Use of advance oxidation process to improve the biodegradability of olive oil mill effluents

In this study, recalcitrant total phenol (TPh) and organic matter removal were investigated at olive mill wastewater (OMW) in sequential Coagulation and Fenton system. This study focused on different operational parameters such as pH, H₂O₂, and Fe²⁺ dosages, and [Fe²⁺]/[H₂O₂] ratios. The optimum conditions were determined as; pH = 3; [Fe²⁺] = 2.5 g/L; [Fe²⁺]/[H₂O₂] = 2.5. A higher treatment efficiency was achieved at sequential Coagulation and Fenton system (COD, 65.5%) and TPh, 87.2%), compared to coagulation process (COD, 51.4%; total organic carbon (TOC), 38.6% and total nitrogen (TN) 52.1%). This study demonstrated that the Coagulation and Fenton process has a potential for efficient removal of phenolic pollutants from wastewater.     

Removal of humic substances from landfill leachate by Fenton oxidation and coagulation

In this study, chemical oxygen demand (COD) was characterized as total organic constituents and the isolated humic substances (HS) were characterized as an individual organic contaminant in landfill leachate. It was found that the HS content of landfill leachate was 83.3%. The results of laboratory tests to determine the roles of HS in reducing the organic content of landfill leachate during Fenton process are presented. Furthermore, the performances of oxidation and coagulation of Fenton reaction on the removal of HS and COD from leachate were investigated. The change curves of HS removal were similar to those of COD. The HS removal was 30% higher than COD removal, which indicated that HS were mostly degraded into various intermediate organic compounds but not mineralized by Fenton reagent. The oxidation removal was greatly influenced by initial pH relative to the coagulation removal. The oxidation and coagulation removals were linear dependent with hydrogen peroxide and ferrous dosages, respectively. Ferrous dosage greatly influenced the coagulation removal of COD at low ratio ([H₂O₂]/[Fe²⁺] < 3.0), but not at extremely high ratio ([H₂O₂]/[Fe²⁺] > 6.0). The coagulation removal of HS was not affected obviously by oxidation due to both Fenton oxidation and coagulation remove high molecular weight organics preferentially. Higher temperature gave a positive effect on oxidation removal at low Fe²⁺ dosage, but this effect was not obvious at high Fe²⁺ dosage.     

Disintegration of municipal waste activated sludge by simultaneous combination of acid and ultrasonic pretreatment

The individual and simultaneous effects of acid and ultrasonic pretreatment on the disintegration of municipal waste activated sludge (WAS) were investigated based on chemical properties of WAS. In the combination of acid and ultrasonic pretreatment methods (ultrasonic-acid pretreatment), lowering pH accelerated and enhanced the disintegration of waste biological sludge. Therefore, the same disintegration efficiency (obtained by ultrasonic pretreatment alone) was achieved by the combined pretreatment in shorter sonication times. Optimum pretreatment conditions were ultrasonic power density of 1.0 W/mL and pretreatment time of 10 min for ultrasonic pretreatment alone, and ultrasonic power density of 1.0 W/mL, pretreatment time of 10 min and initial sludge pH of 2.0 for the combined pretreatment. Sludge disintegration degrees were about 30% and 40% under these optimized conditions, respectively. Optimum sludge concentration was found to be 1.0% total solid (TS) content for the combined pretreatment. As a result, ultrasonic-acid pretreatment has been determined as a new and effective combined sludge pretreatment method to improve the sludge disintegration.     

Improving disintegration and acidification of waste activated sludge by combined alkaline and microwave pretreatment

The individual alkaline or microwave pretreatment has been proved to be effective in disintegration and acidification of waste activated sludge (WAS). In this study, the effects of combined alkaline and microwave pretreatment at different pH and specific energy input (Es) on WAS disintegration were investigated using response surface methodology (RSM). Combined pretreatment achieved disintegration degree (DD) of 65.87% at Es of 38,400 kJ/kg TS and pH 11.0. The ANOVA further demonstrated that pH showed more significant effect on DD than Es. Anaerobic batch experiment results showed that combined pretreatment not only significantly improved volatile fatty acids (VFAs) accumulation but also shortened the time for the highest VFAs accumulation. The maximal VFAs accumulation (1500 mg COD/L) obtained at Es of 28,800 kJ/kg TS and fermentation time of 72 h, which was about two times that of the treatment without microwave (850 mg COD/L) at 96 h. The analysis of VFAs composition showed that the VFAs mainly consisted of acetic and iso-valeric acids, accounting for 57.3–70.1% of total VFAs.     

