Mallavarapu Megharaj

Bioremediation approaches for organic pollutants: A critical perspective

Due to human activities to a greater extent and natural processes to some extent, a large number of organic chemical substances such as petroleum hydrocarbons, halogenated and nitroaromatic compounds, phthalate esters, solvents and pesticides pollute the soil and aquatic environments. Remediation of these polluted sites following the conventional engineering approaches based on physicochemical methods is both technically and economically challenging. Bioremediation that involves the capabilities of microorganisms in the removal of pollutants is the most promising, relatively efficient and cost-effective technology. However, the current bioremediation approaches suffer from a number of limitations which include the poor capabilities of microbial communities in the field, lesser bioavailability of contaminants on spatial and temporal scales, and absence of bench-mark values for efficacy testing of bioremediation for their widespread application in the field. The restoration of all natural functions of some polluted soils remains impractical and, hence, the application of the principle of function-directed remediation may be sufficient to minimize the risks of persistence and spreading of pollutants. This review selectively examines and provides a critical view on the knowledge gaps and limitations in field application strategies, approaches such as composting, electrobioremediation and microbe-assisted phytoremediation, and the use of probes and assays for monitoring and testing the efficacy of bioremediation of polluted sites.

BIOAVAILABILITY AND TOXICITY OF CADMIUM TO MICROORGANISMS AND THEIR ACTIVITIES IN SOIL: A REVIEW

Significant quantities of cadmium (Cd) have been added to the soils globally due to various anthropogenic activities, raising concerns for environmental health. Microorganisms play a unique role in the soil ecosystem, because of their contributions to soil fertility. Contrasting trends, reported on the toxic effects of heavy metals including Cd on soil microorganisms and their activities, are attributable to short-term studies often limited to a single soil type and conducted under controlled laboratory conditions. There is a paucity of reliable field data on Cd alone, since most field studies on Cd-microorganism interactions in soils are based on sewage sludge containing multimetals and organic substances. No single parameter can be used to generalize Cd toxicity and different parameters can provide contrasting results. A battery of relevant tests, rather than just one single assay, involving important microbial activities should therefore be included in ecotoxicity studies. The bioavailability of Cd and associated toxicity to soil biota vary with time, soil type, speciation, ageing, Cd-source, organisms and the environmental factors. The available fraction or soil solution Cd, and not the total concentration of Cd, seems to correlate well with the toxicity parameters.

Toxicity of Hexavalent Chromium and Its Reduction by Bacteria Isolated from Soil Contaminated with Tannery Waste

An Arthrobacter sp. and a Bacillus sp., isolated from a long-term tannery waste contaminated soil, were examined for their tolerance to hexavalent chromium [Cr(VI)] and their ability to reduce Cr(VI) to Cr(III), a detoxification process in cell suspensions and cell extracts. Both bacteria tolerated Cr(VI) at 100 mg/ml on a minimal salts agar medium supplemented with 0.5% glucose, but only Arthrobacter could grow in liquid medium at this concentration. Arthrobacter sp. could reduce Cr(VI) up to 50 μg/ml, while Bacillus sp. was not able to reduce Cr(VI) beyond 20 μg/ml. Arthrobacter sp. was distinctly superior to the Bacillus sp. in terms of their Cr(VI)-reducing ability and resistance to Cr(VI). Assays with permeabilized (treated with toluene or Triton X 100) cells and crude extracts demonstrated that the Cr(VI) reduction was mainly associated with the soluble protein fraction of the cell. Arthrobacter sp. has a great potential for bioremediation of Cr(VI)-containing waste.

Kaolinite-supported nanoscale zero-valent iron for removal of Pb2+ from aqueous solution: Reactivity, characterization and mechanism

The use of nanoscale zero-valent iron (nZVI) to remediate contaminated groundwater is limited due to its lack of durability and mechanical strength. To address this issue, 20% (w/w) nZVI was loaded onto kaolinite as a support material (K-nZVI). More than 96% of Pb(2+) was removed from aqueous solution using K-nZVI at an initial condition of 500 mg/L Pb(2+) within 30 min under the conditions of 10 g/L of K-nZVI, pH 5.10 and a temperature of 30 °C. To understand the mechanism of removal of Pb(2+), various techniques were implemented to characterize K-nZVI. Scanning electron microscopy (SEM) indicated that K-nZVI had a suitable dispersive state with a lower aggregation, where the mean specific surface area and average particle size as determined by the BET-N(2) method and X-ray diffraction (XRD), were 26.11 m(2)/g and 44.3 nm, respectively. The results obtained from XRD, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) indicated that a small number of iron oxides formed on the surface of K-nZVI, suggesting that free Pb(2+) was adsorbed onto K-nZVI and subsequently reduced to Pb(0).

