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.     

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.     

Preparation of iodine doped titanium dioxide to photodegrade aqueous bisphenol A under visible light

Highly photoactive iodine-doped titanium dioxide (I-doped TiO₂) photocatalysts were synthesized to degrade aqueous bisphenol A (BPA) under irradiation by visible light and sunlight. The band gap energies of TiO₂ and I-doped TiO₂ (I/Ti mole ratio = 0.5%) were 3.01 and 3.04, and the BPA photodegradation rate constants were 1.61, and 5.11 h⁻¹, respectively. The most probable reaction mechanism was proposed to involve IO₄⁻ and IO₃⁻ as electron acceptors that generate an inductive effect, increasing the photocatalytic efficiency of TiO₂. Results indicated that I-doped TiO₂ not only acted favorably as a photocatalyst, but also exhibited considerable mineralization effects. In addition, a recycling test after ten experiments demonstrated the stability and reusability of the photocatalyst.     

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.     

Achieving stable partial nitritation using endpoint pH control in an SBR treating landfill leachate

The feasibility of using endpoint pH control to achieve stable partial nitritation (PN) in an SBR for landfill leachate treatment was investigated. By imposing a fixed-time anoxia followed by variable-time aeration in an SBR cycle, successful partial nitritation was maintained for 182 days at a nitrogen loading rate of 0.30–0.89 kg/m³/day. The effluent NO₂⁻-N/NH₄⁺-N ratio and the effluent NO₃⁻-N concentration were 1.30 ± 0.22 and 16 ± 9 mg/L, respectively. High free ammonia (FA) and low dissolved oxygen (DO) concentrations were inhibition factors of nitrate formation. The termination of aeration at a suitable endpoint pH was the key to achieve an effluent NO₂⁻-N/NH₄⁺-N ratio close to the stoichiometric value. This endpoint pH control strategy represents practical potentials in the engineered application of combined PN–ANAMMOX processes.     

Synthesis of Bio-Diesel and Bio-Lubricant by Transesterification of Vegetable Oil with Lower and Higher Alcohols Over Heteropolyacids Supported by Clay (K-10)

The use of different lower and higher alcohols viz; methanol, ethanol, n-propanol and n-octanol, for the synthesis of methyl, ethyl, propyl and octyl fatty acid esters by transesterification of vegetable oil (triglycerides) with respective alcohols also known as ‘Bio-diesel’ and ‘Bio-lubricants’ was studied in detail. The reactions were carried out in a batch process. The activity with different supports like clay (K-10), activated carbon, ZSM-5, H-beta and TS-1 were compared. The superacids (heteropolyacids, HPA) viz; Dodeca-Tungstophosphoric acid [H₃PO₄·12 WO₃·xH₂O] (TPA) and Dodeca-Molybdo phosphoric acid ammonium salt hydrate [H₁₂Mo₁₂N_3-O₄₀P + aq] (DMAA) was used to increase the acidity and so the activity by loading on the most active support viz; clay (K-10). These HPA loaded on clay as a catalyst was used for the following study: effect of percent HPA loading on clay, effect of different vegetable oils, effect of different alcohols on the triglyceride conversion based on glycerol formation and selectivity based on alkyl esters formation. The data is compared at the best-optimized identical set of operating reaction conditions: 170 °C, 170 rpm, catalyst loading: 5% (w/w of reaction mixture), molar ratio (oil: alcohol): 1:15 and time on stream of 8 h. The generated data is also evaluated based on the reported one.     

Optimization of Innovative Ethanol Production from Wheat by Response Surface Methodology

A soft wheat variety has been tested as the raw material for fuel ethanol production via a novel processing route. The bran stream produced by the break section of a Buhler mill was used as the sole nutrient source in solid-state fermentation for the production of hydrolytic enzymes by two fungal strains, Aspergillus awamori and Aspergillus oryzae. Co-fermentation of the two fungi was largely problematic because of a significant difference between their growth rates. A mixture of the two enzyme solutions produced by separate cultivation of the two strains was effective for simultaneous starch and protein hydrolyses. Response surface methodology was used to design ethanol production trials using the flour hydrolysate as the only nutrient source by Saccharomyces cerevisiae. In a medium containing 150 g l⁻¹ glucose and 310 mg l⁻¹ free amino nitrogen, ethanol yield on glucose reached 50.7%, i.e., 99.2% of the theoretical conversion ratio, in 72 h. The yield of CO₂ from glucose was approximated as slightly higher than its theoretical yield due possibly to the availability of O₂ in the early fermentation stage. The overall production of 2-methyl-1-butanol, 1-propanol, 2-methyl-1-propanol and 3-methyl-butanol in all trials of yeast fermentation remained below 1000 ppm. Mass balance calculation concluded conversion ratios of 29.61% (w/w) ethanol and 23.74% (w/w) CO₂ from the wheat.     

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.     

