Virender K. Sharma

Silver nanoparticles : Green synthesis and their antimicrobial activities

This review presents an overview of silver nanoparticles (Ag NPs) preparation by green synthesis approaches that have advantages over conventional methods involving chemical agents associated with environmental toxicity. Green synthetic methods include mixed-valence polyoxometallates, polysaccharide, Tollens, irradiation, and biological. The mixed-valence polyoxometallates method was carried out in water, an environmentally-friendly solvent. Solutions of AgNO(3) containing glucose and starch in water gave starch-protected Ag NPs, which could be integrated into medical applications. Tollens process involves the reduction of Ag(NH(3))(2)(+) by saccharides forming Ag NP films with particle sizes from 50-200 nm, Ag hydrosols with particles in the order of 20-50 nm, and Ag colloid particles of different shapes. The reduction of Ag(NH(3))(2)(+) by HTAB (n-hexadecyltrimethylammonium bromide) gave Ag NPs of different morphologies: cubes, triangles, wires, and aligned wires. Ag NPs synthesis by irradiation of Ag(+) ions does not involve a reducing agent and is an appealing procedure. Eco-friendly bio-organisms in plant extracts contain proteins, which act as both reducing and capping agents forming stable and shape-controlled Ag NPs. The synthetic procedures of polymer-Ag and TiO(2)-Ag NPs are also given. Both Ag NPs and Ag NPs modified by surfactants or polymers showed high antimicrobial activity against gram-positive and gram-negative bacteria. The mechanism of the Ag NP bactericidal activity is discussed in terms of Ag NP interaction with the cell membranes of bacteria. Silver-containing filters are shown to have antibacterial properties in water and air purification. Finally, human and environmental implications of Ag NPs to the ecology of aquatic environment are briefly discussed.

Aquatic arsenic: Toxicity, speciation, transformations, and remediation

This paper reviews the current knowledge on the toxicity, speciation and biogeochemistry of arsenic in aquatic environmental systems. The toxicity of arsenic is highly dependent on the chemical speciation. The effects of pH, E(h), adsorbing surfaces, biological mediation, organic matter, and key inorganic substances such as sulfide and phosphate combine in a complex and interwoven dynamic fashion to produce unique assemblages of arsenic species. The number of different arsenic species found in environmental samples and an understanding of the transformations between arsenic species has increased over the past few decades as a result of new and refined analytical methods. Changes in arsenic speciation and in total arsenic content of foods upon processing have suggested possible risks associated with processed and unprocessed food. Arsenic removal from water using adsorbents, chemical oxidation, photolysis and photocatalytic oxidation techniques is also reviewed.

Potassium ferrate(VI): an environmentally friendly oxidant

Abstract The iron(VI) derivative, potassium ferrate(VI) (Fe(VI)) has properties such as high stability, oxidizing power, selectivity, and a non-toxic by-product Fe(III), that make potassium ferrate(VI) an environmentally friendly oxidant for natural waters. This paper presents a review of its properties and its role in environmental and industrial removal of contaminants. Fe(VI) is a powerful oxidizing agent throughout the entire pH range with a reduction potential varying from +2.2 V to +0.7 V in acidic and basic solutions, respectively. Fe(VI) ion reduces rapidly and exothermally to Fe(III) and oxygen in strong acids, while the oxygen ligands of Fe(VI) exchange very slowly with water at pH 10. In dilute solutions, the lowest rate of reduction of Fe(VI) by water occurs between pH 9.4 and 9.7. Fe(VI) is also a selective oxidant for a large number of organic compounds with Fe(III) as a by-product. Fe(VI) therefore has a role in cleaner (‘greener’) technology for organic synthesis. Other applications of Fe(VI) include production of ferrate(V) by pulse radiolysis, ‘super-iron’ batteries, and wastewater treatment processes. Many of the contaminants in wastewater can be removed by Fe(VI) in seconds to minutes with formation of non-hazardous products. Fe(VI) is also a disinfectant, antifoulant, and coagulant, and therefore a promising multi-purpose wastewater treatment chemical.

Humic Acid-Induced Silver Nanoparticle Formation Under Environmentally Relevant Conditions

The formation of silver nanoparticles (AgNPs) via reduction of silver ions (Ag(+)) in the presence of humic acids (HAs) under various environmentally relevant conditions is described. HAs tested originated from the Suwannee River (SUW), and included samples of three sedimentary HAs (SHAs), and five soils obtained across the state of Florida. The time required to form AgNPs varied depending upon the type and concentration of HA, as well as temperature. SUW and all three SHAs reduced Ag(+) at 22 °C. However, none of the soil HAs formed absorbance-detectable AgNPs at room temperature when allowed to react for a period of 25 days, at which time experiments were halted. The appearance of the characteristic surface plasmon resonance (SPR) of AgNPs was observed by ultraviolet-visible spectroscopy in as few as 2-4 days at 22 °C for SHAs and SUW. An elevated temperature of 90 °C resulted in the accelerated appearance of the SPR within 90 min for SUW and all SHAs. The formation of AgNPs at 90 °C was usually complete within 3 h. Transmission electron microscopy and atomic force microscopy images showed that the AgNPs formed were typically spherical and had a broad size distribution. Dynamic light scattering also revealed polydisperse particle size distributions. HAs appeared to colloidally stabilize AgNPs based on lack of any significant change in the spectral characteristics over a period of two months. The results suggest the potential for direct formation of AgNPs under environmental conditions from Ag(+) sources, implying that not all AgNPs observed in natural waters today may be of anthropogenic origin.

