The photocatalytic degradation of reactive black 5 using TiO2/UV in an annular photoreactor

The textile effluent is a major industrial polluter because it is highly colored, containing about 15% unfixed dyes as well as high levels of salts that can potentially be discharged into the environment. Photocatalytic oxidation using an thin gap annular UV reactor with TiO2 was used to break down the colour of a synthetic effluent ranging up to 400 ppm in dye concentration of Reactive Black 5 and up to 80 g/L in NaCl. Results show that the reaction kinetics was dominated by the TiO2 loading, the initial dye concentration, and the dissolved oxygen concentration; with the other parameters showing less significant effects. High rates of decolorization were found, with a linear fit to the Langmuir-Hinshelwood equation yielding a reaction rate constant (k) of 2.45 ppm/min, and an adsorption equilibrium constant (K) of 0.048 ppm(-1) based on color removal. The presence of the combination of high dissolved oxygen (15 ppm) and sodium chloride (up to 80 g/L) was found to enhance the decolorization and mineralization rates of the reactive dye. However, pH was found to not significantly affect the degradation rate. Since textile effluent is strongly alkaline, this result is significant, as no solution neutralisation is required and direct treatment of the effluent is possible.     

Mathematical model evaluating for degradation of azo dye in contaminated water by UV/persulfate process

In the present study, the photooxidative degradation of Acid Red 14 (AR 14) was investigated in the UV/persulfate process, and the results of the degradation rate of AR 14 were parametrically represented by ordinary differential equations to find mathematical model for the degradation rate of AR 14 in this process. Our experimental observations led to a model for AR 14 degradation in the UV/persulfate system that could be used to predict removal efficiency by changes of S₂O₈²⁻ (X₁) and dye concentration (X₂), pH (X₃), temperature (X₄) and also distance of UV lamp from solution (X₅). It was found that persulfate and dye concentrations were the most important parameters for AR 14 degradation rate. Moreover, the results showed that the degradation rate was in good agreement with the first-order kinetics for all the parameter values studied. Moreover, the results of the mathematical model agree well with the experimental values (R² = 0.96). Our findings in this study showed that degradation efficiency of UV/S₂O₈²⁻ process for AR 14 was obtained as 98%. Therefore, this model could be applicable before scaling up the AR 14 degradation using UV/persulfate process.     

Photocatalytic degradation of reactive black 5 in aqueous solutions: Effect of operating conditions and coupling with ultrasound irradiation

The degradation of reactive black 5 (RB 5), a representative diazo dye found in textile effluents, by means of ultraviolet irradiation (9W UVA) over TiO(2) suspensions, ultrasound irradiation (80kHz, 135W) and their combined application was investigated. Several commercial TiO(2) catalysts were screened and an anatase Hombicat UV 100 sample exhibited considerable activity in terms of solution decoloration, COD and ecotoxicity reduction. Photocatalytic degradation increased with increasing TiO(2) loading (in the range 0.05-1g/L) and decreasing dye concentration (in the range 120-20mg/L) and solution pH (in the range 9-2.6). At the typical conditions employed in this study (60mg/L dye, 0.25mg/L catalyst, ambient pH=5.8, oxygen sparging), complete decoloration was achieved after 60min of reaction. Addition of H(2)O(2) up to 0.01M hindered degradation, scavenging the photogenerated holes and hydroxyl radicals. Ultrasound irradiation resulted in low decoloration, e.g. less than 10% after 60min at 60mg/L dye and oxygen sparging and slightly improved under an argon atmosphere. The simultaneous application of ultraviolet and ultrasound irradiation resulted in increased decoloration compared to that achieved by photocatalysis and sonolysis operating separately; moreover, the overall sonophotocatalytic effect was greater than the additive effect of the two processes, implying possible synergy.     

Degradation of azo dye by an UV/H2O2 advanced oxidation process using an amalgam lamp

The discharge of dyes into water is an ecological problem that can be alleviated by advanced oxidation processes (AOPs), such as UV/H₂O₂ treatments. Searching for more efficient light sources is a way to improve AOPs’ efficiency. This work tested the efficiency of an amalgam lamp on the degradation of an azo dye, studying the effect of dye and H₂O₂ concentrations and pH, and the influence of some salts on the decolouration rate of methyl orange. Actinometry showed that the amalgam lamp system was able to provide a high incident photon irradiance (6.30·10^?5 mol/cm² s). The amalgam lamp‐driven AOP was able to decolourize the dye at pseudo‐first‐order rates of 0.654–4.008 1/min, with increasing rates at low dye concentration and low pH and at high H₂O₂ concentrations until a maximum value is reached. The results show that the amalgam lamp can be an alternative light source for fast dye degradation by AOPs.     

