Effect of surfactants, dispersion and temperature on solubility and biodegradation of phenanthrene in aqueous media

In the present study surfactant addition with the help of either a mechanical dispersion or a thermal treatment was applied in order to increase the solubility and the bioavailability of phenanthrene in aqueous media, and therefore to promote its biodegradation. Among four tested surfactants (Tween 80, Brij 30, sodium dodecyl sulphate and rhamnolipids), Brij 30 (0.5 gL(-1)) showed the best results allowing us to attain about 20 mgL(-1) of soluble phenanthrene. An additional thermal treatment at 60°C for 24h, 200 rpm permitted to increase the solubility of phenanthrene in the presence of Brij 30 (0.5 gL(-1)) to about 30 mgL(-1). Higher dispersions of phenanthrene particles as well as the reduction of their size were obtained using Ultra-Turrax and French press. The biodegradation of phenanthrene by Pseudomonas putida was then investigated. The reduction of size of phenanthrene particles by mechanical dispersion did not influence its biodegradation, suggesting that P. putida consumed only soluble phenanthrene. The addition of Brij 30 (0.5 gL(-1)) permitted to obtain more phenanthrene metabolized. The use of Brij 30 coupled with a transitory heating of phenanthrene-containing medium at 60°C led to an even more complete biodegradation. This might be a promising way to enhance biodegradation of PAHs.     

Characterization and reactivity assessment of organic substrates for sulphate-reducing bacteria in acid mine drainage treatment

Acid mine drainage (AMD), which contains high concentrations of sulphate and dissolved metals, is a serious environmental problem. It can be treated in situ by sulphate reducing bacteria (SRB), but effectiveness of the treatment process depends on the organic substrate chosen to supply the bacteria's carbon source. Six natural organic materials were characterized in order to investigate how well these promote sulphate reduction and metal precipitation by SRB. Maple wood chips, sphagnum peat moss, leaf compost, conifer compost, poultry manure and conifer sawdust were investigated in terms of their carbon (TOC, TIC, DOC) and nitrogen (TKN) content, as well as their easily available substances content (EAS). Single substrates, ethanol, a mixture of leaf compost (30% w/w), poultry manure (18% w/w), and maple wood chips (2% w/w), and the same mixture spiked with formaldehyde were then tested in a 70-day batch experiment to evaluate their performance in sulphate reduction and metal removal from synthetic AMD. Metal removal efficiency in batch reactors was as high as 100% for Fe, 99% for Mn, 99% for Cd, 99% for Ni, and 94% for Zn depending on reactive mixtures. Early metal removal (0-12d) was attributed to the precipitation of (oxy)hydroxides and carbonate minerals. The lowest metal and sulphate removal efficiency was found in the reactor containing poultry manure as the single carbon source despite its high DOC and EAS content. The mixture of organic materials was most effective in promoting sulphate reduction, followed by ethanol and maple wood chips, and single natural organic substrates generally showed low reactivity. Formaldehyde (0.015% (w/v)) provided only temporary bacterial inhibition. Although characterization of substrates on an individual basis provided insight on their chemical make-up, it did not give a clear indication of their ability to promote sulphate reduction and metal removal.     

Removal of thiobencarb in aqueous solution by zero valent iron

A cost-effective method with zero valent iron (ZVI) powder was developed for the purification of thiobencarb (TB)-contaminated water. The removal treatment was performed in the batch system. A sample solution of 10 ml containing 10 microg ml(-1) of TB could be almost completely treated by 100mg of ZVI at 25 degrees C for 12h of treatment time. Since the formation of chloride ion in the aqueous solution during the treatment of TB was observed, the removal of TB with ZVI may contain two processes: reduction (degradation) and adsorption. Because the present treatment for TB is simple, easy handling and cheap, the developed technology with ZVI can contribute to the treatment of agricultural wastewaters.     

Pressurized CO2/zero valent iron system for nitrate removal

A fluidized zero valent iron (ZVI) reactor pressurized by CO(2) gas for controlling pH was employed for nitrate reduction. The proposed CO(2) pressurized system potentially has advantages of using less CO(2) gas and reaching equilibrium pH faster than CO(2)-bubbled system. However, due to weak acid nature of carbonic acid, system pH gradually increased with increasing oxidation of ZVI and reduction of nitrate. As pH increased with progress of reaction, nitrate removal rate decreased continuously. The results indicate that nitrate removal efficiency increases with increasing initial ZVI dosage but reaches plateau at ZVI doses of higher than 8.25gl(-1), and initial nitrate concentration up to 100mg l(-1) as N has minimal impact on the removal efficiency. Unlike the fluidized system with pH control by strong acid reported in our pervious study, near 100% of nitrogen recovery was observed in the current process, indicating that nitrate reduction by ZVI with different pH controlled mechanisms will have different reaction routes.     