Removal of H2S by co-immobilized bacteria and fungi biocatalysts in a bio-trickling filter

Biological control of odor gases has gained more attention in recent years. In this study, removal performance of a vertical bio-trickling filter inoculated with bacteria and fungi was studied. Bacteria and fungi were isolated from activated sludge in a sewage treatment plant. By adopting “three step immobilization method”, the bio-trickling filter could degrade pollutant immediately once hydrogen sulfide (H₂S) passed. The optimal empty bed resident time was 20 s. The optimal elimination capacity was about 60 g H₂S m^?3 h^?1 with removal efficiency of 95%. And the maximum elimination capacity was 170 g H₂S m^?3 h^?1. Pressure drop was ranged between 5 and 15 mm H₂O per bed over the whole operation. Removal efficiency was not affected obviously after terminating nutrient supply. The bio-trickling filter could recover back after shut down H₂S gaseous and liquid supplies simultaneously. Microbial community structure in the bio-trickling filter was not changed significantly.Combining bacteria and fungi would be a better choice for inoculation into a bio-trickling filter because of the quickly degradation of H₂S and rapid recovery under shut-down experiment. This is the first study attempting to combine bacteria and fungi for removal of H₂S in a bio-trickling filter.     

An explosion of a tank car carrying waste hydrogen peroxide

On the Metropolitan Expressway in Tokyo, a tank car exploded because it was carrying hydrogen peroxide (H₂O₂) in a compartment in which copper chloride (CuCl₂) remained. Although the main cause of the accident was trivial, the background on the accident suggested that an induction period in the reaction led to a mistake. This report describes the experimental investigation of the catalytic ability of CuCl₂, and comparing it with two other copper(II) compounds (nitrate: Cu(NO₃)₂; and copper sulfate: CuSO₄) and three iron(III) compounds (chloride: FeCl₃; nitrate: Fe(NO₃)₃; and sulfate: Fe₂(SO₄)₃).The experiments were performed using a reaction calorimeter. During the experiments at 35 °C, 2×10⁻⁵ mol of copper compounds slowly reacted with H₂O₂ and generated a precipitate. The iron compounds allowed the hydrogen peroxide to violently decompose. A 1×10⁻⁴ mol solution of CuCl₂, however, produced a violent decomposition at 35 °C. At 15 °C, a moderate heat release occurred.Based on these results, the concentration and temperature dependence of the catalytic ability of CuCl₂ were postulated to contribute to the induction period observed in the accident.     

Kinetics of nitrate reductive denitrification by nanoscale zero-valent iron

Nanoscale zero-valent iron (Fe⁰) was synthesized for nitrate denitrification. The reduction efficiency of nitrate decreased quickly with increasing initial pH value, increased considerably with the increasing dosage of nanoscale Fe⁰, and did not vary much with initial nitrate concentrations changing from 20 to 50 mg l^?1 when the excessive amount of nanoscale Fe⁰ was utilized. With reductive denitrification of nitrate by nanoscale Fe⁰, the removal rate of nitrate reached 96.4% in 30 min with nanoscale Fe⁰ dosage of 1.0 g l^?1 and pH_in 6.7, and more than 85% of the nitrate was transformed into ammonia. Kinetics analysis in batch studies demonstrates that the denitrification of nitrate by nanoscale Fe⁰ involves reaction on the metal surface, which fits well the pseudo-first order reaction with respect to nitrate concentration. The observed reaction rate constant of reductive denitrification of nitrate was determined to be 0.086 min^?1 with a nanoscale Fe⁰ dosage of 1.0 g l^?1 and pH_in 6.7. Fast and highly effective denitrification can be achieved by nanoscale Fe⁰ compared with commercial Fe⁰ powder, this is due to the extremely high surface area and high reactivity for nanoscale Fe⁰, which can enhance the denitrification efficiencies remarkably.     