Aggregation and toxicity of titanium dioxide nanoparticles in aquatic environment—A Review

The use of nanoparticles—particles with size ∼1–100 nm is increasing worldwide. This is particularly the case for applications of titanium dioxide nanoparticles (nano-TiO2) in consumer products, which have expanded at a fast rate in the last decade. The properties of nano-TiO2 differ significantly from bulk-TiO2 of the same composition because of an increase in surface area. A release of nano-TiO2 from application sources to the aquatic environment may pose possible risks due to their bioavailability and toxicity. The aggregation of nano-TiO2 plays an important role in the environmental effects of nanoparticles because the size and shape of nanoparticles will determine the magnitude of any potentially toxic effect. Aggregation is affected by pH, ionic strength, and ionic identity (inorganic and organic) of aqueous suspensions and is reviewed in this paper. The current information on the evaluation of ecotoxicological hazards of nano-TiO2 to bacteria, algae, invertebrates, nematodes, and rainbow trout is also given.

Organic-coated silver nanoparticles in biological and environmental conditions: fate, stability and toxicity.

This review paper presents the overview of processes involved in transformation of organic-coated silver nanoparticles (AgNPs) in biological systems and in the aquatic environment. The coating on AgNPs greatly influences the fate, stability, and toxicity of AgNPs in aqueous solutions, biological systems, and the environment. Several organic-coated AgNP systems are discussed to understand their stability and toxicity in biological media and natural water. Examples are presented to demonstrate how a transformation of organic-coated AgNPs in an aqueous solution is affected by the type of coating, pH, kind of electrolyte (mono- or divalent), ionic strength, organic ligands (inorganic and organic), organic matter (fulvic and humic acids), redox conditions (oxic and anoxic), and light. Results of cytotoxicity, genotoxicity, and ecotoxicity of coated AgNPs to food chain members (plants, bacteria, and aquatic and terrestrial organisms) are reviewed. Key factors contributing to toxicity are the size, shape, surface coating, surface charge, and conditions of silver ion release. AgNPs may directly damage the cell membranes, disrupt ATP production and DNA replication, alternate gene expressions, release toxic Ag(+) ion, and produce reactive oxygen species to oxidize biological components of the cell. A progress made on understanding the mechanism of organic-coated AgNP toxicity using different analytical techniques is presented.

Oxidative transformations of environmental pharmaceuticals by Cl2, ClO2, O3, and Fe(VI): Kinetics assessment

Several pharmaceuticals have been detected globally in surface water and drinking water, which indicate their insufficient removal from water and wastewater using conventional treatment methods. This paper reviews the kinetics of oxidative transformations of pharmaceuticals (antibiotics, lipid regulators, antipyretics, anticonvulsants, and beta-blockers) by Cl(2), ClO(2), O(3), and ferrate(VI) (Fe(VI)O(4)(2-),Fe(VI)) under treatment conditions. In the chlorination of sulfonamide antibiotics, HOCl is the major reactive Cl(2) species whereas in the oxidation by Fe(VI), HFeO(4)(-) is the dominant reactive species. Both oxidation processes can oxidize sulfonamides in seconds at a neutral pH (t(1/2)≤ 220 s; 1 mg L(-1) HOCl or K(2)FeO(4)). The reactivity of O(3) with pharmaceuticals is generally higher than that of HOCl (k(app,pH 7) (O(3))=1-10(7)M(-1)s(-1); k(app,pH 7) (HOCl)=10(-2)-10(5)M(-1)s(-1)). Ozone selectively oxidizes pharmaceuticals and reacts mainly with activated aromatic systems and non-protonated amines. Oxidative transformation of most pharmaceuticals by O(3) occurs in seconds (t(1/2)≤ 100 s; 1 mg L(-1) O(3)) while half-lives for oxidations by HOCl differ by at least two orders of magnitude. Ozone appears to be efficient in oxidizing pharmaceuticals in aquatic environments. The limited work on Fe(VI) shows that it can also potentially transform pharmaceuticals in treatment processes.