Paracetamol oxidation from aqueous solutions by means of ozonation and H2O2/UV system

Paracetamol oxidation from aqueous solutions is studied by means of ozonation and H(2)O(2) photolysis. Both oxidative systems are able to destroy the aromatic ring of the substrate with a partial conversion of the initial carbon content into carbon dioxide. For the adopted experimental conditions mineralization degrees up to 30% and 40% are observed with ozonation and H(2)O(2) photolysis, respectively. Main reaction intermediates and products are identified for both systems by HPLC and GC-MS analyses and a kinetic characterization is achieved.     

Effect of ferric ion added on photodegradation of alachlor in the presence of TiO2 and UV radiation

The effect of in situ photodeposited ferric ion onto TiO2 surface on the degradation of alachlor was investigated in the presence of the UV radiation. The photodegradation rate of alachlor could be described as an apparent first order. The rate constant (K(a)) of alachlor increased from 0.021 to 0.060 h(-1) as the number of coating times increased from 1- to 5-times in the absence of ferric ion, where the corresponding thicknesses of the TiO2 film were 67 and 174 nm. The rate constant (K(a)) increased from 0.030 to 0.060 h(-1) as pH value decreasd from pH 9 to 5 in the presence of only TiO2 immobilised with 5-times of coating. The rate constant increased slightly from 0.031 to 0.050 h(-1) as the concentration of ferric ion increased from 0.75 to 7.5 mg Fe3+ l(-1) in the absence of TiO2. However, those increased from 0.051 to 0.110 h(-1) in the presence of both TiO2 and ferric ion. In situ photodeposition of ferric ion onto the TiO2 surface enhanced the rate constant of photodegradation of alachlor by about 80% with an adding 7.5 mgFe3+ l(-1). During the alachlor photodegradation, three kinds of non-toxic organic compounds derived from alachlor were detected in 1 h.     

Influence of organic matter on the transport of Cryptosporidium parvum oocysts in a ferric oxyhydroxide-coated quartz sand saturated porous medium

To assess the effect of organic matter on the transport of Cryptosporidium parvum oocysts in a geochemically heterogeneous saturated porous medium, we measured the breakthrough and collision efficiencies of oocysts as a function of dissolved organic matter concentration in a flow-through column containing ferric oxyhydroxide-coated sand. We characterized the surface properties of the oocysts and ferric oxyhydroxide-coated sand using microelectrophoresis and streaming potential, respectively, and the amount of organic matter adsorbed on the ferric oxyhydroxide-coated sand as a function of the concentration of dissolved organic matter (a fulvic acid isolated from Florida Everglades water). The dissolved organic matter had no significant effect on the zeta potential of the oocysts. Low concentrations of dissolved organic matter were responsible for reversing the charge of the ferric oxyhydroxide-coated sand surface from positive to negative. The charge reversal and accumulation of negative charge on the ferric oxyhydroxide-coated sand led to increases in oocyst breakthrough and decreases in oocyst collision efficiency with increasing dissolved organic matter concentration. The increase in dissolved organic matter concentration from 0 to 20 mg L⁻¹ resulted in a two-fold decrease in the collision efficiency.     

Evaluation of UV/H2O2 treatment for the oxidation of pharmaceuticals in wastewater

Advanced oxidation treatment using low pressure UV light coupled with hydrogen peroxide (UV/H₂O₂) was evaluated for the oxidation of six pharmaceuticals in three wastewater effluents. The removal of these six pharmaceuticals (meprobamate, carbamazepine, dilantin, atenolol, primidone and trimethoprim) varied between no observed removal and >90%. The role of the water quality (i.e., alkalinity, nitrite, and specifically effluent organic matter (EfOM)) on hydroxyl radical (OH) exposure was evaluated and used to explain the differences in pharmaceutical removal between the three wastewaters. Results indicated that the efficacy of UV/H₂O₂ treatment for the removal of pharmaceuticals from wastewater was a function of not only the concentration of EfOM but also its inherent reactivity towards OH. The removal of pharmaceuticals also correlated with reductions in ultraviolet absorbance at 254 nm (UV₂₅₄), which offers utilities a surrogate to assess pharmaceutical removal efficiency during UV/H₂O₂ treatment.     