Column experiments to assess the effects of electron donors on the efficiency of in situ precipitation of Zn,Cd, Co and Ni in contaminated groundwater applying the biological sulfate removal technology

BACKGROUND, AIMS AND SCOPE: In a previous study, we explored the use of acetate, lactate, molasses, Hydrogen Release Compound (HRC, which is based on a biodegradable poly-lactate ester), methanol and ethanol as carbon source and electron donor to promote bacterial sulfate reduction in batch experiments, this with regards to applying an in situ metal precipitation (ISMP) process as a remediation tool to treat heavy metal contaminated groundwater at the site of a nonferrous metal work company. Based on the results of these batch tests, column experiments were conducted with lactate, molasses and HRCI as the next step in our preliminary study for a go-no go decision for dimensioning an on site application of the ISMP process that applies the activity of the endogenous population of sulfate-reducing bacteria (SRB). Special attention was given to the sustainability of the metal precipitation process under circumstances of changing chemical oxygen demand (COD) to [SO4(2-)] ratios or disrupted substrate supply. METHODS: To optimize the ISMP process, an insight is needed in the composition and activity of the indigenous SRB community, as well as information on the way its composition and activity are affected by process conditions such as the added type of C-source/ electron donor, or the presence of other prokaryotes (e.g. fermenting bacteria, methane producing Archaea, acetogens). Therefore, the biological sulfate reduction process in the column experiments was evaluated by combining classical analytical methods [measuring heavy metal concentration, SO4(2-)-concentration, pH, dissolved organic carbon (DOC)] with molecular methods [denaturing gradient gel electrophoresis (DGGE) fingerprinting and phylogenetic sequence analysis] based on either the 16S rRNA-gene or the dsr (dissimilatory sulfite reductase) gene, the latter being a specific biomarker for SRB. RESULTS AND DISCUSSION: All carbon sources tested promoted SRB activity, which resulted within 8 weeks in a drastic reduction of the sulfate and heavy metal contents in the column effluents. However, unexpected temporal decreases in the efficiency of the ISMP process, accompanied by the release of precipitated metals, were observed for most conditions tested. The most dramatic observation of the failing ISMP process was observed within 12 weeks for the molasses amended column. Subsequent lowering the COD/ SO4(2-) ratio from 1.9 to 0.4 did not alter the outcome of sulfate reduction and metal precipitation efficiency in this set-up. Remarkably, after 6 months of inactivity, bacterial sulfate reduction was recovered in the molasses set up when the original COD/ SO4(2-) ratio of 1.9 was applied again. Intentional disruption of the lactate and HRC supplies resulted in an immediate stagnation of the ISMP processes and in a rapid release of precipitated metals into the column effluents. However, the ISMP process could be restored after substrate amendment. 16S rDNA-based DGGE analysis revealed that the SRB population, in accordance with the results of the previously performed batch experiments, consisted exclusively of members of the genus Desulfosporosinus. The community of Archaea was characterized by sequencing amplicons of archaeal and methanogen-specific PCR reactions. This approach only revealed the presence of non-thermophilic Crenarchaeota, a novel group of organisms which is only distantly related to methane producing Euryarchaeota. DGGE on the dsrB genes was successfully used to link the results of the ISMP process to the community composition of the sulfate reducing bacteria. CONCLUSIONS: In the case of an intentional disruption of substrate supply, the ISMP process failed most likely because the growth and activity of the indigenous SRB community stopped due to a lack of a carbon and electron donor. On the other hand, the cause of the sudden temporal shortcomings of the ISMP process in the presence of different substrates was not immediately clear. It was first thought to be the result of competition between methanogenic prokaryotes (MP) and sulfate reducers, since the formation of small amounts of CH4 (0.01-0.03 ppm ml(-1) was detected. However, the results of molecular analyzes indicate that methanogens do not constitute a major fraction of the microbial communities that were enriched in the column experiments. Therefore, we postulate that the SRB population becomes inhibited by the formed metal sulfides. RECOMMENDATION AND PERSPECTIVE: Our results indicate that the ISMP process is highly dependent on SRB-stimulation by substrate amendments and suggest that this remedial approach might not be viable for long-term application unless substrate amendments are continued and environmental conditions are strictly controlled. This will include the removal of affected aquifer material from the metal precipitation zone at the end of the remediation process, or removal of metal precipitates when the microbial activity decreases. Additional tests are necessary to investigate what will happen when clear groundwater passes through the reactive zone while no more C-sources are amended and all indigenous carbon is consumed. Also, the effects of dramatic increases in sulfate- or HM-concentrations on the SRB-community and the concomitant ISMP process need to be studied in more detail.     

