Zero-valent aluminum-mediated degradation of Bisphenol A in the presence of common oxidants.

The use of a commercial, nano-scale zero-valent aluminum (ZVA) powder was explored for the treatment of aqueous Bisphenol A (BPA). The study focused on the (i) activation of hydrogen peroxide (HP) and persulfate (PS) oxidants with ZVA to accelerate BPA degradation, (ii) comparison of the treatment performance in pure and real surface water (SW) samples, (iii) effects on toxicity and (iv) reuse potential of ZVA nanoparticles after ZVA/HP and ZVA/PS treatments. In pure water, ZVA coupled with HP or PS provided an effective means of BPA treatment particularly when PS was employed as the oxidant. On the other hand, in BPA-spiked SW, the ZVA/HP treatment combination outperformed ZVA/PS oxidation in terms of BPA removal, whereas ZVA/PS oxidation was superior in terms of organic carbon removal. According to the bioassays conducted in pure and real SW samples with the marine photobacteria Vibrio fischeri and the freshwater microalgae Pseudokirchneriella subcapitata, the toxicity response of BPA and its oxidation products was sensitive to the test organism and water matrix. The inhibitory effect of the reaction solution increased at the early stages of ZVA/PS treatment. The reuse potential of the ZVA/HP treatment system was higher than that of the ZVA/PS treatment system.

Enhanced degradation of micropollutants by zero-valent aluminum activated persulfate: assessment of toxicity and genotoxic activity.

Advanced oxidation of the aqueous Triton™ X-45 (TX-45), iopamidol (IOPA), ciprofloxacin (CIP) and bisphenol A (BPA) solutions via activation of persulfate (PS) with zero-valent aluminum (ZVA) was investigated. The study aimed at assessing the effectiveness of the PS/ZVA process in terms of target micropollutants (MPs) and toxicity abatements in raw surface water (RSW) and distilled water (DW). TX-45, CIP and BPA were completely degraded after 90-minute, 120-minute and 40-minute treatment, respectively, with PS/ZVA in DW, whereas 95% IOPA removal was achieved after 120-minute (MPs = 2 mg/L; ZVA = 1 g/L; PS = 0.25 mM for CIP and BPA; PS = 0.50 mM for TX-45 and IOPA; pH = 3). TX-45 (59%), IOPA (29%), CIP (73%) and BPA (46%) removal efficiencies decreased after 120-minute PS/ZVA treatment in RSW. In DW, Vibrio fischeri toxicities of original (untreated) MPs were found as: CIP (51%) > BPA (40%) > TX-45 (15%) > IOPA (1%), and as BPA (100%) > CIP (66%) > IOPA (62%) > TX-45 (35%) in RSW. Acute toxicities of MPs and their degradation products fluctuated during PS/ZVA treatment both in DW and RSW samples and resulted in different relative inhibition values after 120-minute. The original and PS/ZVA-treated TX-45, IOPA and BPA in DW exhibited neither cytotoxic nor genotoxic effects, whereas CIP oxidation ended up in degradation products with genotoxic effects.

Degradation and toxicity assessment of the nonionic surfactant Triton™ X-45 by the peroxymonosulfate/UV-C process.

The degradation and mineralization of the nonionic surfactant octylphenol ethoxylate (OPEO), commercially known as Triton™ X-45, by the peroxymonosulfate (PMS)/UV-C process were investigated. Three different toxicity tests (Daphnia magna, Vibrio fischeri and Pseudokirchneriella subcapitata) as well as the Yeast Estrogen Screen (YES) bioassay were undertaken to evaluate the potential toxic and estrogenic effects of OPEO and its oxidation products. OPEO removal was very fast and complete after 7 min via PMS/UV-C treatment under the investigated reaction conditions (OPEO = 20 mg L(-1) (47 µM); TOC = 12 mg L(-1); PMS = 2.5 mM; initial reaction pH = 6.5; applied UV-C dose = 21 Wh L(-1)). TOC removal also proceeded rapidly; a gradual decrease was observed resulting in an overall TOC removal of 84%. The toxic responses of PMS/UV-C treated OPEO solutions varied according to the test organism used in the bioassay. Daphnia magna was found to be most sensitive to aqueous OPEO, whereas Pseudokirchneriella subcapitata appeared to be the least sensitive one. Daphnia magna and Vibrio fischeri tests revealed that the inhibitory effect of OPEO decreased significantly during the course of treatment. On the other hand, PMS/UV-C oxidation products exhibited a high toxic effect towards Pseudokirchneriella subcapitata (around 60%). YES test results underlined the need for improving the PMS/UV-C treatment performance to remove the estrogenic activity of OPEO and its oxidation products.

Treatment of aqueous bisphenol A using nano-sized zero-valent iron in the presence of hydrogen peroxide and persulfate oxidants.