Partial nitritation of landfill leachate with varying influent composition under intermittent aeration conditions

The start-up and operation of a partial nitritation sequencing batch reactor for the treatment of landfill leachate were carried out on intermittent aeration mode. Partial nitrite accumulation was established in 15 days after the mode was changed from continuous aeration to intermittent aeration. Despite the varying influent composition, partial nitritation could be maintained by adjusting the hydraulic retention time (HRT) and the air flow rate. An increase in the air flow rate together with a decrease in air off duration can improve the partial nitritation capacity and eventually result in the development of granular sludge with fine diameters. A nitrogen loading rate of 0.71 ± 0.14 kg/m³/d and a COD removal rate of 2.21 ± 0.13 kg/m³/d were achieved under the conditions of an air flow rate of 19.36 ± 1.71 m³ air/m³/h and an air on/off duration of 1.5 min/0.7 min. When the ratio of total air flux (TAF) to the influent loading rate (ILR) was controlled at the range of 163–256 m³ air/kg COD, a stable effluent NO₃^?–N/NO_x^?–N (NO₂^?–N plus NO₃^?–N) ratio below 13% was achieved. Interestingly, the effluent pH was found to be a good indicator of the effluent NO₂^?–N/NH₄⁺–N ratio, which is an essential parameter for a subsequent anaerobic ammonium oxidation (Anammox) reactor.     

Drop in dry mass and organic substance content in the process of autothermal thermophilic aerobic digestion

This paper presents the results of a study of a sludge subjected to the (ATAD) process – Autothermal Thermophilic Aerobic Digestion occurring in a two-stage installation operated in a municipal wastewater treatment plant in Olecko, Poland. The study of the sludge and the analysis of obtained results were conducted over 2011 and 2014. The subject of the study was a thickened sludge in an intermediate tank from which it was next transferred to facility reactors. The stabilization of processed sludge was evaluated analyzing the change in the dry mass (DS) content in the sludge. Measurements were carried out in thickened sludge samples and after the ATAD process. Collected results were then subjected to a statistical analysis and it was determined to which extent as resulted from the subject process the dry mass and the dry organic mass (VS) content was changing in the sludge. Also, it was analyzed how the oxygen chemical demand (COD) was changing. The dry mass content in the thickened sludge was from 60 g/l to 160 g/l. After the process, this amount was from 35 to 76 g/l. Similarly, the organic mass content in a dry sludge mass changed from initial values within a range of 44–135 g/l to 23–60 g/l after the ATAD process. Also, the organic substance content expressed as COD decreased from 80 to 467 g O₂/l in a thickened sludge to 51–261 g O₂/l in the sludge after the process. The article presents conclusions from the result of the conducted study as well as personal experience.     

Biohydrogen production using waste activated sludge as a substrate from fructose-processing wastewater treatment

Biohydrogen production by dark fermentation in a series of batch tests under different environmental control conditions was evaluated to determine the optimal initial cultivation pH and temperature for a continuous-flow kinetic test to validate the kinetic model system. The waste activated sludge (WAS) from fructose-processing manufacturing was used as the model substrate for biohydrogen production. The batch experiments for biohydrogen production were conducted in a 6 l bioreactor. Fifteen batch kinetic tests were investigated when pH was controlled at 6, 7, 8 and 9 as well as the temperature was controlled at 37 °C, 45 °C and 55 °C, respectively. The experimental results indicated that the optimal operational condition for hydrogen production occurred while pH was 7 and temperature was 55 °C with the highest hydrogen production of 7.8 mmol. The optimal recovery time for hydrogen was 25 h in the batch experiments. Furthermore, the kinetic test of biohydrogen production was performed by anaerobic mixed microbial culture in the continuous-flow experiment when pH and temperature was maintained at 7 and 55 °C. Approximately 60% and 7% of substrate solution was converted into acetate and hydrogen, respectively, at the steady state. Roughly only 0.77% and 2.7% of substrate solution was converted into propionate and butyrate, respectively, at a steady-state condition. The experimental and modeling approaches presented in this study could be employed for the design of pilot-scale and full-scale anaerobic biohydrogen fermentors using food-processing waste activated sludge (WAS) as a substrate solution.     