Removal of methyl orange from aqueous solution using bentonite-supported nanoscale zero-valent iron.

Zero-valent iron (ZVI) nanoparticles tend to agglomerate, resulting in a significant loss in reactivity. To address this issue, synthesized bentonite-supported nanoscale zero-valent iron (B-nZVI) was used to remove azo dye methyl orange (MO) in aqueous solution. Batch experiments show that various parameters, such as pH, initial concentration of MO, dosage, and temperature, were affected by the removal of MO. Scanning electron microscopy (SEM) confirmed that B-nZVI increased their reactivity and a decrease occurred in the aggregation of iron nanoparticles for the presence of bentonite (B). Using B-nZVI, 79.46% of MO was removed, whereas only 40.03% when using nZVI after reacting for 10 min with an initial MO concentration of 100 mg/L (pH=6.5). Furthermore, after B-nZVI reacted to MO, XRD indicated that iron oxides were formed. FTIR showed that no new bands appeared, and UV-vis demonstrated that the absorption peak of MO was degraded. Kinetics studies showed that the degradation of MO fitted well to the pseudo first-order model. A degradation mechanism is proposed, including the following: oxidation of iron, adsorption of MO to B-nZVI, formation of Fe(II)-dye complex, and cleavage of azo bond. Finally, the removal rate of MO from actual wastewater was 99.75% when utilizing B-nZVI.

Consortia of cyanobacteria/microalgae and bacteria: Biotechnological potential

Microbial metabolites are of huge biotechnological potential and their production can be coupled with detoxification of environmental pollutants and wastewater treatment mediated by the versatile microorganisms. The consortia of cyanobacteria/microalgae and bacteria can be efficient in detoxification of organic and inorganic pollutants, and removal of nutrients from wastewaters, compared to the individual microorganisms. Cyanobacterial/algal photosynthesis provides oxygen, a key electron acceptor to the pollutant-degrading heterotrophic bacteria. In turn, bacteria support photoautotrophic growth of the partners by providing carbon dioxide and other stimulatory means. Competition for resources and cooperation for pollutant abatement between these two guilds of microorganisms will determine the success of consortium engineering while harnessing the biotechnological potential of the partners. Relative to the introduction of gene(s) in a single organism wherein the genes depend on the regulatory- and metabolic network for proper expression, microbial consortium engineering is easier and achievable. The currently available biotechnological tools such as metabolic profiling and functional genomics can aid in the consortium engineering. The present review examines the current status of research on the consortia, and emphasizes the construction of consortia with desired partners to serve a dual mission of pollutant removal and commercial production of microbial metabolites.

Illicit drugs and the environment — A review

Illicit drugs and their metabolites are the latest group of emerging pollutants. Determination of their concentration in environment (such as water bodies, soil, sediment, air) is an indirect tool to estimate the community level consumption of illicit drug and to evaluate potential ecotoxicological impacts from chronic low level exposure. They enter the wastewater network as unaltered drugs and/or their active metabolites by human excretion after illegal consumption or by accidental or deliberate disposal from clandestine drug laboratories. This article critically reviews the occurrence and concentration levels of illicit drugs and their metabolites in different environmental compartments (e.g., wastewater, surface waters, groundwater, drinking water, and ambient air) and their potential impact on the ecosystem. There is limited published information available on the presence of illicit drugs in the environment, reports are available mainly from European countries, UK, USA, and Canada but there is a lack of information from the remainder of the world. Although the environmental concentrations are not very high, they can potentially impact the human health and ecosystem functioning. Cocaine, morphine, amphetamine, and MDMA have potent pharmacological activities and their presence as complex mixtures in water may cause adverse effect on aquatic organisms and human health. However, there is no current regulation demanding the determination of occurrence of these emerging pollutants in treated wastewater, surface water, drinking water, or atmosphere. Thus, critical investigation on distribution pattern of this new group of emerging contaminant and their potential harmful impact on our environment needs immediate attention.

