Dye reduction

Uses. The principal uses of NaBH are ia synthesis of pharmaceuticals (qv) and fine organic chemicals removal of trace impurities from bulk organic chemicals wood-pulp bleaching, clay leaching, and vat-dye reductions and removal and recovery of trace metals from plant effluents. 

Sodium Tetrahydroborate, Na[BH ]. This air-stable white powder, commonly referred to as sodium borohydride, is the most widely commercialized boron hydride material. It is used in a variety of industrial processes including bleaching of paper pulp and clays, preparation and purification of organic chemicals and pharmaceuticals, textile dye reduction, recovery of valuable metals, wastewater treatment, and production of dithionite compounds. Sodium borohydride is produced in the United States by Morton International, Inc., the Alfa Division of Johnson Matthey, Inc., and Covan Limited, with Morton International supplying about 75% of market. More than six million pounds of this material suppHed as powder, pellets, and aqueous solution, were produced in 1990. 

Fig. 4. Spectrally sensitized speed for dyed silver haUdes as influenced by dye reduction or oxidation potential.

It is known that Selenium catalyzes reaction of some dye reduction by Sulphide. On this basis spectrophotometric and test-techniques for Selenium determination are developed. Inefficient reproducibility and low sensitivity are their deficiencies. In the present work, solid-phase reagent on silica gel modified first with quaternary ammonium salt and then by Indigocarmine was proposed for Selenium(IV) test-determination. Optimal conditions for the Selenium determination by method of fixed concentration were found. The detection limit of Se(IV) is 10 ftg/L = 2 ng/sample). Calibration curve is linear in the range 50-400 ftg/L of Se(IV). The proposed method is successfully applied to the Selenium determination in multivitamins and bioadditions. 

This enzyme is of wide occurrence in bacteria where it is concerned with the reduction of nitrate and CO2 as well as sulphur. Methods for its estimation depend on measuring some activity of hydrogenase by (a) dye reduction (benzyl viologen or methylene blue), (b) isotopic exchange and (c) evolution of molecular hydrogen. Interpretation of quantitative results is difficult due to the complex relationship between the enzyme cell structure and the particular method selected. ... 

Figure 12.25 Reaction scheme of the steps occurring in a vat dye reduction process [240]...

Pinheiro HM, Touraud E, Thomas O (2004) Aromatic amines from azo dye reduction status review with emphasis on direct UV spectrophotometric detection in textile industry waste-waters. Dyes Pigm 61 121-139... 

Pearce Cl, Christie R, Boothman C et al (2006) Reactive azo dye reduction by Shewanella strain J18 143. Biotechnol Bioengin 95 692-703... 

Kudlich M, Keck A, Klein J, Stolz A (1997) Localization of the enzyme system involved in anaerobic reduction of azo dyes by Sphingomonas sp. strain BN6 and effect of artificial redox mediators on the rate of azo dye reduction. Appl Env Microbiol 63 3691-3694... 

Fig. I Mechanism of anaerobic azo dye reduction. RM redox mediator ED electron donor b bacteria (enzyme) [14]...

Anaerobic azo dye reduction can be mediated by enzymes, low molecular weight redox mediators, and chemical reduction by biogenic reductants. These reactions can be located either intracellular or extracellular. Reduction of highly polar azo dyes, which cannot pass through the cell membranes, is located outside the cell. Like azo dyes, nicotinamide adenine dinucleotide phosphate, which is believed to be the main source of electrons, also cannot pass through the cell membranes. Azo reductase enzyme, which is oxygen-sensitive and released extracellularly, is found to be responsible for the reduction of azo dyes. 

Ferric iron can act as an electron acceptor under the anaerobic conditions the azo dye is in. Like sulfate, it was found that addition of ferric iron to the reactor stimulates the azo dye reduction. Indeed, the reactions are dealing with the redox couple Fe (III)/Fe (II), which can act as an electron shuttle for transferring electrons from electron donor to the electron accepting azo dye. Meanwhile, reactions of both reduction of Fe (III) to Fe (II) and oxidation of Fe (II) to Fe (III) facilitate the electron transport from the substrate to azo dye, thus acting as an extracellular redox mediator [31]. 

Since long retention times are often applied in the anaerobic phase of the SBR, it can be concluded that reduction of many azo dyes is a relatively a slow process. Reactor studies indicate that, however, by using redox mediators, which are compounds that accelerate electron transfer from a primary electron donor (co-substrate) to a terminal electron acceptor (azo dye), azo dye reduction can be increased [39,40]. By this way, higher decolorization rates can be achieved in SBRs operated with a low hydraulic retention time [41,42]. Flavin enzyme cofactors, such as flavin adenide dinucleotide, flavin adenide mononucleotide, and riboflavin, as well as several quinone compounds, such as anthraquinone-2,6-disulfonate, anthraquinone-2,6-disulfonate, and lawsone, have been found as redox mediators [43—46]. 

Though accelerating effect of redox mediators is proved, differences in electrochemical factors between mediator and azo dye is a limiting factor for this application. It was reported that redox mediator applied for biological azo dye reduction must have redox potential between the half reactions of the azo dye and the primary electron donor [37], The standard redox potentials for different azo dyes are screened generally between -430 and -180 mV [47],... 

Since anaerobic azo dye reduction is an oxidation-reduction reaction, a liable electron donor is essential to achieve effective color removal rates. It is known that most of the bond reductions occurred during active bacterial growth [48], Therefore, anaerobic azo dye reduction is extremely depended on the type of primary electron donor. It was reported that ethanol, glucose, H2/CO2, and formate are effective electron donors contrarily, acetate and other volatile fatty acids are normally known as poor electron donors [42, 49, 50]. So far, because of the substrate itself or the microorganisms involved, with some primary substrates better color removal rates have been obtained, but with others no effective decolorization have been observed [31]. Electron donor concentration is also important to achieve... 

Though treatment of azo dye-containing wastewaters needs combined anaerobic-aerobic phases, microorganisms are subjected to continually alternating anaerobic and aerobic conditions. Thus, it is presumable that anaerobic enzymes involved in the azo dye reduction may be adversely affected by aerobic conditions, as well as aerobic enzymes involved in the aromatic amine mineralization may be adversely affected by anaerobic conditions. Since little is known about the regulations of the enzymes involved in complete biodegradation of colored wastewaters, this approach seems to need advanced investigation to improve color removal and aromatic amine mineralization. 

The bio-treatment technology of dyes, especially anaerobic azo dye reduction, has been thoroughly investigated, and most researchers agree that it is a nonspecific and presumably extracellular process in which reducing equivalents from either biological or chemical source are transferred to the dye. 

Anaerobic bio-reduction of azo dye is a nonspecific and presumably extracellular process and comprises of three different mechanisms by researchers (Fig. 1), including the direct enzymatic reduction, indirect/mediated reduction, and chemical reduction. A direct enzymatic reaction or a mediated/indirect reaction is catalyzed by biologically regenerated enzyme cofactors or other electron carriers. Moreover, azo dye chemical reduction can result from purely chemical reactions with biogenic bulk reductants like sulfide. These azo dye reduction mechanisms have been shown to be greatly accelerated by the addition of many redox-mediating compounds, such as anthraquinone-sulfonate (AQS) and anthraquinone-disulfonate (AQDS) [13-15],... 

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