Electrochemical removal of nitrate using ZVI packed bed bipolar electrolytic cell

The present study investigates the performance of the zero valent iron (ZVI, Fe⁰) packed bed bipolar electrolytic cell for nitrate removal. The packing mixture consists of ZVI as electronically conducting material and silica sand as non-conducting material between main cathode and anode electrodes. In the continuous column experiments for the simulated groundwater (initial nitrate and electrical conductivity of about 30 mg L⁻¹ as N and 300 μS cm⁻¹, respectively), above 99% of nitrate was removed at the applied potential of 600 V with the main anode placed on the bottom of reactor. The influx nitrate was converted to ammonia (20% to maximum 60%) and nitrite (always less than 0.5 mg L⁻¹ as N in the effluent). The optimum packing ratio (v/v) of silica sand to ZVI was found to be 1:1-2:1. Magnetite was observed on the surface of the used ZVI as corrosion product. The reduction at the lower part of the reactor in acidic condition and adsorption at the upper part of the reactor in alkaline condition are the major mechanism of nitrate removal.     

Removal of chromium from synthetic plating waste by zero-valent iron and sulfate-reducing bacteria.

Experiments were conducted to evaluate the potential of zero-valent iron and sulfate-reducing bacteria (SRB) for reduction and removal of chromium from synthetic electroplating waste. The zero-valent iron shows promising results as a reductant of hexavalent chromium (Cr+6) to trivalent chromium (Cr+3), capable of 100% reduction. The required iron concentration was a function of chromium concentration in the waste stream. Removal of Cr+3 by adsorption or precipitation on iron leads to complete removal of chromium from the waste and was a slower process than the reduction of Cr+6. Presence SRB in a completely mixed batch reactor inhibited the reduction of Cr+6. In a fixed-bed column reactor, SRB enhanced chromium removal and showed promising results for the treatment of wastes with low chromium concentrations. It is proposed that, for waste with high chromium concentration, zero-valent iron is an efficient reductant and can be used for reduction of Cr+6. For low chromium concentrations, a SRB augmented zero-valent iron and sand column is capable of removing chromium completely.     

Contributions of fermentative acidogenic bacteria and sulfate-reducing bacteria to lactate degradation and sulfate reduction

The roles of fermentative acidogenic bacteria and sulfate-reducing bacteria (SRB) in lactate degradation and sulfate reduction in a sulfidogenic bioreactor were investigated by traditional chemical monitoring and culture-independent methods. A continuously stirred tank reactor fed with synthetic wastewater containing lactate and SO(2-)(4) at 35 degrees C, 10h of hydraulic retention time was used. The results showed that sulfate removal efficiency reached 99%, and sulfide and acetate were the main end products after 20 d of operation. 16S rRNA gene based clone libraries and single-strand conformation polymorphism profiles demonstrated that the proportion of SRB increased from 16% to 95%, and that Desulfobulbus spp., Desulfovibrio spp., Pseudomonas spp. and Clostridium spp. formed a stable, dominant community structure. The decreasing COD/SO(2-)(4) ratio had little effect on the community pattern except that Pseudomonas spp. and Desulfobulbus spp. increased slightly. The addition of molybdate to the influent significantly changed the microbial community, sulfate removal efficiency and the pattern of end products. Clostridium spp., Bacteroides spp. and Ruminococcus spp. became the dominant community members. The main end products switched from acetate to ethanol and then to propionate with the oxidation-reduction potentials increasing from -420 to -290 mV. A lactate degradation pathway was deduced: lactate served as the electronic donor for Desulfovibrio spp., or was fermented by Clostridium spp. and Bacteroides spp. to produce propionate or ethanol, which were subsequently utilized by Desulfobulbus spp. and Desulfovibrio spp. The acidotrophic SRB oxidized part of the acetate finally.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH^? · pH^?1. The sediments were spiked with atrazine at 7.25-36.23 mg kg^?1 (6.21 × 10^?7–3.09 × 10^?6 mol atrazine · g^?1 sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 × 10^?2?7.04 × 10^?2 d^?1 for the atrazine-spiked sediments.     