Removal mechanism of trace oxytetracycline by aerobic sludge

To investigate the mechanism of removal of selected pharmaceuticals in activated sludge systems, laboratory-scale batch experiments were conducted to assess the adsorption and degradation behavior of trace oxytetracycline (OTC). The adsorption equilibrium of OTC was observed in 30 min and the adsorption process could be well described by a pseudo-second-order model with a rate of 0.362 L μg^?1 min^?1. The OTC adsorption rate decreased with increasing temperature and could be fitted by the Freundlich isotherm. The linear partition coefficients (K_d) were 1.19, 0.999, and 0.841 L g^?1 at temperatures of 15, 20, and 25 °C, respectively. Thermodynamic analysis revealed that the adsorption of OTC onto the inactivated sludge was spontaneous (ΔG = ?16.7 to ?17.0 kJ mol^?1), enthalpy-driven (ΔH = ?24.9 kJ mol^?1), entropy-retarded (ΔS = ?27.4 J (mol K)^?1), and predominantly a physical adsorption.     

Performance of a pilot scale up-flow septic tank for on-site decentralized treatment of residential wastewater

The aim of this research was to study the on-site anaerobic treatment of a medium-strength residential wastewater in a pilot-scale up-flow septic tank (UST). The effects of three different hydraulic retention times (HRTs) of 24, 12 and 6 h on the UST performance were investigated. The UST removed 85, 77, and 86% of biochemical oxygen demand (BOD₅), chemical oxygen demand (COD) and total suspended solids (TSS), respectively, at steady state operation and with a 24 h HRT. Decreasing the HRT to 12 and then 6 h resulted in deteriorated effluent quality and significantly reduced reactor performance. The sludge showed a high specific methanogenic activity (SMA) of 15.2 mL CH₄ g^?1 VSS d^?1 with raw wastewater substrate. The solids accumulated in the tank by the end of the experiment had a VSS/TSS of 0.57, demonstrating significant stabilization. Overall, the UST is concluded to be a technically and economically promising alternative to conventional septic tanks for the on-site decentralized treatment of residential wastewater, particularly in the rural communities of developing countries.     

Calorimetric behaviors of N2H4 by DSC and superCRC

The objective of this study is to obtain information about the thermal decomposition behaviors of hydrazine (N₂H₄) caused by metals, using differential scanning calorimeter (DSC) and SuperCRC. The DSC measurements revealed that the exothermic reactions of N₂H₄ were caused by the reaction conditions such as the type of cells; the T_DSC with a gold pan is 485.2 K and that with a glass capillary is 620.5 K. Besides, the activation energy of the thermal decomposition of N₂H₄, calculated from the Kissinger and Ozawa methods, were found to be about 38±2 kJ mol⁻¹ in the gold pan and 141±8 kJ mol⁻¹ in the glass capillary. Moreover, a heat flow profile was observed with SuperCRC during the mixing of N₂H₄ and the metal ion solution at 298 K. The maximum heat flow was related to the metal ion oxidative characters. The higher oxidative characters would provide a faster acceleration for the exothermic behavior than the lower oxidative ions. Based on this study, Mn(VII) and Cr(VI) were considered to exhibit strongly oxidative characteristics during mixing with N₂H₄.     

Decolorization of synthetic Methyl Orange wastewater by electrocoagulation with periodic reversal of electrodes and optimization by RSM

