technology based on the enzymatic treatment of dyes present in the industrial effluents/wastewater will play a vital role. Treatment of wastewater on a large scale will also be possible by using reactors containing immobilized enzymes.     

Potential of fruit and vegetable wastes as novel biosorbents: summarizing the recent studies

Fruit and vegetable wastes produced in astronomical quantities from food processing and agriculture industries often cause nuisance in municipal landfills owing to their high biodegradability. Biosorption by these waste-based adsorbents can be used as a cost effective and efficient technique for the removal of toxic heavy metals and dyes from wastewater. Recently, many papers claiming the feasible use of these biosorbents for water decontamination, treatment of industrial and agricultural wastewater and valuable metal recovery have been published. The organic waste-based adsorbents, characterized by good uptake capacity and rapid kinetics are expected to be economically and ecologically viable. This paper presents a judicious and pragmatic review depicting the key advances in implications of the fruit and vegetable wastes in pollution mitigation, the underlying mechanisms, major challenges and the future implementations. This compilation is expected to provide an impetus to the bioremediation research and promote green technology.     

Adsorption of metal complex dyes from aqueous solutions by pine sawdust

An attempt to alleviate the problem caused by the presence of metal complex dyes, mostly used in textile industries, in the textile effluents was undertaken. The effects of adsorbent particle size, pH, adsorbent dose, contact time and initial dye concentrations on the adsorption of metal complex dyes by pine sawdust was investigated. Acidic pH was favorable for the adsorption of metal complex dyes. A contact time of 120 min was required to reach the equilibrium. The experimental isotherm data were analyzed using the Langmuir, Freundlich and Temkin equations. The equilibrium data fit well the Langmuir isotherm. The monolayer adsorption capacities are 280.3 and 398.8 mg dye per g of pine sawdust for Metal Complex Blue and Metal Complex Yellow, respectively. The results indicate that pine sawdust could be employed as low-cost alternative to commercial activated carbon in aqueous solution for the removal of metal complex dyes.     

MOLECULARLY IMPRINTED POLYMERS FOR SOME REACTIVE DYES

Depending upon their structure, azo- and anthraquinonic dyes are the two major classes and together represent 90% of all organic colorants. Adsorption of dye molecules onto a sorbent can be an effective, low-cost method of color removal. Most of the techniques used for removal of dyes are of high production cost, and the regeneration also makes them uneconomical. There is much interest in the development of cheaper and effective newer materials for use as adsorbents. Molecular imprinting is a new kind of materials that can be alternative adsorbents. In this study, molecularly imprinted polymers of three textile dyes (Cibacron Orange P-4R, Cibacron Red P-4B, Cibacron Black PSG) were prepared. Methacrylic acid was used as a monomer for red and orange dyes and acrylamide was used for black dye. Methanol:acetonitrile was used as a porogen. The selective recognition ability of the molecularly imprinted polymers was studied by an equilibrium–adsorption batch method. The adsorption data are for Cibacron Black PSG 65% and nonimprinted polymer (NIP) 25%; Cibacron Red P-4B 72% and NIP 18%; and Cibacron Orange P-4R 45% and NIP 10%, respectively. Dye-imprinted polymers were used as a solid-phase extraction material for selective adsorption from wastewater of textile factory.     

Molecularly imprinted polymers for some reactive dyes

Depending upon their structure, azo- and anthraquinonic dyes are the two major classes and together represent 90% of all organic colorants. Adsorption of dye molecules onto a sorbent can be an effective, low-cost method of color removal. Most of the techniques used for removal of dyes are of high production cost, and the regeneration also makes them uneconomical. There is much interest in the development of cheaper and effective newer materials for use as adsorbents. Molecular imprinting is a new kind of materials that can be alternative adsorbents. In this study, molecularly imprinted polymers of three textile dyes (Cibacron Orange P-4R, Cibacron Red P-4B, Cibacron Black PSG) were prepared. Methacrylic acid was used as a monomer for red and orange dyes and acrylamide was used for black dye. Methanol:acetonitrile was used as a porogen. The selective recognition ability of the molecularly imprinted polymers was studied by an equilibrium-adsorption batch method. The adsorption data are for Cibacron Black PSG 65% and nonimprinted polymer (NIP) 25%; Cibacron Red P-4B 72% and NIP 18%; and Cibacron Orange P-4R 45% and NIP 10%, respectively. Dye-imprinted polymers were used as a solid-phase extraction material for selective adsorption from wastewater of textile factory.     