Kinetics of chemical decolorization of the azo dye C.I. Reactive Orange 96 by sulfide

The mechanism of decolorization of azo dyes based on the extracellular chemical reduction with sulfide (H2S, HS-, S2-) was postulated for sulfate reducing environments. To design technical decolorization processes of textile wastewater treatment with sulfide produced by sulfate reducing bacteria (SRB), kinetics is of great significance. Batch experiments were made in order to investigate the kinetics of abiotic decolorization of the reactive mono-azo dye C.I. Reactive Orange 96 (RO 96) with sulfide, with varying pH. The decolorization of RO 96 by sulfide under the exclusion of O2 corresponded to first-order kinetics with respect to both dye and sulfide concentration. The decolorization of RO 96 with sulfide at neutral pH (7.1) was advantageous compared with that at pH for 4.1, 6.3, and 6.5. This is attributed to an increase in the fraction of HS- of total sulfide species at neutral pH. The rate constants k for the decolorization at 37 degrees C were obtained as 0.01 for pH = 4.1, 0.06 for pH = 6.3, 0.08 for pH = 6.5, and 0.09 for pH = 7.1 in mM(-1) min(-1). The high rate constants for sulfide at pH 6.5-7.1 support that the decolorization through SRB (i.e. by bio-sulfide) can be effective in anaerobic bacterial systems with sulfate.     

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets

Chromate transport through columns packed with zeolite/zero valent iron (Z/ZVI) pellets, either untreated or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow rates. In the presence of sorbed HDTMA, the chromate retardation factor increased by a factor of five and the pseudo first-order rate constant for chromate reduction increased by 1.5-5 times. The increase in rate constant from the column studies was comparable to a six-fold increase in the rate constant determined in a batch study. At a fast flow rate, the apparent delay in chromate breakthrough from the HDTMA modified Z/ZVI columns was primarily caused by the increase in chromate reduction rate constant. In contrast, at a slower flow rate, the retardation in chromate transport from the HDTMA modified Z/ZVI columns mainly originated from chromate sorption onto the HDTMA modified Z/ZVI pellets. Due to dual porosity, the presence of immobile water was responsible for the earlier breakthrough of chromate in columns packed with zeolite and Z/ZVI pellets. The results from this study further confirm the role of HDTMA in enhancing sorption and reduction efficiency of contaminants in groundwater remediation.     

Fluidized zero valent iron bed reactor for nitrate removal

A fluidized zero valent iron (ZVI) reactor is examined for nitrate reduction. Using the system, the pH of solution can be maintained at optimal conditions for rapid nitrate reduction. For hydraulic retention times of 15 min, the nitrate reduction efficiency increases with increasing ZVI dosage. At ZVI loadings of 33 gl-1, results indicate that the nitrate removal efficiency increases from less than 13% for systems without pH control to more than 92% for systems operated at pH of 4.0. By maintaining pH at 4.0, we are able to decrease the hydraulic retention time to 3 min and still achieve more than 87% nitrate reduction. The recovery of total nitrogen added as nitrate, ammonium, and nitrite was less than 50% for the system operated at pH4.0, and was close to 100% for a system without pH control. The possibility of nitrate and ammonium adsorption onto iron corrosion products was ruled out by studying the behavior of their adsorption onto freshly hydrous ferric oxide at variable pH. Results indicate the probable formation of nitrogen gas species during reaction in pH4.0.     

Zero valent iron remediation of a mixed brominated ethene contaminated groundwater

The suitability of a granulated zero valent iron (ZVI) permeable reactive barrier (PRB) remediation strategy was investigated for tribromoethene (TriBE), cis-1,2-dibromoethene (c-DBE), trans-1,2-dibromoethene (t-DBE) and vinyl bromide (VB), via batch and large-scale column experiments that were subsequently analysed by reactive transport modelling.The brominated ethenes in both batch and large-scale column experiments showed rapid (compared to controls and natural attenuation) degradation in the presence of ZVI. In the large-scale column experiment, degradation half-lives were 0.35 days for TriBE, 0.50 days for c-DBE, 0.31 days for t-DBE and 0.40 days for VB, under site groundwater flow conditions, resulting in removal of brominated ethenes within the first 0.2 m of a 1.0 m thick ZVI layer, indicating that a PRB groundwater remediation strategy using ZVI could be used successfully.In the model simulations of the ZVI induced brominated ethene degradation, assuming a dominant reductive β-elimination pathway via bromoacetylene and acetylene production, simulated organic compound concentrations corresponded well with both batch and large-scale column experimental data. Changes of inorganic reactants were also well captured by the simulations. The similar ZVI induced degradation pathway of TriBE and TCE suggests that outcomes from research on ZVI induced TCE remediation could also be applied to TriBE remediation.     