Treatment of Methyl Orange (MO), an azo dye, synthetic wastewater by electrocoagulation with periodic reversal of the electrodes (PREC) was examined. Response Surface Methodology (RSM) was used to optimize the influence of experimental conditions for color removal (CR), energy consumption (ENC), electrode consumption (ELC) and sludge production (SP) per kg MO removed (kg(MO_r)) with optimal conditions being found to be pH 7.4, solution conductivity (к) 9.4 mS cm⁻¹, cell voltage (U) 4.4 V, current density (j) 185 mA cm⁻², electrocoagulation time (T) 14 min, cycle of periodic reversal of electrodes (t) 15 s, inter-electrode distance (d) 3.5 cm and initial MO concentration of 125 mg L⁻¹. Under these conditions, 97 ± 2% color was removed and ENC, ELC and SP were 44 ± 3 kWh kg(MO_r)⁻¹, 4.1 ± 0.2 kg(Al) kg(MO_r)⁻¹ and 17.2 ± 0.9 kg(sludge) kg(MO_r)⁻¹, respectively. With the enhanced electrochemical efficiency resulting from the periodic electrode reversal, the coefficients of increased resistance and decreased current density between the two electrodes in the PREC setup were 2.48 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.29 mA cm⁻² min⁻¹, respectively, as compared to 7.72 × 10⁻⁴ Ω cm⁻² min⁻¹ and 0.79 mA cm⁻² min⁻¹ as measured for the traditional electrocoagulation process. The rate constant of decolorization was also enhanced by 20.4% from 0.152 min⁻¹ in the traditional electrocoagulation process to 0.183 min⁻¹ in the PREC process. These performance characteristics indicate that the PREC approach may be more promising in terms of practical application, as a cost-effective treatment, than conventional electrocoagulation for textile dye removals.     

An Experimental Study on Pyrolysis of Biomass

In this study, pyrolysis of sugarcane bagasse was performed in fixed bed tubular reactor under the conditions of nitrogen atmosphere, by varying temperature and different particle sizes. The effect of final pyrolysis temperature from 400 to 500°C and the nitrogen flow rate from 50 to 200 cc min⁻¹ on the pyrolysis product yields from sugarcane bagasse have been investigated. The Maximum bio-oil yield obtained is 24.12 wt% at the final pyrolysis temperature of 450°C, N₂ flow rate of 50 cc min⁻¹ and particle size of mesh number −8 + 12. The yield of bio-oil decreases with increase in temperature from 450 to 550°C and N₂ flow rate from 50 to 200 cc min⁻¹. The various characteristics of pyrolysis oil obtained under these conditions were identified on the basis of standard test methods. The empirical formula of pyrolysis oil with a heating value of 37.01 MJ Kg⁻¹ was established as CH_1.434 O_0.555 N_0.004. The results from the pyrolysis show the potential of sugarcane bagasse as an important source of liquid hydrocarbon fuel.     

Growing Carbon Nanotube on Aluminum Oxides: An Inherently Safe Approach for Environmental Applications

Using micron-sized Al₂O₃ particles as carriers to grow carbon nanotubes (CNTs) under 700°C atmosphere of methane and hydrogen after pre-planted catalysts of Fe–Ni nanoparticles, those composite CNTs (CCNTs) have demonstrated several unique properties compared to CNTs—medium specific surface area and zeta potential, high adsorption capacity for metal ions, high recovery rate by acids, low decomposition heat for exothermal reaction, and so on. The adsorption behaviours of Pb²⁺, Cu²⁺ and Cd²⁺ in aqueous solutions by CCNTs are in good agreement with the Langmuir adsorption isotherm and second order kinetic model with maximum individual adsorption capacities of 67.11, 26.59 and 8.89 mg g⁻¹. The individual and competitive adsorption behaviours indicated that the preference order of adsorption were Pb²⁺ > Cu²⁺ > Cd²⁺ for aluminum oxides, activated carbon, commercial CNTs, and CCNTs as well as other researchers’ CNTs. We suggest that future development of CNTs to combine with metals and/or other materials, such as TiO₂, should consider attached to carriers or surface in order to avoid concerns on environment, health and safety. Thus, growing CNTs on Al₂O₃ particles to form CCNTs is an inherently safe approach for many promising environmental applications.     

Effects of applied voltage on hydrogen production rate of a single reactor BML with Clostridium sp.

