Removal of refractory compounds from stabilized landfill leachate using an integrated H2O2 oxidation and granular activated carbon (GAC) adsorption treatment

This study investigated the treatment performances of H₂O₂ oxidation alone and its combination with granular activated carbon (GAC) adsorption for raw leachate from the NENT landfill (Hong Kong) with a very low biodegradability ratio (BOD₅/COD) of 0.08. The COD removal of refractory compounds (as indicated by COD values) by the integrated H₂O₂ and GAC treatment was evaluated, optimized and compared to that by H₂O₂ treatment alone with respect to dose, contact time, pH, and biodegradability ratio. At an initial COD concentration of 8000 mg/L and NH₃-N of 2595 mg/L, the integrated treatment has substantially achieved a higher removal (COD: 82%; NH₃-N: 59%) than the H₂O₂ oxidation alone (COD: 33%; NH₃-N: 4.9%) and GAC adsorption alone (COD: 58%) at optimized experimental conditions (p ≤ 0.05; t-test). The addition of an Fe(II) dose at 1.8 g/L further improved the removal of refractory compounds by the integrated treatment from 82% to 89%. Although the integrated H₂O₂ oxidation and GAC adsorption could treat leachate of varying strengths, treated effluents were unable to meet the local COD limit of less than 200 mg/L and the NH₃-N of lower than 5 mg/L. However, the integrated treatment significantly improved the biodegradability ratio of the treated leachate by 350% from 0.08 to 0.36, enabling the application of subsequent biological treatments for complementing the degradation of target compounds in the leachate prior to their discharge.     

Greywater treatment by UVC/H2O2

Greywater treatment by UVC/H₂O₂ was investigated with regard to the removal of chemical oxygen demand (COD). A COD reduction from 225 to 30 mg l⁻¹ (overall removal of 87%) was achieved after settling overnight and subsequent irradiation for 3 h with 10 mM H₂O₂. Most of the contaminants were removed by oxidation since only 13% COD was removed by settlement.The removal of COD in the greywater followed a second-order kinetic equation, r = 0.0637[COD][H₂O₂], up to 10 mM H₂O₂. A slightly enhanced COD removal was observed at the initial pH of 10 compared with pH 3 and 7. This was attributed to the dissociation of H₂O₂ to O₂H⁻. The treatment was not affected by total concentration of carbonate (c_T) of at least 3 mM, above which operation between pH 3 and 5 was essential. The initial biodegradability of the settled greywater (as BOD₅:COD) was 0.22. After 2 h UVC/H₂O₂ treatment, a higher proportion of the residual contaminants was biodegradable (BOD₅:COD = 0.41) which indicated its potential as a pre-treatment for a biological process.     

Advanced treatment of biologically pretreated coking wastewater by electrochemical oxidation using boron-doped diamond electrodes

Electrochemical oxidation is a promising technology to treatment of bio-refractory wastewater. Coking wastewater contains high concentration of refractory and toxic compounds and the water quality usually cannot meet the discharge standards after conventional biological treatment processes. This paper initially investigated the electrochemical oxidation using boron-doped diamond (BDD) anode for advanced treatment of coking wastewater. Under the experimental conditions (current density 20-60 mA cm⁻², pH 3-11, and temperature 20-60 °C) using BDD anode, complete mineralization of organic pollutants was almost achieved, and surplus ammonia-nitrogen (NH₃-N) was further removed thoroughly when pH was not adjusted or at alkaline value. Moreover, the TOC and NH₃-N removal rates in BDD anode cell were much greater than those in other common anode systems such as SnO₂ and PbO₂ anodes cells. Given the same target to meet the National Discharge Standard of China, the energy consumption of 64 kWh kgCOD⁻¹ observed in BDD anode system was only about 60% as much as those observed in SnO₂ and PbO₂ anode systems. Further investigation revealed that, in BDD anode cell, organic pollutants were mainly degraded by reaction with free hydroxyl radicals and electrogenerated oxidants (S₂O₈²⁻, H₂O₂, and other oxidants) played a less important role, while direct electrochemical oxidation and indirect electrochemical oxidation mediated by active chlorine can be negligible. These results showed great potential of BDD anode system in engineering application as a final treatment of coking wastewater.     