Decolorization and detoxification of textile dyes with a laccase from Trametes hirsuta

Trametes hirsuta and a purified laccase from this organism were able to degrade triarylmethane, indigoid, azo, and anthraquinonic dyes. Initial decolorization velocities depended on the substituents on the phenolic rings of the dyes. Immobilization of the T. hirsuta laccase on alumina enhanced the thermal stabilities of the enzyme and its tolerance against some enzyme inhibitors, such as halides, copper chelators, and dyeing additives. The laccase lost 50% of its activity at 50 mM NaCl while the 50% inhibitory concentration (IC(50)) of the immobilized enzyme was 85 mM. Treatment of dyes with the immobilized laccase reduced their toxicities (based on the oxygen consumption rate of Pseudomonas putida) by up to 80% (anthraquinonic dyes). Textile effluents decolorized with T. hirsuta or the laccase were used for dyeing. Metabolites and/or enzyme protein strongly interacted with the dyeing process indicated by lower staining levels (K/S) values than obtained with a blank using water. However, when the effluents were decolorized with immobilized laccase, they could be used for dyeing and acceptable color differences (DeltaE*) below 1.1 were measured for most dyes.     

Non-conventional low-cost adsorbents for dye removal: a review

Adsorption techniques are widely used to remove certain classes of pollutants from waters, especially those that are not easily biodegradable. Dyes represent one of the problematic groups. Currently, a combination of biological treatment and adsorption on activated carbon is becoming more common for removal of dyes from wastewater. Although commercial activated carbon is a preferred sorbent for color removal, its widespread use is restricted due to high cost. As such, alternative non-conventional sorbents have been investigated. It is well-known that natural materials, waste materials from industry and agriculture and biosorbents can be obtained and employed as inexpensive sorbents. In this review, an extensive list of sorbent literature has been compiled. The review (i) presents a critical analysis of these materials; (ii) describes their characteristics, advantages and limitations; and (iii) discusses various mechanisms involved. It is evident from a literature survey of about 210 recent papers that low-cost sorbents have demonstrated outstanding removal capabilities for certain dyes. In particular, chitosan might be a promising adsorbent for environmental and purification purposes.     

Heavy metal pollution in aquatic ecosystems and its phytoremediation using wetland plants: an ecosustainable approach

This review addresses the global problem of heavymetal pollution originating from increased industrialization and urbanization and its amelioration by using wetland plants both in a microcosm as well as natural/field condition. Heavymetal contamination in aquatic ecosystems due to discharge of industrial effluents may pose a serious threat to human health. Alkaline precipitation, ion exchange columns, electrochemical removal, filtration, and membrane technologies are the currently available technologies for heavy metal removal. These conventional technologies are not economical and may produce adverse impacts on aquatic ecosystems. Phytoremediation of metals is a cost-effective "green" technology based on the use of specially selected metal-accumulating plants to remove toxic metals from soils and water. Wetland plants are important tools for heavy metal removal. The Ramsar convention, one of the earlier modern global conservation treaties, was adopted at Ramsar, Iran, in 1971 and became effective in 1975. This convention emphasized the wise use of wetlands and their resources. This review mentions salient features of wetland ecosystems, their vegetation component, and the pros and cons involved in heavy metal removal. Wetland plants are preferred over other bio-agents due to their low cost, frequent abundance in aquatic ecosystems, and easy handling. The extensive rhizosphere of wetland plants provides an enriched culture zone for the microbes involved in degradation. The wetland sediment zone provides reducing conditions that are conducive to the metal removal pathway. Constructed wetlands proved to be effective for the abatement of heavymetal pollution from acid mine drainage; landfill leachate; thermal power; and municipal, agricultural, refinery, and chlor-alkali effluent. the physicochemical properties of wetlands provide many positive attributes for remediating heavy metals. Typha, Phragmites, Eichhornia, Azolla, Lemna, and other aquatic macrophytes are some of the potent wetland plants for heavy metal removal. Biomass disposal problem and seasonal growth of aquatic macrophytes are some limitations in the transfer of phytoremediation technology from the laboratory to the field. However, the disposed biomass of macrophytes may be used for various fruitful applications. An ecosustainable model has been developed through the author's various works, which may ameliorate some of the limitations. The creation of more areas for phytoremediation may also aid in wetlands conservation. Genetic engineering and biodiversity prospecting of endangered wetland plants are important future prospects in this regard.