This study aimed to explore the influences of single-chamber systems with different applied voltage on bio-hydrogen (H₂) production. The reactor used was the bio-electrochemically assisted microbial reactor (BEAMR) membrane-less (BEAMR-membrane-less, BML). The microbial dark fermentative H₂ production method was adopted. After the hot screening process and the DNA sequencing, the domesticated dominant microflora was Clostridium sp. This study discussed the influences of the cases with (continuous and intermittent) and without applied voltage separately. The results showed that, the H₂ production rate of the case with intermittent applied voltage (117 mL/h g VSS) of 0.24 V was increased of 1.7 folds higher than the without applied voltage (69 mL/h g VSS) and 1.3 folds higher than the case with continuous applied voltage (88.2 mL/h g VSS) of 0.24 V. The produced H₂ concentration with intermittent applied voltage was 18.9% (18.6–19.1%) higher than the without applied voltage, while there was no significant difference with continuous applied voltage.     

7 mT static magnetic exposure enhanced synthesis of poly-3-hydroxybutyrate by activated sludge at low temperature and high acetate concentration

The effect of 7 mT (milliTesla) SMF (static magnetic field) on poly-3-hydroxybutyrate (PHB) production was studied at an acetate concentration of 260 Cmmol l^?1 and temperature of 10 °C. The SMF decreased the specific acetate uptake rate by 29%, but increased the maximum PHB content and the yield of PHB on acetate by 32 and 28% respectively. The ratio q_P/(q_S ? q_P), which described specific PHB production rate over the difference between specific acetate uptake rate and specific PHB production rate, was introduced for evaluation of the ratio of carbon flux into PHB synthesis and into the TCA (tricarboxylic acid) cycle. This value reached 2.3 when activated sludge culture was exposed to magnetic field of 7 mT, which was 1.1 times higher than the q_P/(q_S ? q_P) value obtained without magnetic exposure. Therefore, the SMF promoted diversion of more acetyl-CoA towards PHB synthesis and could offset adverse effects of high acetate concentration and low temperature. These results provide evidence that SMF enhances PHB production by activated sludge.     

Optimization and evaluation of an air-recirculated stripping for ammonia removal from the anaerobic digestate of pig manure

An air-recirculated stripping involved two processes and did not require any pretreatment. First, stripping CO₂ decreased the buffer capacity of the anaerobic digestate, thereby reducing the amount of lime used to achieve a high pH. Second, lime was added to increase pH and remove ammonia from the anaerobic digestate of pig manure. pH increased from 8.03 to 8.86 by stripping CO₂ in the first process (gas-to-liquid ratio = 180) and further reached 12.38 in the second process (gas-to-liquid ratio = 300). During process optimization, the maximum ammonia removal efficiency reached 96.78% with a lime dose of 22.13 g. The value was close to 98.25%, which was the optimal result predicted by response surface methodology using the software Design-Expert 8.05b. All these results indicated that air-recirculated stripping coupled with absorption was a promising technology for the removal and recovery of nitrogen in the anaerobic digestate of pig manure.     

Refinery wastewater degradation with titanium dioxide,zinc oxide,and hydrogen peroxide in a photocatalytic reactor

This paper presents the photo-catalytic degradation of real refinery wastewater from National Refinery Limited (NRL) in Karachi, Pakistan, using TiO₂, ZnO, and H₂O₂. The pretreatment of the refinery effluent was carried out on site and pretreated samples were tested at 32–37 °C in a stirrer bath reactor by using ultra-violet photo oxidation process. The degradation of wastewater was measured as a change in initial chemical oxygen demand (COD) and with time. Optimal conditions were obtained for catalyst type, and pH. The titanium dioxide proved to be very effective catalysts in photo-catalytic degradation of real refinery wastewater. The maximum degradation achieved was 40.68% by using TiO₂ at 37 °C and pH of 4, within 120 min of irradiations. When TiO₂ was combined with H₂O₂ the degradation decreased to 25.35%. A higher reaction rate was found for titanium dioxide. The results indicate that for real refinery wastewater, TiO₂ is comparatively more effective than ZnO and H₂O₂. The experiments indicated that first-order kinetics can successfully describe the photo-catalytic reaction. The ANOVA results for the model showed satisfactory and reasonable adjustment of the second-order regression model with the experimental data. The ANOVA results also showed that pH is significant than reaction time and catalyst dosage of TiO₂; and in case of ZnO, reaction time is significant than pH and catalyst dosage. This study proves that real refinery wastewater reacts differently than synthetic refinery wastewater, oil field produced water or oil water industrial effluent.