Continuous treatment of the organic fraction of municipal solid waste in an anaerobic two-stage membrane process with liquid recycle

The stability and performance of a two-stage anaerobic membrane process was investigated at different organic loading rates (OLRs) and Hydraulic Retention Times (HRTs) over 200 days. The Hydrolytic Reactor (HR) was fed with the Organic Fraction of Municipal Solid Waste (OFMSW), while the leachate from the HR was fed continuously to two Submerged Anaerobic Membrane Bioreactors (SAMBR1 and 2). The Total COD (TCOD) of the leachate varied over a wide range, typically between 4000 and 26,000 mg/L while the Soluble COD (SCOD) in the permeate was in the range 400-600 mg/L, achieving a COD removal greater than 90% at a HRT of 1.6-2.3 days in SAMBR1. The operation was not sustainable below this HRT due to a membrane flux limitation at 0.5-0.8 L/m² h (LMH), which was linked to the increasing MLTSS. SCOD in the recycled permeate did not build up indicating a slow degradation of recalcitrants over time. SAMBR2 was run in parallel with SAMBR1 but its permeate was treated aerobically in an Aerobic Membrane Bioreactor (AMBR). The AMBR acted as a COD-polishing and ammonia removal step. About 26% of the recalcitrant SCOD from SAMBR2 could be aerobically degraded in the AMBR. In addition, 97.7 % of the ammonia-nitrogen was converted to nitrate in the AMBR at a maximum nitrogen-loading rate of 0.18 kg NH₄⁺-N/m³ day. GC-MS analysis was performed on the reactor effluents to determine their composition and what compounds were recalcitrant.     

Aerobic degradation of sulfanilic acid using activated sludge

This paper evaluates the aerobic degradation of sulfanilic acid (SA) by an acclimatized activated sludge. The sludge was enriched for over three months with SA (>500 mg/L) as the sole carbon and energy source and dissolved oxygen (DO, >5 mg/L) as the primary electron acceptor. Effects of aeration rate (0-1.74 L/min), DO concentration (0-7 mg/L) and initial SA concentration (104-1085 mg/L) on SA biodegradation were quantified. A modified Haldane substrate inhibition model was used to obtain kinetic parameters of SA biodegradation and oxygen uptake rate (OUR). Positive linear correlations were obtained between OUR and SA degradation rate (R² ≥ 0.91). Over time, the culture consumed more oxygen per SA degraded, signifying a gradual improvement in SA mineralization (mass ratio of O₂: SA at day 30, 60 and 120 were 0.44, 0.51 and 0.78, respectively). The concomitant release of near stoichiometric quantity of sulphate (3.2 mmol SO₄²⁻ released from 3.3 mmol SA) and the high chemical oxygen demand (COD) removal efficacy (97.1%) indicated that the enriched microbial consortia could drive the overall SA oxidation close to a complete mineralization. In contrast to other pure-culture systems, the ammonium released from the SA oxidation was predominately converted into nitrate, revealing the presence of ammonium-oxidizing bacteria (AOB) in the mixed culture. No apparent inhibitory effect of SA on the nitrification was noted. This work also indicates that aerobic SA biodegradation could be monitored by real-time DO measurement.     

Removal of veterinary antibiotics from sequencing batch reactor (SBR) pretreated swine wastewater by Fenton's reagent

The large-scale application of veterinary antibiotics in livestock industry makes swine wastewater an important source of antibiotics pollution. This work investigated the degradation of six selected antibiotics, including five sulfonamides and one macrolide, by Fenton's reagent in swine wastewater pretreated with sequencing batch reactor (SBR). The dosing mode and practical dosage of Fenton's reagent were optimized to achieve an effective removal of antibiotics while save the treatment cost. The effects of initial pH, chemical oxygen demand (COD) and suspended solids (SS) of the SBR effluent on antibiotics degradation were examined. The results indicate that the optimal conditions for Fenton's reagent with respect to practical application were as follows: batch dosing mode, 1.5:1 molar ratio of [H₂O₂]/[Fe²⁺], initial pH 5.0. Under the optimal conditions, Fenton's reagent could effectively degrade all the selected antibiotics and was resistant to the variations in the background COD (0-419 mg/L) and SS (0-250 mg/L) of the SBR effluent. Besides, Fenton's reagent helped to not only remove total organic carbon (TOC), heavy metals (As, Cu and Pb) and total phosphorus (TP), but also inactivate bacteria and reduce wastewater toxicity. This work demonstrates that the integrated process combining SBR with Fenton's reagent could provide comprehensive treatment to swine wastewater.     