Effect of initial sulfide concentration on sulfide and phenol oxidation under denitrifying conditions

The objective of this work was to evaluate the effect of the initial sulfide concentration on the kinetics and metabolism of phenol and sulfide in batch bioassays using nitrate as electron acceptor. Complete oxidation of sulfide (20 mg L(-1) of S(2-)) and phenol (19.6 mg L(-1)) was linked to nitrate reduction when nitrate was supplemented at stoichiometric concentrations. At 32 mg L(-1) of sulfide, oxidation of sulfide and phenol by the organo-lithoautotrophic microbial culture was sequential; first sulfide was rapidly oxidized to elemental sulfur and afterwards to sulfate; phenol oxidation started once sulfate production reached a maximum. When the initial sulfide concentration was increased from 20 to 26 and finally to 32 mg L(-1), sulfide oxidation was inhibited. In contrast phenol consumption by the denitrifying culture was not affected. These results indicated that sulfide affected strongly the sulfide oxidation rate and nitrate reduction.     

Microbial processes as key drivers for metal (im)mobilization along a redox gradient in the saturated zone

Two sites representing different aquifer types, i.e., Dommel (sandy) and Flémalle (gravelly loam) along the Meuse River, have been selected to conduct microcosm experiments. Various conditions ranging from aerobic over nitrate- to sulphate reducing were imposed. For the sandy aquifer, nitrate reducing conditions predominated, which specifically in the presence of a carbon source led to pH increases and enhanced Zn removal. For the calcareous gravelly loam, sulphate reduction was dominant resulting in immobilization of both Zn and Cd. For both aquifer types and almost all redox conditions, higher arsenic concentrations were measured in the groundwater. Analyses of different specific microbial populations by polymerase chain reaction (PCR) revealed the dominance of denitrifiers for the Dommel site, while sulfate reducing bacteria (SRB) were the prevailing population for all redox conditions in the Flémalle samples.     

Rapid removal of flutriafol in water by zero-valent iron powder

A study of the effect of zero-valent iron (ZVI) powder is carried out for the first time on the degradation of flutriafol ((RS)-2,4'-difluoro-alpha-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, C(16)H(13)F(2)N(3)O), a bifluorinated soil and water persistent triazole pesticide using a laboratory scale device consisting of a 20 ml pyrex serum vials fixed to a Vortex agitator. Different amounts of ZVI powder (10-50 g l(-1)) at pH 6.6 and room temperature were investigated. Experiments showed an observed degradation rate k(obs) directly proportional to the surface of contact of flutriafol with ZVI. Flutriafol degradation reactions demonstrated first order kinetic with a half-live of about 10.8+/-0.5 min and 3.6+/-0.2 min when experiments were conducted at [ZVI]=10 g l(-1) into oxygenated and anoxic solutions, respectively. Three analytical techniques were employed to monitor flutriafol degradation and to understand solution and by-products behaviors: (1) A UV-Vis spectrophotometer; (2) a high performance liquid chromatography (HPLC) coupled with a photo diode array (PDA) and fluorescence detectors; (3) a similar HPLC coupled with a PDA and a mass spectrometer detectors equipped with an atmospheric pressure photoionization source. Results showed a complete disappearance of flutriafol after 20 min of contact with ZVI, the loss of fluorescence properties of the final by-products, the defluorination of the triazole pesticide via hydroxylation reaction and finally the hydrogenation of the triazole ring.     