Comparison of UV/H(2)O(2) and UV/TiO(2) for the degradation of metaldehyde: Kinetics and the impact of background organics

The kinetics of photodegradation of the pesticide metaldehyde by UV/H₂O₂ and UV/TiO₂ in laboratory grade water and a natural surface water were studied. Experiments were carried out in a bench scale collimated beam device using UVC radiation. Metaldehyde was efficiently degraded by both processes in laboratory grade water at identical rates of degradation (0.0070 and 0.0067 cm² mJ⁻¹ for UV/TiO₂ and UV/H₂O₂ respectively) when optimised doses were used. The ratio between oxidant and metaldehyde was significantly higher for H₂O₂ due to its low photon absorption efficiency at 254 nm. However, the presence of background organic compounds in natural water severely affected the rate of degradation, and whilst the pseudo first-order rate constant of degradation by UV/H₂O₂ was slowed down (0.0020 cm² mJ⁻¹), the degradation was completely inhibited for the UV/TiO₂ process (k′ = 0.00007 cm² mJ⁻¹) due to the blockage of active sites on TiO₂ surface by the background organic material.     

Dual roles of CO2*- for degrading synthetic organic chemicals in the photo/ferrioxalate system

In this study, the relative importance of the dual reaction pathways of CO2*- in the photo/ferrioxalate system, where it acts both as a reductant for reducing the ferric ion and as an agent for the formation of H(2)O(2), was investigated as a function of the concentrations of ferrioxalate and oxygen. We studied the two competitive reactions of CO2*- in the photo/ferrioxalate system, which depend on the relative concentrations of ferrioxalate to oxygen, with the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D), which was used as a target pollutant. At high concentrations of ferrioxalate, almost all of the CO2*- reacted with ferrioxalate to reduce Fe(III) to Fe(II), whereas at low concentrations of ferrioxalate, a majority of the CO2*- contributed to the formation of H(2)O(2), as a result of its reaction with oxygen, which allows the Fenton reaction to occur without any external supply of H(2)O(2).     

Kinetics and mechanisms of DMSO (dimethylsulfoxide) degradation by UV/H(2)O(2) process

The objective of this study was to elucidate the degradation pathways of dimethylsulfoxide (DMSO) during its mineralization caused by UV/H(2)O(2) treatment. In order to accomplish this, we measured the concentration time-profiles of DMSO and its degradation intermediates during the UV/H(2)O(2) treatment. In addition, we proposed a kinetic model that could account for the degradation pathways of DMSO during its UV/H(2)O(2) treatment. The results show that the degradation of DMSO by the UV/H(2)O(2) treatment can be classified into two major pathways, and this is supported by both the analysis of the intermediates and total organic carbon (TOC) measurements. Firstly, DMSO was degraded into sulfate (SO(4)(2-)) through the formation of methansulfinate (CH(3)SO(2)(-)) and methansulfonate (CH(3)SO(3)(-)) as sulfur-containing intermediates. One of the two carbon constituents of DMSO was highly resistant to mineralization, due to the formation of methansulfonate, which reacted very slowly with (.-)OH k = 0.8 x 10(7) M(-1)s(-1)). Secondly, the other carbon constituent of DMSO was relatively easily mineralized through the formation of formaldehyde (HCHO) and formate (HCO(2)(-)) as non-sulfur-containing intermediates. The kinetic model proposed in this study for the degradation of DMSO by (.-)OH in the UV/H(2)O(2) process was able to successfully predict the patterns of concentration time-profiles of all components during the UV/H(2)O(2) treatment of DMSO.     

A comparison of several nanoscale photocatalysts in the degradation of a common pollutant using LEDs and conventional UV light

A comparative study on the photocatalytic activities of four different catalysts, P-25 TiO₂, TiO₂ nanofibers, tin-doped TiO₂ nanofibers under UV light irradiation at 350 nm, and coumarin (C-343) coated TiO₂ nanofibers at 436 nm light emitting diodes (LED) is reported. Catalysts performance has been compared based on their reflectance spectrum and activity. A common water contaminant 4-chlorophenol was used as a substrate to compare the activity of the different catalysts under both direct and dye sensitized conditions. Results indicated that amongst the four different catalysts the activity of P-25 was the highest. However the activity of C-343 coated TiO₂ nanofibers in the LED (436 nm) based reactor was competitive. Identification of reaction intermediates implied that the reaction pathways under UV (band gap) and visible (dye sensitized) irradiation were different. Nonetheless, ring opening took place in all reactions with both maleic and dihydroxymaleic have been identified as intermediates. The study indicates that ordered arrays of TiO₂ irradiated by panels of arrays of low cost high intensity LEDs might be used for the design of reactors. The near monochromaticity, long life, and operation under direct currents are advantages of using LEDs.     