Contribution of the ozonation pre-treatment to the biodegradation of aqueous solutions of 2,4-dichlorophenol

The effect of ozonation on the biodegradability of 100-ppm aqueous solutions of 2,4-dichlorophenol has been investigated. BOD at 5, 10 and 21 days, BOD/COD and BOD/TOC ratios and the average oxidation state are presented. Biodegradability measured as BOD₅/COD ratio was increased from 0 of the original solution to 0.25 at the moment of removing all the initial compound (corresponding to an ozone dose of 0.12 g L⁻¹, 0.48 for BOD₂₁/COD ratio). To test the effect of this pre-treatment, the biological oxidation of these pre-ozonated solutions was performed in two semi-continuous stirred tank reactors, one with non-acclimated sludge and one with acclimated-to-phenol sludge. The study showed that the TOC content of the pre-treated solution could be removed up to 68% by an aerobic biological treatment as well as co-digested with municipal wastewater (TOC removal up to 82%), with similar operating retention times to a municipal wastewater plant (12-24 h). Kinetic studies based on Monod model have also been carried out. Pseudo-first-order kinetic constants were found to be in the range of 0.5-0.8 L g TVSS⁻¹ h⁻¹.     

Electrochemical oxidation of table olive processing wastewater over boron-doped diamond electrodes: treatment optimization by factorial design

The electrochemical treatment of an effluent from edible olive processing over boron-doped diamond electrodes was investigated. The effect of operating conditions, such as initial organic loading (from 1340 to 5370 mg/L chemical oxygen demand (COD)), reaction time (from 30 to 120 min), current intensity (from 5 to 14 A), initial pH (from 3 to 7) and the use of 500 mg/L H2O2 as an additional oxidant, on treatment efficiency was assessed implementing a factorial experimental design. Of the five parameters tested, the first three had a considerable effect on COD and total phenols removal, while the other two were statistically insignificant. In most cases, high levels of phenols degradation and decolorization were achieved followed by moderate mineralization. The analysis was repeated at more intense conditions, i.e., initial COD up to 10,000 mg/L, reaction times up to 240 min and current up to 30 A; at this level, the effect of treatment time and applied current was far more important than the starting COD concentration. Treatment for 14 h at optimal conditions (30 A and an initial loading of about 10,000 mg/L) led to 73% COD removal with a zero-order kinetic constant of 8.5mg/(L min) and an energy consumption efficiency of 16.3 g COD/(m3 A h).     

The development of a novel hybrid aerating membrane-anaerobic baffled reactor for the simultaneous nitrogen and organic carbon removal from wastewater

A novel hybrid aerating membrane-anaerobic baffled reactor (HMABR), based on the installation of aerating membrane into an anaerobic baffled reactor (ABR), to achieve simultaneous removal of nitrogenous and carbonaceous organic pollutants was developed in this study. The results demonstrated that after the installation of membrane module, total VFA and COD concentration in the HMABR effluent were decreased by 68.1 and 59.5% respectively, with increased nitrogenous pollutant remove efficiency by 83.5%, at influent COD concentration of 1600 mg/L and NH₄⁺-N concentration of 80 mg/L. Fluorescence in situ hybridization (FISH) results of the aerating membrane biofilm showed that the biofilm stratification for the spatial profiles of ammonia-oxidizing bacteria, nitrite-oxidizing bacteria, aerobic heterotrophic bacteria, and denitrifying bacteria. The potential usage of HMABR widens the usage of aerobic-anaerobic combination technology for industrial wastewater treatment.     