Bisphenol A (BPA) is an industrial pollutant considered as one of the major endocrine-disrupting chemicals found in natural waters. In the present study, the use of a commercial, air-stable, zero-valent iron (ZVI) powder, consisting of Fe0 surface stabilized nanoparticles was examined for the treatment of 20 mg/L, aqueous BPA solutions. The influence of pH (3, 5, 7), addition of hydrogen peroxide (HP) and persulfate (PS) oxidants (0.0, 1.25 and 2.5 mM) as well as temperature (25 and 50 °C) was studied for BPA treatment with 1 g/L ZVI. ZVI coupled with HP or PS provided an effective treatment system, which was based on rapid ZVI-mediated decomposition of the above-mentioned oxidants, resulting in complete BPA as well as significant total organic carbon (TOC) (88%) removals, in particular when PS was employed as the oxidant. Increasing the PS concentration and reaction temperature dramatically enhanced PS decomposition and BPA removal rates, whereas HP was not very effective in TOC removals and at elevated temperatures. According to the bioassays conducted with Vibrio fischeri and Pseudokirchneriella subcapitata, the acute toxicity of aqueous BPA fluctuated at first but decreased appreciably at the end of ZVI/PS treatment.

Organic matter and heavy metal removals from complexed metal plating effluent by the combined electrocoagulation/Fenton process.

In the present study, the treatment of metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation (EC) using stainless steel electrodes was explored. In order to improve the organic matter removal efficiency, the effect of H(2)O(2) addition to the electrocoagulation (the combined EC/Fenton process) application was investigated. For this purpose, a wide range of H(2)O(2) concentrations varying between 15 and 230 mM was tested. All EC and EC/Fenton processes were performed at an initial pH of 2.6 and at an optimized current density of 22 mA/cm(2). Although up to 30 mM H(2)O(2) addition improved the EC process performance in terms of organic matter abatement, the highest COD and TOC removal efficiencies were obtained for the combined EC/Fenton process in the presence of 20 mM H(2)O(2). Nickel and zinc were completely removed for all runs tested in the present study after pH adjustments. At the optimized operation conditions, the combined EC/Fenton process proved to be an alternative treatment method for the improvement of organic matter reduction as well as complexed metal removal from metal plating industry wastewater.

Effect of Fenton's treatment on the biodegradability of chromium-complex azo dyes.

Pretreatment of an acid dyebath effluent bearing a new generation chromium complex azo dyestuff (C0 = 350 mg/L) with Fenton's reagent was investigated. Preliminary optimisation (baseline) experiments were conducted to determine the Fe2+, H2O2 concentrations and pH required to the highest possible COD and colour removals. Kinetic studies were carried out at varying temperatures (20 degrees C < T < 70 degrees C) to establish a relationship between COD abatement and H2O2 consumption. The activation energy found for catalytic H2O2 decomposition (Ea = 9.8 kJ/mol) appeared to be significantly less than that of fermentative (Ea = 23 kJ/mol) and of thermal (Ea = 76 kJ/mol) H2O2 decomposition, implying that H2O2 decomposition during the Fenton's reaction occurs more spontaneously. The experimental studies indicated that approximately 30% COD and complete colour removal could be achieved under optimised Fenton pretreatment conditions (Fe2+ = 2 mM; H2O2 = 30 mM; pH = 3; at T = 60 degrees C). Long-term activated sludge experiments revealed that although the raw and pretreated acid dyebath effluent contained practically the same amount of "readily biodegradable" COD (inert COD fraction < or = 10%), biodegradation of the chemically pretreated acid dye effluent proceeded appreciably faster than that of the untreated acid dyebath effluent.

Comparison of electrocoagulation, coagulation and the fenton process for the treatment of reactive dyebath effluent.

In this paper, experimental studies were performed on a simulated reactive dyebath effluent to compare coagulation-flocculation and Fenton's oxidation with electrocoagulation using stainless steel (SS 304) and aluminium electrodes in terms of colour and COD removals as well as AOX formation potential and improvement of biological treatability. Results have indicated that FeCl3 and alum coagulation had little effect on colour removal whereas comparable colour removal efficiencies with those of electrocoagulation with steel electrodes and Fenton's oxidation were attained by FeSO4 coagulation. Almost complete colour removals accompanied with 77% COD abatement were obtained by both electrocoagulation with steel electrodes and Fenton's oxidation under optimised reaction conditions. Although electrocoagulation with aluminium electrodes yielded very limited colour removal and produced a high amount of sludge upon extended reaction time, this application brought about a marked improvement in biodegradability.

Treatability of cefazolin antibiotic formulation effluent with O3 and O3/H2O2 processes.