Advanced oxidation of the pharmaceutical drug diclofenac with UV/H2O2 and ozone

Diclofenac, a widely used anti-inflammatory drug, has been found in many Sewage Treatment Plant effluents, rivers and lake waters, and has been reported to exhibit adverse effects on fish. Advanced oxidation processes, ozonation and H2O2/UV were investigated for its degradation in water. The kinetic of the degradation reaction and the nature of the intermediate products were still poorly defined. Under the conditions adopted in the present study, both ozonation and H2O2/UV systems proved to be effective in inducing diclofenac degradation, ensuring a complete conversion of the chlorine into chloride ions and degrees of mineralization of 32% for ozonation and 39% for H2O2/UV after a 90 min treatment. The reactions were found to follow similar, but not identical, reaction pathways leading to hydroxylated intermediates (e.g. 2-[(2,6-dichlorophenyl)amino]-5-hydroxyphenylacetic acid) and C-N cleavage products (notably 2,5-dihydroxyphenylacetic acid) through competitive routes. Subsequent oxidative ring cleavage leads to carboxylic acid fragments via classic degradation pathways. In the pH range 5.0-6.0 kinetic constants (1.76 x 10(4)-1.84 x 10(4) M(-1) s(-1)) were estimated for diclofenac ozonation.     

Efficiency and energy requirements for the transformation of organic micropollutants by ozone, O3/H2O2 and UV/H2O2

The energy consumptions of conventional ozonation and the AOPs O₃/H₂O₂ and UV/H₂O₂ for transformation of organic micropollutants, namely atrazine (ATR), sulfamethoxazole (SMX) and N-nitrosodimethylamine (NDMA) were compared. Three lake waters and a wastewater were assessed. With p-chlorobenzoic acid (pCBA) as a hydroxyl radical (^•OH) probe compound, we experimentally determined the rate constants of organic matter of the selected waters for their reaction with ^•OH (k_OH,DOM), which varied from 2.0 × 10⁴ to 3.5 × 10⁴ L mgC⁻¹ s⁻¹. Based on these data we calculated ^•OH scavenging rates of the various water matrices, which were in the range 6.1-20 × 10⁴ s⁻¹. The varying scavenging rates influenced the required oxidant dose for the same degree of micropollutant transformation. In ozonation, for 90% pCBA transformation in the water with the lowest scavenging rate (lake Zürich water) the required O₃ dose was roughly 2.3 mg/L, and in the water with the highest scavenging rate (Dübendorf wastewater) it was 13.2 mg/L, corresponding to an energy consumption of 0.035 and 0.2 kWh/m³, respectively. The use of O₃/H₂O₂ increased the rate of micropollutant transformation and reduced bromate formation by 70%, but the H₂O₂ production increased the energy requirements by 20-25%. UV/H₂O₂ efficiently oxidized all examined micropollutants but energy requirements were substantially higher (For 90% pCBA conversion in lake Zürich water, 0.17-0.75 kWh/m³ were required, depending on the optical path length). Energy requirements between ozonation and UV/H₂O₂ were similar only in the case of NDMA, a compound that reacts slowly with ozone and ^•OH but is transformed efficiently by direct photolysis.     

HPLC/UV analysis of chlorfenapyr residues in cabbage and soil to study the dynamics of different formulations

The chlorfenapyr analysis method of residue, its degradation and final residue in soil and cabbage were studied. Residues of chlorfenapyr were extracted from soil and cabbage with acetone/water, purified by liquid/liquid partition and chromatographic column, concentrated to a small volume, and then determined by HPLC equipped with UV detector. The mean accuracy of analytical method were 93.3% and 90.6% in soil and cabbage, respectively; the precision (repeatability) in cabbage ranging from 1.7% to 11.8%, in soil ranging from 2.8% to 11.2%; the precision (reproducibility) in cabbage ranged from 2.2% to 12.1%, in soil it ranged from 2.4% to 11.5%. The minimum detectable amount of chlorfenapyr was 0.65 ng, the minimum detectable concentration was 0.0162 mg kg-1. The degradation of chlorfenapyr formulations in soil and cabbage was determined. The results showed that chlorfenapyr nanoformulation and suspension concentration degradation in soil coincided with C=0.2538 e-0.1612t, C=0.537 e-0.1754t, respectively; the half-lives were about 4.3 d and 3.9 d, respectively. Two kinds of chlorfenapyr formulation degradation in cabbage coincided with C=4.0431 e-0.3103t, C=6.9611 e-0.2686t respectively; the half-lives were about 2.2 d and 2.6, d, respectively. When chlorfenapyr formulations were applied according to the double recommended dose, the final residues in cabbage were much lower than the USA EPA's maximum residue limit of 1 mg kg-1 in vegetables. The degradation rate of chlorfenapyr nanoformulation was faster than that of suspension concentration, and the former residue was also less in soil. Therefore, a harvest interval should be more than 5 d, and a dosage of 900 mL/hm2 was suggested for chlorfenapyr suspension concentration, which could be considered as safe to human beings and animals. Chlorfenapyr nanoformulation was safer than suspension concentration, its harvest interval and dosage can attain a high level.     