Sulfate and metal removal in bioreactors treating acid mine drainage dominated with iron and aluminum

Bioreactors represent an emerging technology for removing metals and sulfate commonly found in acid mine drainage (AMD). Six continuously fed anaerobic bioreactors employing organic and alkaline waste materials were operated to investigate relationships between metal and sulfate removal from AMD. Median AMD influent chemistry was 65.8 mg/L Fe (49.7-113 mg/L), 46.5 mg/L Al (33.5-72.4 mg/L) and 608 mg/L sulfate (493-1007 mg/L). Bioreactors containing mussel shells as an alkaline substrate amendment were more effective at removing metals and sulfate than those containing limestone. Experimental results indicated bioreactor design and operation should be dependent on treatment goals. These include 0.3 mol sulfate loading/m³/day for sulfate removal (mean of 94.1% (87.6-98.0%), 0.4 mol metals/m³/day for metal (mean of 99.0% (98.5-99.9%)) and partial sulfate (mean of 46.0% (39.6-57.8%)) removal and 0.8 mol metals/m³/day for metal (mean of 98.4% (98.2-98.6%) and minimal sulfate (mean of 16.6% (11.9-19.2%)) removal. Aluminum removal efficiency was on average 1.72% (0.04-3.42%) greater than Fe during stable operating conditions.     

The sensitivity of fixed-bed biological perchlorate removal to changes in operating conditions and water quality characteristics

Flow rate, electron donor addition, and biomass control were evaluated in order to optimize perchlorate (ClO₄⁻) removal from drinking water using biologically active carbon (BAC) filtration. Influent dissolved oxygen (DO) was lowered from ambient conditions to approximately 2.5 mg/L for all experiments using a nitrogen sparge. When influent nitrate concentration was 0-2.0 mg/L, 1.6-2.8 mg/L as carbon of acetate or ethanol was required to achieve and sustain the complete removal of 50 μg/L perchlorate in a BAC filter. Most or all of the exogenous acetate and ethanol was removed during biofiltration. When a 72-h electron donor feed failure was simulated, a maximum perchlorate breakthrough of 18 μg/L was observed and, once electron donor was reapplied, 9 days were required to reestablish complete perchlorate removal. During a 24-h electron donor feed failure simulation, the maximum effluent perchlorate concentration detected was 6.7 μg/L. Within 24 h of reactivating the electron donor, the filter regained its capacity to consistently remove 50 μg/L perchlorate to below detection. Although biomass growth diminished the filter's ability to consistently remove perchlorate, a cleaning procedure immediately restored stable, complete perchlorate removal. This cleaning procedure was required approximately every 50 days (4800 bed volumes) when influent DO concentration was 2.5 mg/L. Empty-bed contact time (EBCT) experiments showed that 80% perchlorate removal was achieved using a 5-min EBCT, and complete perchlorate removal was observed for an EBCT of 9 min. It was also demonstrated that BAC filtration consistently removed perchlorate to below detection for influent perchlorate concentrations ranging from 10 to 300 μg/L, influent sulfate concentrations between 0 and 220 mg/L, influent pH values of 6.5-9.0, and operating temperatures of 5-22°C.     

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 33,400 mg/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.     

Drugs degrading photocatalytically: Kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions

The conversion of the antibiotic ofloxacin and the β-blocker atenolol by means of TiO₂ photocatalysis was investigated. Irradiation was provided by a UVA lamp at 3.37 × 10⁻⁶ einstein/s photon flux, while emphasis was given on the effect of catalyst type and loading (50-1500 mg/L), initial substrate concentration (5-20 mg/L), initial pH (3-10) and the effect of H₂O₂ (0.07-1.4 mM) as an additional oxidant on substrate conversion and mineralization in various matrices (i.e. pure water, groundwater and treated municipal effluent). Conversion was assessed measuring sample absorbance at 288 and 224 nm for ofloxacin and atenolol, respectively, while mineralization measuring the dissolved organic carbon. Degussa P25 TiO₂ was found to be more active than other TiO₂ samples for either substrate degradation, with ofloxacin being more reactive than atenolol. Conversion generally increased with increasing catalyst loading, decreasing initial substrate concentration and adding H₂O₂, while the effect of solution pH was substrate-specific. Reaction rates, following a Langmuir-Hinshelwood kinetic expression, were maximized at a catalyst to substrate concentration ratio (w/w) of 50 and 15 for ofloxacin and atenolol, respectively, while higher ratios led to reduced efficiency. Likewise, high concentrations of H₂O₂ had an adverse effect on reaction, presumably due to excessive oxidant scavenging radicals and other reactive species. The ecotoxicity of ofloxacin and atenolol to freshwater species Daphnia magna was found to increase with increasing substrate concentration (1-10 mg/L) and exposure time (24-48 h), with atenolol being more toxic than ofloxacin. Photocatalytic treatment eliminated nearly completely toxicity and this was more pronounced for atenolol.     

Ultrasonic enhancement of waste activated sludge hydrolysis and volatile fatty acids accumulation at pH 10.0

Volatile fatty acids (VFA), the preferred carbon source for biological nutrients removal, can be produced by waste activated sludge (WAS) anaerobic fermentation. However, because the rate of VFA accumulation is limited by that of WAS hydrolysis and VFA is always consumed by methanogens at acidic or neutral pHs, the ultrasonic pretreatment which can accelerate the rate of WAS hydrolysis, and alkaline adjustment which can inhibit the activities of methanogens, were, therefore, used to improve WAS hydrolysis and VFA accumulation in this study. Experiment results showed that the combination of ultrasonic pretreatment and alkaline adjustment caused significant enhancements of WAS hydrolysis and VFA accumulation. The study of ultrasonic energy density effect revealed that energy density influenced not only the total VFA accumulation but also the percentage of individual VFA. The maximal VFA accumulation (3109.8 mg COD/L) occurred at ultrasonic energy density of 1.0 kW/L and fermentation time of 72 h, which was more than two times that without ultrasonic treatment (1275.0 mg COD/L). The analysis of VFA composition showed that the percentage of acetic acid ranked the first (more than 40%) and those of iso-valeric and propionic acids located at the second and third places, respectively. Thus, the suitable ultrasonic conditions combined with alkaline adjustment for VFA accumulation from WAS were ultrasonic energy density of 1.0 kW/L and fermentation time of 72 h. Also, the key enzymes related to VFA formation exhibited the highest activities at ultrasonic energy density of 1.0 kW/L, which resulted in the greatest VFA production during WAS fermentation at pH 10.0.     

High-rate anaerobic treatment of Fischer-Tropsch wastewater in a packed-bed biofilm reactor

This study investigates the anaerobic treatment of an industrial wastewater from a Fischer-Tropsch (FT) process in a continuous-flow packed-bed biofilm reactor operated under mesophilic conditions (35 °C). The considered synthetic wastewater has an overall chemical oxygen demand (COD) concentration of around 28 g/L, mainly due to alcohols. A gradual increase of the organic load rate (OLR), from 3.4 gCOD/L/d up to 20 gCOD/L/d, was adopted in order to overcome potential inhibitory effects due to long-chain alcohols (>C6). At the highest applied OLR (i.e., 20 gCOD/L/d) and a hydraulic retention time of 1.4 d, the COD removal was 96% with nearly complete conversion of the removed COD into methane. By considering a potential of 200 tCOD/d to be treated, this would correspond to a net production of electric energy of about 8 × 10⁷ kWh/year.During stable reactor operation, a COD balance and batch tests showed that about 80% of the converted COD was directly metabolized through H₂⁻ and acetate-releasing reactions, which proceeded in close syntrophic cooperation with hydrogenotrophic and acetoclastic methanogenesis (contributing to about 33% and 54% of overall methane production, respectively). Finally, energetic considerations indicated that propionic acid oxidation was the metabolic conversion step most dependent on the syntrophic partnership of hydrogenotrophic methanogens and accordingly the most susceptible to variations of the applied OLR or toxicity effects.     