Catalytic degradation of chlorothalonil in water using bimetallic iron-based systems

Modified zero valent iron (MZVI) was used to study the transformation of a chlorothalonil (CLT) solution and the variation of the observed degradation rate of the reduction reactions. This was carried out when transition metals e.g. Pd, Cu and Co plated on the surface of micrometric iron particles (< 150 microm) were used as reducing catalytic agents for pesticide removal. Reactions were undertaken under both oxic and anoxic conditions in the presence and the absence of a phosphate buffer solution (PBS). Results of batch studies in nitrogen sparged solutions revealed that incomplete slow dechlorination merely occurred with zero valent iron (ZVI), however, complete rapid dechlorination reactions took place with MZVI especially Fe/Pd. Dechlorination was depicted by studying UV absorbance and MS spectra of CLT and all corresponding by-products. Typical blue shifts (deltalambda = 4-6 nm/chlorine atom) were observed at the same time as chlorine cluster isotopes disappeared. After the plating process, metal loading was controlled by analyzing the remaining metal in the solution by atomic absorption spectroscopy. Experiments showed that CLT degradation mechanism is faster in nitrogen sparged solutions in the absence of PBS. Time needed for complete removal of 2.08 +/- 0.19 microM CLT solution was about 2 h when experiments were conducted with ZVI (t1/2 = 15.0 min) and about 10 min when the reaction was carried out under the same conditions with Fe/Pd 1% (t1/2 = 1.0 min). Degradation rates for all bimetallic systems were determined showing that Pd is the more exciting catalytic transition metal followed by Cu and Co. Furthermore, MZVI method showed obvious advantage to traditional CLT treatment methods.     

微氧环境下无色硫细菌和硫酸盐还原菌脱硫

通过间歇曝气形成微氧环境让SRB和CSB实现共生,使含硫酸盐有机废水中硫酸根最终转化成单质硫达到脱硫目的.研究考察了曝气量对SRB还原和CSB氧化的影响,确定了合适的曝气强度和水力停留时间,使得单质硫占系统内总硫比值最大.实验结果显示,在进水COD/SO42-=2000/1500 mg/L、曝气开关时间为2 s/2 min、生化时间为10 h时,单质硫产率最大,为89.53％,SO42-浓度降至最低值72.7 mg/L,还原率达95.1％,此时脱硫效果较好.     

Sorption and reduction of tetrachloroethylene with zero valent iron and amphiphilic molecules

Effects of surfactants and natural organic matter (NOM) on the sorption and reduction of tetrachloroethylene (PCE) with zero valent iron (ZVI) were examined in this study. PCE reduction by ZVI depended on the ionic type of the surfactants. The removal of PCE and production of TCE with non-ionic Triton X-100 and cationic hexadecyltrimethyl-ammonium (HDTMA) at one-half and two times the critical micelle concentration (CMC) were 1.2-1.8 times higher than without surfactants because of the enhanced PCE partitioning and surface concentration by the sorbed surfactants. When anionic sodium dodecyl benzene sulfonate (SDDBS) at one-half and two times CMC and NOM at 20 mg l(-1) and 50 mg l(-1) concentrations were used, the removal of PCE doubled and TCE production decreased. In the presence of SDDBS, TCE production by ZVI was lower than with HDTMA and Triton X-100 while PCE removal was higher than with the other surfactants.     

Biogenic sulphide plays a major role on the riboflavin-mediated decolourisation of azo dyes under sulphate-reducing conditions

The effect of high concentrations of sulphate on the reductive decolourisation of different azo dyes by anaerobic sludge was studied in batch cultures. Sludge cultures were pre-incubated under sulphate-reducing conditions prior addition of dyes. Little or no effects of sulphate (5-10 g sulphate l(-1)) on the rate of decolourisation of Reactive Orange 14 (RO14), Direct Blue 53 (DB53) and Direct Blue 71 (DB71) were observed when no external redox mediator was provided. However, an increase in sulphate concentration, in the presence of riboflavin (20 microM), enhanced the decolourisation of all dyes. The first-rate constant of decolourisation (k) was increased up to 2-, 3.6- and 2-fold for RO14, DB53 and DB71, respectively, by supplying high sulphate concentrations, compared to the controls lacking sulphate, in the presence of the redox mediator. Sulphate reduction did not take place during the course of azo reductions, but was only evident before dye addition and after complete decolourisation, suggesting azo dyes reduction out-competed sulphate reduction for the available reducing equivalents. The experimental data suggest that reduction of azo dyes by riboflavin, which had been reduced by biogenic sulphide, was the major mechanism implicated during decolourisations, which was corroborated by abiotic incubations. Riboflavin greatly accelerated the abiotic reduction of RO14, so that the k value was increased up to 44-fold compared to the control lacking riboflavin.