Comparison of the efficiency of *OH radical formation during ozonation and the advanced oxidation processes O3/H2O2 and UV/H2O2

Comparison of advanced oxidation processes (AOPs) can be difficult due to physical and chemical differences in the fundamental processes used to produce OH radicals. This study compares the ability of several AOPs, including ozone, ozone+H2O2, low pressure UV (LP)+H2O2, and medium pressure UV (MP)+H2O2 in terms of energy required to produce OH radicals. Bench scale OH radical formation data was generated for each AOP using para-chlorobenzoic acid (pCBA) as an OH radical probe compound in three waters, Lake Greifensee water, Lake Zurich water, and a simulated groundwater. Ozone-based AOPs were found to be more energy efficient than the UV/H2O2 process at all H2O2 levels, and the addition of H2O2 in equimolar concentration resulted in 35% greater energy consumption over the ozone only process. Interestingly, the relatively high UV/AOP operational costs were due almost exclusively to the cost of hydrogen peroxide while the UV portion of the UV/AOP process typically accounted for less than 10 percent of the UV/AOP cost and was always less than the ozone energy cost. As the *OH radical exposure increased, the energy gap between UV/H2O2 AOP and ozone processes decreased, becoming negligible in some water quality scenarios.     

Application of an energy management and control system to assess the potential of different control strategies in HVAC systems

The significant and continuous increment in the global electricity consumption is asking for energy saving strategies. Efficient control for heating, ventilation and air-conditioning systems (HVAC) is the most cost-effective way to minimize the use of energy in buildings. In this framework, an energy management and control system (EMCS) has been developed to schedule electricity end-uses in the campus of the Universidad Politécnica de Valencia (UPV), Spain. This paper presents an evaluation performed by using the EMCS of different control strategies for HVAC split systems. It analyzed the effect of different schedules for a common air-conditioning device and demand response strategies are tested in several situations. The economic saving is calculated taking into account the electricity contract clauses. Finally, a test is made for the control of a group of similar devices in order to reduce the maximum peak power in consumption and to obtain a flexible load shape with the HVAC loads. The studies are then extrapolated to a larger system, the whole University campus, for which energy and economic savings are quantified.     

Variation in indoor particle number and PM2.5 concentrations in a radio station surrounded by busy roads before and after an upgrade of the HVAC system

Indoor particle number and PM_2.5 concentrations were investigated in a radio station surrounded by busy roads. Two extensive field measurement campaigns were conducted to determine the critical parameters affecting indoor air quality. The results indicated that indoor particle number and PM_2.5 concentrations were governed by outdoor air, and were significantly affected by the location of air intake and design of HVAC system. Prior to the upgrade of the HVAC system and relocation of the air intake, the indoor median particle number concentration was 7.4×10³ particles/cm³ and the median PM_2.5 concentration was 7 μg/m³. After the relocation of air intake and the redesign of the HVAC system, the indoor particle number concentration was between 2.3×10³ and 3.4×10³ particles/cm³, with a median value of 2.7×10³ particles/cm³, and the indoor PM_2.5 concentration was in the range of 3–5 μg/m³, with a median value of 4 μg/m³. By relocating the air intake of the HVAC, the outdoor particle number and PM_2.5 concentrations near the air intake were reduced by 35% and 55%, respectively. In addition, with the relocation of air intake and the redesign of the HVAC system, the particle number penetration rate was reduced from 42% to 14%, and the overall filtration efficiency of the HVAC system (relocation of air intake, pre-filter, AHU and particle losses in the air duct) increased from 58% to 86%. For PM_2.5, the penetration rate after the upgrade was approximately 18% and the overall filtration efficiency was 82%. This study demonstrates that by using a comprehensive approach, including the assessment of outdoor conditions and characterisation of ventilation and filtration parameters, satisfactory indoor air quality can be achieved, even for those indoor environments facing challenging outdoor air conditions.