The effect of applying ozonation and perozonation to antibiotic cefazolin-Na formulation effluents were investigated in this study. Twenty minutes of ozonation at a rate of 1,500 mg/L-h was observed to remove COD by 38%, whereas a COD removal efficiency of 40% was achieved via H2O2 enhanced ozonation (same conditions + 31.25 mM H2O2). Both of the pretreatment alternatives were monitored to elevate the BOD5/COD ratio from 0.01 to 0.08. The initially inert COD was reduced by 38% using ozonation and by 60% employing H2O2 enhanced ozonation. In terms of the lowest achievable effluent COD levels after bio-treatment, ozonation was observed to yield a residual COD of 205 mgL(-1), while a residual COD of 135 mgL(-1) was involved for perozonation. According to the results of acute toxicity on Phaedactylum tricornutum, ozonated and perozonated samples exhibited more toxicity than the untreated effluent after 4 days. The activated sludge inhibition test demonstrated that both of the pretreatment alternatives efficiently eliminated the inhibition of investigated formulation effluent.

Ozonation of synthetic versus natural textile tannins: recalcitrance and toxicity towards Phaeodactylum tricornutum.

A sound in-plant pollution control strategy can only be defined by paying due attention to bio-recalcitrance and toxicity. In this context the levels of toxicity and inert COD introduced to textile dyebath discharges by two alternative auxiliary chemicals, namely natural tannin (NT) and synthetic tannin (ST), were investigated. The effect of 40 minutes ozonation at 1,000 mg h(-1) at pH 3.5 on the segregated effluent streams containing the above-mentioned tannin formulations was evaluated in terms of changes in toxicity and recalcitrance. The effect of ozonation on the COD distribution of raw and ozonated NT and ST samples according to their molecular weight cut-offs was also assessed. Both untreated tannin formulations exerted high acute toxicity towards marine microalgae Phaeodactylum tricornutum. Moderate decrease in the toxicity levels of both tannins was observed upon ozonation. The raw NT formulation with a COD content more than twice that of its alternative raw ST had an initially inert soluble COD content of only 25 mg/L, while the initially inert COD was 135 mg/L for ST. As the initially inert soluble COD content of NT was considerably lower, this textile auxiliary did not need chemical pretreatment to improve its biodegradability. On the other hand, the initially inert soluble COD content of ST was reduced by 70% by ozone pretreatment. In terms of residual COD contents achievable after passing through a biological treatment system, raw NT and pretreated ST formulations yielded 100 and 95 mg/L COD, respectively. The highest proportion of COD (46% for NT and 88% for ST) was found in the <1 kDa range. The same fraction increased to 93% for NT after ozonation, while for ST no significant change was observed in the COD distribution of the molecular weight cut-offs after ozonation.

Biological treatability of raw and ozonated synthetic penicillin formulation effluent.

Chemical pre-treatment of synthetic Procaine Penicillin G (PPG) effluent with ozone (applied dose = 1440 mg/h; treatment duration = 60 min) at pH = 7 was investigated. Successive biological treatability studies were performed with raw, ozonated penicillin formulation effluent and synthetic readily biodegradable substrate as simulated domestic wastewater. The PPG effluent additions were adjusted to constitute approximately 30% of the total COD in the reactor. Ozonation of PPG effluent resulted in practically complete removal of the parent pollutant accompanied by 40% COD abatement. Speaking for the raw PPG effluent, prolonged acclimation periods were necessary to obtain significant COD removal efficiencies. Batch activated sludge treatment experiments and respirometric studies have demonstrated that the selection of true retention time is extremely crucial for having high amount of slowly hydrolysable substrate or complex wastewater, like pharmaceutical effluent. The effect of ozonation time on biological treatability performance of PPG has been evaluated in the study. Pre-ozonation of PPG effluent did not improve its ultimate biodegradability.

Advanced oxidation of commercial textile biocides in aqueous solution: effects on acute toxicity and biomass inhibition.

In the present study, the decomposition of two biocides used in the textile finishing process with Advanced Oxidation Processes (AOPs) has been studied. Different AOPs, i.e O3/OH-, TiO2/UV-A and Fe2+/H2O2 have been used representing mutually combined components of the chemically and photochemically driven advanced oxidation systems. The course of reaction was examined by changes in chemical oxygen demand (COD), total organic carbon (TOC) and acute toxicity towards the water flea Daphnia magna (assessed in terms of the effective dilution ratio LD50). Particular attention has been paid to determine the inhibitory effect of raw and ozonated biocides on biological activated sludge consortium at concentrations typically encountered in textile finishing effluents. Significant oxidation and mineralization of both biocides could be achieved employing ozonation at pH = 11.5 and heterogeneous photocatalysis (TiO2/UV-A) at pH = 5.0, whereas Fenton's reagent appeared to be less effective in COD and acute toxicity abatement.

Photodegradation of hydrophobic disperse dyes and dye-bath effluents by silicadodecatungstate (SiW12O40(4-/5-)) nanoparticles.