Operation of suspended-growth shortcut biological nitrogen removal (SSBNR) based on the minimum/maximum substrate concentration

This study exploited the concept of the minimum/maximum substrate concentrations (MSC values) for identifying proper start-up conditions and achieving stable and low effluent total ammonium nitrogen (TAN) concentrations in suspended-growth short-cut biological nitrogen removal (SSBNR). Calculations based on the MSC concept indicated that S_Dmax, the TAN concentration above which ammonium-oxidizing bacteria (AOB) are washed out, was around 450 mgTAN/L at the given operating conditions of 2 mg/L of dissolved oxygen and pH 8, while nitrite-oxidizing bacteria (NOB) should be washed out at around 40 mgTAN/L. Therefore, the experimental research was focused on the optimal TAN-concentration range for SSBNR, between 50 and 100 mg/L. Experimental results showed that a nitrification reactor with initial TAN concentration above 450 mg/L did not give a successful start-up. However, two days of starvation, which decreased the TAN concentration in the reactor to 95 mg/L, stabilized the reaction quickly, and stable SSBNR was sustained thereafter with 80 mgTAN/L and 98% nitrite accumulation in the reactor. During stable SSBNR, the removal ratio of chemical oxygen demand per nitrite nitrogen (ΔCOD/ΔNO₂-N) for denitrification was 1.94 gCOD/gN, which is around 55% of that required for nitrate denitrification. Based on a clone library, Nitrosomonas occupied 14% of the total cells, while the sum of Nitrobacter and Nitrospira was less than the detection cut-off of 2%, confirming the NOB were washed out during SSBNR. A spiking test that doubled the influent ammonium loading caused the TAN concentration in the reactor to reach washout for AOB, which lasted until the loading was reduced. Thus, a loading increase should be controlled carefully such that the system does not exceed the washout range for AOB.     

Bioaugmentation with the nicotine-degrading bacterium Pseudomonas sp. HF-1 in a sequencing batch reactor treating tobacco wastewater: Degradation study and analysis of its mechanisms

The highly effective nicotine-degrading bacterium Pseudomonas sp. HF-1 was augmented in an SBR system that is used to treat tobacco wastewater. Compared to the non-bioaugmented (non-BA) system, the bioaugmented (BA) system exhibited considerably stronger pollution disposal abilities, with 100% nicotine degradation and more than 84% chemical oxygen demand (COD) removal within 12 h. Nicotine degradation had a significant effect on COD removal in SBRs (r = 0.928, p < 0.01). The mechanisms of bioaugmentation were systematically investigated using a combination of polymerase chain reaction and denaturing gradient gel electrophoresis (PCR-DGGE) and a toxicity assay (protein carbonyl (PC) and DNA-protein crosslinking (DPC)). DGGE fingerprint profiles showed that the number of bands and the Shannon-Wiener index decreased at a nicotine load of 250 mg/L compared to a 40-130 mg/L nicotine load in the non-BA system. However, a stepwise increase in the Shannon-Wiener index was found during all periods in the BA system. A comparison of sequences excised from DGGE gels demonstrated significant differences in the dominant microbial species between the two SBRs. This result suggested that bioaugmentation of strain HF-1 could select cooperators for treating complicated tobacco wastewater. The PC content and the DPC coefficient increased significantly at levels higher than 80 mg/L in the non-BA system; nevertheless, no increase was observed in the BA system during the stepwise nicotine load. This indicated that bioaugmentation of strain HF-1 resulted in the maintenance of high treatment activity by minimizing the nicotine toxicity for other microbes in the BA system. In conclusion, the rapid nicotine degradation of strain HF-1 performed a vital function in SBR by influencing the microbial community structure, dynamics and activity of the activated sludge system.     