Nonylphenol, octylphenol, and bisphenol-A in the aquatic environment: A review on occurrence, fate, and treatment

The aim of this study was to assess the performance of a method of analyzing pesticides in rice by using pressurized liquid extraction (PLE) and to perform a preliminary monitoring by using that method. The instrumental quantification limit, instrumental detection limit, method quantification limit, and method detection limit were determined. PLE temperature was also optimized for 6 target pesticides. Mean recoveries of spiked rice with target pesticides (4 ng/g and 40 ng/g) were 83%-109% with the repeatability of the analysis, represented as relative standard deviations, ranged from 1.3% to 11% (n = 5) for PLE at 130 degrees C. These results were satisfactory according to the method of positive list in Japan. In a preliminary analysis of 10 target pesticides in 54 commercial rice samples, ferimzone was detected in only one unpolished rice sample.This paper reviews the current knowledge on the occurrence, biodegradation, and photooxidation of nonylphenol (NP), octylphenol (OP), and bisphenol-A (BPA) in aquatic environment. Generally, the concentrations determined were 0.006–32.8, < 0.001–1.44, and 0.0005–4.0 μ g L−1 for NP, OP, and BPA respectively in river waters worldwide. Anthropogenic activities that can lead to run-off and storm water discharge may contribute to such concentrations in rivers. Pathways for biodegradation of NP and BPA appear to be similar. The influence of ferric ions, oxalate, hydrogen peroxide, and dissolved organic matter (DOM) on the photooxidation of NP and BPA in natural water is presented. Several techniques including nanofiltration, adsorption, sonochemical, photocatalytic, chlorination, ozonation, and ferrate(VI) oxidation for removals of NP, OP, and BPA are also reviewed.

Oxidation of inorganic contaminants by ferrates (VI, V, and IV)--kinetics and mechanisms: a review.

Inorganic contaminants are found in water, wastewaters, and industrial effluents and their oxidation using iron based oxidants is of great interest because such oxidants possess multi-functional properties and are environmentally benign. This review makes a critical assessment of the kinetics and mechanisms of oxidation reactions by ferrates (Fe(VI)O(4)(2-), Fe(V)O(4)(3-), and Fe(IV)). The rate constants (k, M(-1) s(-1)) for a series of inorganic compounds by ferrates are correlated with thermodynamic oxidation potentials. Correlations agree with the mechanisms of oxidation involving both one-electron and two-electron transfer processes to yield intermediates and products of the reactions. Case studies are presented which demonstrate that inorganic contaminants can be degraded in seconds to minutes by ferrate(VI) with the formation of non-toxic products.

Ferrates: greener oxidants with multimodal action in water treatment technologies.

CONSPECTUS: One of the biggest challenges for humanity in the 21st century is easy access to purified and potable water. The presence of pathogens and toxins in water causes more than two million deaths annually, mostly among children under the age of five. Identifying and deploying effective and sustainable water treatment technologies is critical to meet the urgent need for clean water globally. Among the various agents used in the purification and treatment of water, iron-based materials have garnered particular attention in view of their special attributes such as their earth-abundant and environmentally friendly nature. In recent years, higher-valent tetraoxy iron(VI) (Fe(VI)O4(2-), Fe(VI)), commonly termed, ferrate, is being explored for a broad portfolio of applications, including a greener oxidant in synthetic organic transformations, a water oxidation catalyst, and an efficient agent for abatement of pollutants in water. The use of Fe(VI) as an oxidant/disinfectant and further utilization of the ensuing iron(III) oxides/hydroxide as coagulants are other additional attributes of ferrate for water treatment. This multimodal action and environmentally benign character of Fe(VI) are key advantages over other commonly used oxidants (e.g., chlorine, chlorine dioxide, permanganate, hydrogen peroxide, and ozone). This Account discusses current state-of-the-art applications of Fe(VI) and the associated unique chemistry of these high-valence states of iron. The main focus centers around the description and salient properties of ferrate species involving various electron transfer and oxygen-atom transfer pathways in terms of presently accepted mechanisms. The mechanisms derive the number of electron equivalents per Fe(VI) (i.e., oxidation capacity) in treating various contaminants. The role of pH in the kinetics of the reactions and in determining the removal efficiency of pollutants is highlighted; the rates of competing reactions of Fe(VI) with itself, water, and the contaminants, which are highly pH dependent, determine the optimum pH range of maximum efficacy. The main emphasis of this account is placed on cases where various modes of ferrate action are utilized, including the treatment of nitrogen- and sulfur-containing waste products, antibiotics, viruses, bacteria, arsenic, and heavy metals. For example, the oxidative degradation of N- and S-bearing contaminants by Fe(VI) yields either Fe(II) or Fe(III) via the intermediacy of Fe(IV) and Fe(V) species, respectively (e.g., Fe(VI) → Fe(IV) → Fe(II) and Fe(VI) → Fe(V) → Fe(III)). Oxidative transformations of antibiotics such as trimethoprim by Fe(VI) generate products with no residual antibiotic activity. Disinfection and inactivation of bacteria and viruses can easily be achieved by Fe(VI). Advanced applications involve the use of ferrate for the degradation of cyanobacteria and microcystin originating from algal blooms and for covalently embedding arsenic and heavy metals into the structure of formed magnetic iron(III) oxides, therefore preventing their leaching. Applications of state-of-the-art analytical techniques, namely, in situ Mössbauer spectroscopy, rapid-freeze electron paramagnetic resonance, nuclear forward scattering of synchrotron radiation, and mass spectrometry will enhance the mechanistic understanding of ferrate species. This will make it possible to unlock the true potential of ferrates for degrading emerging toxins and pollutants, and in the sustainable production and use of nanomaterials in an energy-conserving environment.