Polyoxometalate (POM) silicadodecatungstic acid has been applied as a photochemical catalyst for the degradation of SETAPERS Black WNSP, a disperse dyestuff preparation widely used to dye polyester and polyamide fabrics. It could be demonstrated that the disperse dyestuff was photo-reduced by SiW12O40(5-), the one-electron reduced form of POM, as evidenced by Heteropolyblue (HPB) formation. For completion of the photochemical redox cycle, isopropanol (IsOH) was required. Acetone (Ac) served solely as an effective solute and photosensitizer; however this effect was suppressed in the presence of POM. Threshold (0.087 mM) and optimum (0.375 mM) POM concentrations existed and decolorization kinetics were inhibited upon the addition of dye auxiliary chemicals. Increasing the dyestuff concentration from 50 mg/L to 150 mg/L did not affect initial decolorization kinetics revealing that not the formation of the excited [POM-Substrate]* complex, but its reduction to HPB was the rate limiting step. POM-mediated, IsOH-assisted UV-photodegradation of disperse dyes and dye-baths is by far more effective than applying other, more well known chemical oxidation methods (O3, H202/UV, Power Ultrasound). Key to the action of POM redox catalysts is the feature that particularly heteropoly tungstates undergo facile re-oxidation to their original state, thus allowing regeneration of the photocatalyst, a feature that may become critical for real-scale application.

Is the naphthalene sulfonate H-acid biodegradable in mixed microbial cultures under aerobic conditions?

Synthetically prepared wastewater originating from the H-acid (4-Amino-5-hydroxy-2,7-naphthalene disulfonic acid) manufacturing process was subjected to respirometric analysis for evaluating the level of achievable biodegradation in the presence of this commercially important azo dye precursor. For this purpose, H-acid was mixed with synthetic substrate having the same characteristics as sewage at a concentration and composition being typical for H-acid manufacturing wastewater. Experimental results indicated that H-acid was not biodegradable under activated sludge treatment conditions even after prolonged acclimation periods. The results were also confirmed by model evaluation of oxygen uptake rate profiles. H-acid also did not inhibit the biodegradation of synthetic sewage but accumulated as soluble inert COD in the treated wastewater.

Effect of Fenton's oxidation on the particle size distribution of organic carbon in olive mill wastewater.

The study evaluated the effect of Fenton's oxidation on the particle size distribution (PSD) of significant parameters reflecting the organic carbon content of olive oil mill wastewater (OMW). The organic carbon content of the studied OMW was characterized by a COD level of around 40,000 mg/L, with 13,500 mg/L of TOC and 1670 mg/L of total phenols. The corresponding antioxidant activity (AOA) was determined as 33,400mg/L. PSD of the selected organic carbon parameters was investigated using a sequential filtration/ultrafiltration procedure. COD fractionation based on PSD revealed two major components, a soluble fraction below 2 nm and a particulate fraction above 1600 nm representing 49% and 20% of the total COD, respectively. The remaining COD was distributed in the colloidal and supracolloidal zones. The PSD of TOC, total phenols and AOA exhibited similar profiles with peaks at the two ends of the studied size range. Overall COD removals achieved via Fenton's oxidation both at pH=3.0 and pH=4.6 (the original pH of the OMW) remained in the range of 40-50%. As anticipated, the effect of Fenton's treatment was more pronounced in the soluble size range. Fenton's oxidation at pH=3.0 resulted in 46% and 63% removals for total phenols and AOA, respectively. The results obtained indicated that Fenton's process could only be useful as an alternative preliminary treatment option of the required full treatment scheme that could involve a sequence of filtration, oxidation and/or biological treatment steps.

Biodegradability assessment of ozonated raw and biotreated pharmaceutical wastewater.

The activated sludge specific oxygen uptake rate (SOUR) and BOD(5)/COD ratios of biologically pretreated pharmaceutical wastewater were analyzed and compared to assess relative changes in biotreatability during ozonation at a rate of 7.4 g/(L x h) for 4 h. An appreciable COD removal (41%) was achieved by the initial biological treatment process, whereas ozonation was more effective in reducing the UV-sensitive aromatic compounds present in the pretreated effluent. Sequential treatment using activated sludge + ozonation processes resulted in an average COD removal efficiency of 48%, and a proceeding biotreatment stage increased the overall COD removal to 53%. An optimum ozone dose in the range of 1,854-3,708 mg/L corresponding to a specific ozone input rate of 0.23-0.46 mg O(3)/mg COD(o) existed where SOUR (3.7 x 10(-3) mg O(2)/[mg MLSS x min] for ozonation at pH 8) and BOD(5)/COD (0.57) as well as the proceeding biological COD removal yield Y(COD) (average 8 mg COD/mg MLSS) exerted maximum values.