Polyaluminum chloride with high Al30 content as removal agent for arsenic-contaminated well water

Polyaluminum chloride (PACl) is a well-established coagulant in water treatment with high removal efficiency for arsenic. A high content of Al₃₀ nanoclusters in PACl improves the removal efficiency over broader dosage and pH range. In this study we tested PACl with 75% Al₃₀ nanoclusters (PACl_Al30) for the treatment of arsenic-contaminated well water by laboratory batch experiments and field application in the geothermal area of Chalkidiki, Greece, and in the Pannonian Basin, Romania. The treatment efficiency was studied as a function of dosage and the nanoclusters’ protonation degree. Acid-base titration revealed increasing deprotonation of PACl_Al30 from pH 4.7 to the point of zero charge at pH 6.7. The most efficient removal of As(III) and As(V) coincided with optimal aggregation of the Al nanoclusters at pH 7-8, a common pH range for groundwater. The application of PACl_Al30 with an Al_tot concentration of 1-5 mM in laboratory batch experiments successfully lowered dissolved As(V) concentrations from 20 to 230 μg/L to less than 5 μg/L. Field tests confirmed laboratory results, and showed that the WHO threshold value of 10 μg/L was only slightly exceeded (10.8 μg/L) at initial concentrations as high as 2300 μg/L As(V). However, As(III) removal was less efficient (<40%), therefore oxidation will be crucial before coagulation with PACl_Al30. The presence of silica in the well water improved As(III) removal by typically 10%. This study revealed that the Al₃₀ nanoclusters are most efficient for the removal of As(V) from water resources at near-neutral pH.     

Electro-oxidative abatement of low-salinity reverse osmosis membrane concentrates

The present study encompasses the application of electrolysis as novel treatment technique for the abatement of low-salinity concentrates generated from the filtrative treatment of water and wastewater. Four different materials have been tested as anode for a number of brine samples in a one-compartment electrolytic cell in galvanostatic mode. It was found that PbO(2) and SnO(2) anodes initiated electrochemical precipitation through an increase of the pH. Boron-doped diamond (BDD) and RuO(2) anodes successfully oxidised the pollutants in the brine and a linear removal of total ammonia nitrogen (TAN) and chemical oxygen demand (COD) was observed during the first phase of oxidation. Oxidation was predominantly achieved through indirect hypochlorite bulk oxidation; the higher oxidation rate and extent for the BDD anode was attributed to the higher selectivity and activity of the latter. Overall performance of the BDD electrode was higher than for RuO(2): higher rates for TAN (17.9 vs. 13.5mg/Ah) and COD (74.5 vs. 20.0mg/Ah) removal as well as higher overall current efficiencies (35.2% vs. 14.5%). Extensive colour removal was observed for both anodes (>90% decrease in absorbency at 455 nm).     

Effect of COD/SO4ratio and Fe(II) under the variable hydraulic retention time (HRT) on fermentative hydrogen production

The effect of chemical oxygen demand/sulfate (COD/SO₄²⁻) ratio on fermentative hydrogen production using enriched mixed microflora has been studied. The chemostat system maintained with a substrate (glucose) concentration of 15 g COD L⁻¹ exhibited stable H₂ production at inlet sulfate concentrations of 0-20 g L⁻¹ during 282 days. The tested COD/SO₄²⁻ ratios ranged from 150 to 0.75 (with control) at pH 5.5 with hydraulic retention time (HRT) of 24, 12 and 6 h. The hydrogen production at HRT 6 h and pH 5.5 was not influenced by decreasing the COD/SO₄²⁻ ratio from 150 to 15 (with control) followed by noticeable increase at COD/SO₄²⁻ ratios of 5 and 3, but it was slightly decreased when the COD/SO₄²⁻ ratio further decreased to 1.5 and 0.75. These results indicate that high sulfate concentrations (up to 20,000 mg L⁻¹) would not interfere with hydrogen production under the investigated experimental conditions. Maximum hydrogen production was 2.95, 4.60 and 9.40 L day⁻¹ with hydrogen yields of 2.0, 1.8 and 1.6 mol H₂ mol⁻¹ glucose at HRTs of 24, 12 and 6 h, respectively. The volatile fatty acid (VFA) fraction produced during the reaction was in the order of butyrate > acetate > ethanol > propionate in all experiments. Fluorescence In Situ Hybridization (FISH) analysis indicated the presence of Clostridium spp., Clostridium butyricum, Clostridium perfringens and Ruminococcus flavefaciens as hydrogen producing bacteria (HPB) and absence of sulfate reducing bacteria (SRB) in our study.