Optimizing the preparation parameters of mesoporous nanocrystalline titania and its photocatalytic activity in water: Physical properties and growth mechanisms

Titania nanomaterial with an anatase structure and 5.6 nm crystallite size and 280.7 m² g⁻¹ specific surface areas had been successfully prepared by sol–gel/hydrothermal route. The effect of pH as a type of autoclave and calcination was studied. Crystallite size and phase composition of the prepared samples were identified. X-ray diffraction analyses showed the presence of anatase with little or no rutile phases. The crystallite size of the prepared TiO₂ with acidic catalyst was both smaller than that prepared with basic catalyst, and was increasing after acidic calcinations by a factor 4–5. Basic calcinations produced a specific increase of 1.5. Rutile ratio and the particle size were increased after calcination at 500 °C. However, TiO₂ powder synthesized using a basic catalyst persisted the anatase phase and a loosely aggregation of particles. Anatase TiO₂ as prepared with acidic catalyst in Teflon lined stainless steel autoclave demonstrated the highest photocatalytic activity for degradation of 2,6-dichlorophenol-indophenol under ultraviolet irradiation with t_½ 0.8 min.     

Pretreatment of municipal landfill leachate by a combined process

Biodegradability enhancement of landfill leachate using air stripping followed by coagulation/ultrafiltration (UF) processes was introduced. The air stripping process obtained a removal efficiency of 88.6% for ammonia nitrogen (NH₄–N) at air-to-liquid ratio of 3500 (pH 11) for stripping 18 h. The single coagulation process increased BOD/COD ratio by 0.089 with the FeCl₃ dosage of 570 mg l^?1 at pH 7.0, and the single UF process increased the BOD/COD ratio to 0.311 from 0.049. However, the combined process of coagulation/UF increased the BOD/COD ratio from 0.049 to 0.43, and the final biological oxygen demand (BOD), chemical oxygen demand (COD), NH₄–N and colour of leachate were 1223.6 mg l^?1, 2845.5 mg l^?1, 145.1 mg l^?1 and 2056.8, respectively, when 3 kDa molecular weight cut-off (MWCO) membrane was used at the operating pressure 0.7 MPa. In ultrafiltration process, the average solution flux (J_V), concentration multiple (M_C) and retention rate (R) for COD was 107.3 l m^?2 h^?1, 6.3% and 84.2%, respectively.     

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.     

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.     

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.     

Rotating biological contactors for wastewater treatment – A review

Rotating biological contactors (RBCs) for wastewater treatment began in the 1970s. Removal of organic matter has been targeted within organic loading rates of up to 120 g m⁻² d⁻¹ with an optimum at around 15 g m⁻² d⁻¹ for combined BOD and ammonia removal. Full nitrification is achievable under appropriate process conditions with oxidation rates of up to 6 g m⁻² d⁻¹ reported for municipal wastewater. The RBC process has been adapted for denitrification with reported removal rates of up to 14 g m⁻² d⁻¹ with nitrogen rich wastewaters. Different media types can be used to improve organic/nitrogen loading rates through selecting for different bacterial groups. The RBC has been applied with only limited success for enhanced biological phosphorus removal and attained up to 70% total phosphorus removal. Compared to other biofilm processes, RBCs had 35% lower energy costs than trickling filters but higher demand than wetland systems. However, the land footprint for the same treatment is lower than these alternatives. The RBC process has been used for removal of priority pollutants such as pharmaceuticals and personal care products. The RBC system has been shown to eliminate 99% of faecal coliforms and the majority of other wastewater pathogens. Novel RBC reactors include systems for energy generation such as algae, methane production and microbial fuel cells for direct current generation. Issues such as scale up remain challenging for the future application of RBC technology and topics such as phosphorus removal and denitrification still require further research. High volumetric removal rate, solids retention, low footprint, hydraulic residence times are characteristics of RBCs. The RBC is therefore an ideal candidate for hybrid processes for upgrading works maximising efficiency of existing infrastructure and minimising energy consumption for nutrient removal. This review will provide a link between disciplines and discuss recent developments in RBC research and comparison of recent process designs are provided (Section 2). The microbial features of the RBC biofilm are highlighted (Section 3) and topics such as biological nitrogen removal and priority pollutant remediation are discussed (Sections 4 Biological nutrient removal in RBCs, 5 Priority pollutant remediation in RBCs). Developments in kinetics and modelling are highlighted (Section 6) and future research themes are mentioned.     

Fate of trace tetracycline with resistant bacteria and resistance genes in an improved AAO wastewater treatment plant

The fate of trace tetracycline, tetracycline resistant bacteria (TRB) and tetracycline resistant genes (TRGs) in an improved anaerobic-anoxic-oxic (AAO) wastewater treatment plant (WWTP) was investigated in this study. Quantitative real-time polymerase chain reaction (qPCR) and conventional heterotrophic plate count method were used to measure eight tet genes (tetA, tetB, tetC, tetE, tetM, tetO, tetS and tetX) and TRB, respectively. The TRB percent of total heterotrophic bacteria (THB) is about 1.31–24.1% in WWTP influent. Tet gene abundance in the WWTP varied greatly among the gene types. The concentrations of TRGs in effluent samples ranged from 7.11 × 10⁻⁹ to 1.53 × 10⁻⁴ copies/copy 16S rRNA gene. TRB and THB, tetM and tetO, tetE and tetX, but not the others, showed a significant correlation with each other (p < 0.01). The relationships between ribosomal protection protein genes, enzymatic modification gene and corresponding concentrations of antibiotics were found to be considerably significant (R² = 0.898, p < 0.01 for ribosomal protection protein genes and R² = 0.872, p < 0.05 for enzymatic modification gene).     