Green synthesis of Fe nanoparticles using eucalyptus leaf extracts for treatment of eutrophic wastewater

Iron nanoparticles were firstly synthesized through a one-step room-temperature biosynthetic route using eucalyptus leaf extracts (EL-Fe NPs). Scanning electron microscopy (SEM) and X-ray energy-dispersive spectrometer (EDS) confirmed the successful synthesis of the spheroidal iron nanoparticles. Furthermore, X-ray diffraction (XRD) and Fourier Transform Infrared spectrometer (FTIR) indicated that some polyphenols are bound to the surfaces of EL-Fe NPs as a capping/stabilizing agent. Reactivity of EL-Fe NPs was evaluated for the treatment of swine wastewater and results indicated that 71.7% of total N and 84.5% of COD were removed, respectively. This demonstrated the tremendous potential of EL-Fe NPs for in situ remediation of eutrophic wastewater.

Chemistry of chromium in soils with emphasis on tannery waste sites

Worldwide chromium contamination of soils has arisen predominantly from the common practice of land-based disposal of tannery wastes under the assumption that the dominant species in the tannery waste would be the thermodynamically stable Cr(III) species. However, significant levels of toxic Cr(VI) recently detected in surface water and groundwater in India, China, Australia, and elsewhere raise critical questions relating to current disposal criteria for Cr-containing wastes. It now appears that despite the thermodynamic stability of Cr(III), the presence of certain naturally occurring minerals, especially Mn oxides, can enhance oxidation of Cr(III) to Cr(VI) in the soil environment. This factor is of public concern because at high pH, Cr(VI) is bioavailable, and it is this form that is highly mobile and therefore poses the greatest risk of groundwater contamination. A review of the current literature indicates that extensive research has been performed on the speciation of Cr in soil, the effect of pH on soil solution concentrations of Cr(III) and Cr(VI), soil adsorption phenomenon of Cr species, redox reactions, and transformation of Cr(II) and Cr(VI) together with remediation strategies to decontaminate Cr-contaminated soils. Most of the studies were conducted using an uncontaminated soil artificially spiked with Cr, and very limited research has been conducted in the contaminated soil environment. Furthermore, studies on tannery waste contaminated soils are limited, and obviously a serious gap of knowledge exists in understanding the influence of long-term tannery waste contamination on Cr behavior in soil.

Heterogeneous Fenton-like oxidation of monochlorobenzene using green synthesis of iron nanoparticles

Iron nanoparticles (Fe NPs) were synthesized using tea extracts as a catalyst for the Fenton-like oxidation of monochlorobenzene (MCB), where 69%, 53%, and 39% of MCB were, respectively, degraded by Fe NPs synthesized using green tea extracts, oolong tea extracts, and black tea extracts. Fe NPs synthesized using green tea extracts (GT-Fe NPs) demonstrated the best degradation since green tea contains a high concentration of caffeine/polyphenols used as both reducing and capping agents in the synthesis of Fe NPs. This was confirmed by SEM image, EDS, and XRD pattern of GT-Fe NPs. In addition, batch experiments show that the oxidation of MCB and the removal of chemical oxygen demand (COD) using GT-Fe NPs were 81% and 31%, respectively, at optimal conditions, where dosages were 0.6g/L GT-Fe NPs, 0.045 mol/L H2O2, and initial pH of 3.0. Compared to homogeneous Fenton oxidation of MCB, GT-Fe NPs as a heterogeneous catalyst indicate that Fe(2+) and Fe(3+) leached from GT-Fe NPs nanoparticles and consequently reduced the formation of iron sludge. Finally, GT-Fe NPs were successful in removing MCB from wastewaters, and the possible Fenton-like oxidative mechanism of MCB was proposed. The proposition was based on adsorption of MCB on the surface of GT-Fe NPs, decomposition of H2O2, generation of hydroxyl radicals, and oxidation of MCB.