Pb(II) adsorption from aqueous solutions by raw and treated biomass of maize stover – A comparative study

The potential to remove Pb(II) ion from wastewater treatment systems using raw and treated maize stover through adsorption was investigated in batch experiments. To achieve this, batch mode experiments were conducted choosing specific parameters such as pH (2–8), dosage concentration (2–30 g L⁻¹), contact time (5–180 min), temperature (20–45 °C) and metal ion concentrations (10–50 mg L⁻¹). Adsorption was pH-dependent showing a maximum at pH value 5. The equilibrium sorption capacities of raw and treated maize stover were 19.65 and 27.10 mg g⁻¹, respectively. The adsorption data fitted well to the Langmuir isotherm model. Kinetic studies revealed that the adsorption process followed pseudo-second-order model. The calculated thermodynamic parameters showed that the adsorption of Pb(II) was spontaneous and exothermic in nature. Consequently, this study demonstrated that both raw and treated maize stover could be used as adsorbents for the treatment of Pb(II) from industrial wastewaters.     

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.     

Conscientious personality and young drivers' crash risk

Introduction: Personality characteristics are associated with many risk behaviors. However, the relationship between personality traits, risky driving behavior, and crash risk is poorly understood. The purpose of this study was to examine the association between personality, risky driving behavior, and crashes and near-crashes, using naturalistic driving research methods. Method: Participants' driving exposure, kinematic risky driving (KRD), high-risk secondary task engagement, and the frequency of crashes and near-crashes (CNC) were assessed over the first 18 months of licensure using naturalistic driving methods. A personality survey (NEO-Five Factor Inventory) was administered at baseline. The association between personality characteristics, KRD rate, secondary task engagement rate, and CNC rate was estimated using a linear regression model. Mediation analysis was conducted to examine if participants' KRD rate or secondary task engagement rate mediated the relationship between personality and CNC. Data were collected as part of the Naturalistic Teen Driving Study. Results: Conscientiousness was marginally negatively associated with CNC (path c = − 0.034, p = .09) and both potential mediators KRD (path a = − 0.040, p = .09) and secondary task engagement while driving (path a = − 0.053, p = .03). KRD, but not secondary task engagement, was found to mediate (path b = 0.376, p = .02) the relationship between conscientiousness and CNC (path c′ = − 0.025, p = .20). Conclusions: Using objective measures of driving behavior and a widely used personality construct, these findings present a causal pathway through which personality and risky driving are associated with CNC. Specifically, more conscientious teenage drivers engaged in fewer risky driving maneuvers, and suffered fewer CNC. Practical Applications: Part of the variability in crash risk observed among newly licensed teenage drivers can be explained by personality. Parents and driving instructors may take teenage drivers' personality into account when providing guidance, and establishing norms and expectations about driving.     

An improved method of removal for high concentrations of NO by electro-scrubbing process

In the Ag(II)/Ag(I) redox mediator integrated scrubber system, NO reacts with the Ag(II) ions produced by the electrochemical oxidation of Ag(I) in an electrochemical cell present in the scrubbing solution (aqueous HNO₃ acid) to form NO₂. This NO₂ is then absorbed into the scrubbing solution and degraded to nitrate. Numerous experimental runs were carried out to evaluate the feasibility of the integrated system to treat industrial waste gases containing high NO_x levels. The results showed that the levels of NO and NO_x removal increased with increasing Ag(II) loading and contact time. Under optimized conditions, 93.5% and 73.3% of the NO and NO_x, respectively, were removed by a single stage gas scrubber with 1.62 g L^?1 Ag(II) operating at 25 °C and atmospheric pressure.     

Investigation on removal of p-nitrophenol using a hybridized photo-thermal activated persulfate process: Central composite design modeling

The aim of this work is the study of p-nitrophenol (PNP) removal, as a nitroaromatic compound, using a hybridized photo-thermally activated potassium persulfate (KPS) in a fully recycled batch reactor. Response surface method was used for modeling the process. Reaction temperature, KPS initial dosage and initial pH of the solution were selected as variables, besides PNP degradation efficiency was selected as the response. ANOVA analysis reveals that a second order polynomial model with F-value of 41.7, p-value of 0.0001 and regression coefficient of 0.95 is able to predict the response. Based on the model, the process optimum conditions were introduced as initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 66 °C. Also experiments showed that using thermolysis and photolysis of the persulfate simultaneously, the role of thermolysis is not considerable. A pseudo first order kinetic model was established to describe the degradation reaction. Operational cost, as a vital industrial criterion, was estimated so that the condition of initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 25 °C showed the highest cost effective case. Under the preferred mild condition, the process will reach to 84% and 89% of degradation and mineralization efficiencies, after 60 and 120 min, respectively.