Assessment and optimisation of VOC mass transfer enhancement by advanced oxidation process in a compact wet scrubber

Dimethyl disulphide (DMDS) removal was investigated in a compact scrubber (hydraulic residence time ≈20 ms), composed of a wire mesh packing structure where liquid and gas flow at co-current and high gas superficial velocity (>12 m s⁻¹). In order to regenerate the scrubbing liquid and to maintain a driving force in the scrubber, ozone and hydrogen peroxide were added to water since they allow the generation of nonselective and highly reactive species, hydroxyl radicals HO. Three ways of reagent distribution were tested. The influence of several parameters (liquid flow rate(s), ozone flow rate, pH and reagent concentrations) was investigated. The best configuration was obtained when ozone is transferred in the scrubbing liquid before introduction at the top of the scrubber simultaneously with the hydrogen peroxide solution, allowing to generate hydroxyl radical in the scrubber. With this configuration, DMDS removal could be increased from 16% with water to 34% at the same gas and liquid flow rates in the scrubber showing the potentiality of advanced oxidation process.     

Toxicity of nanoparticulate and bulk ZnO, Al2O3 and TiO2 to the nematode Caenorhabditis elegans

Limited information is available on the environmental behavior and associated potential risk of manufactured oxide nanoparticles (NPs). In this research, toxicity of nanoparticulate and bulk ZnO, Al₂O₃ and TiO₂ were examined to the nematode Caenorhabditis elegans with Escherichia coli as a food source. Parallel experiments with dissolved metal ions from NPs were also conducted. The 24-h median lethal concentration (LC₅₀) and sublethal endpoints were assessed. Both NPs and their bulk counterparts were toxic, inhibiting growth and especially the reproductive capability of the nematode. The 24-h LC₅₀ for ZnO NPs (2.3 mg L⁻¹) and bulk ZnO was not significantly different, but significantly different between Al₂O₃ NPs (82 mg L⁻¹) and bulk Al₂O₃ (153 mg L⁻¹), and between TiO₂ NPs (80 mg L⁻¹) and bulk TiO₂ (136 mg L⁻¹). Oxide solubility influenced the toxicity of ZnO and Al₂O₃ NPs, but nanoparticle-dependent toxicity was indeed observed for the investigated NPs.     

SMX degradation by ozonation and UV radiation: a kinetic study

The rate constants of sulfamethoxazole (SMX) degradation by ozonation and UV₂₅₄ radiation were investigated under various parameters including influent ozone gas concentration, initial SMX concentration, UV light intensity, ionic strength, water quality in terms of varying anions (bicarbonate, sulfate and nitrate), humic acid (HA) and pH. The results indicated that the removal of SMX by ozonation and UV₂₅₄ radiation fitted well to a pseudo first-order kinetic model and the rate constants were in the range of (0.9-9.8) × 10⁻³ and (1.7-18.9) × 10⁻³ s⁻¹, respectively. The second-order rate constants of SMX with ozone (k_O3), under varying operational parameters, were also determined and varied in the range of (0.60-3.38) ± 0.13 × 10⁵ M⁻¹ s⁻¹. In addition, SMX degradation through UV pretreatment followed by ozonation in the presence of HA was proved to be an effective method which can remove SMX with a low ozone dose. The results suggested that ozonation of SMX was more affected by concentration of influent ozone gas, alkalinity, and HA, while incident UV light intensity, pH, and HA were the dominant factors influencing UV degradation of SMX.     

The oxidation mechanism of polychlorinated dibenzo-p-dioxins under the atmospheric conditions - A theoretical study

The atmospheric polychlorinated dibenzo-p-dioxins (PCDDs) partition appreciably in the gas phase, where they undergo rapid oxidation. The atmospheric oxidation mechanisms of a few PCDDs, initiated by OH radical, are studied using density functional theory calculations. The oxidations start with OH-addition to the aromatic rings, dominantly at γ-sites, followed by the non-chlorinated β-sites; while additions to the α-sites or chlorinated sites are negligible. For PCDDs with all β-sites being chlorinated, formation of PCDD-γ-OH adducts become virtually the only reaction path. Under the atmospheric conditions, the PCDD-β/γ-OH adducts combine with O₂ slowly at rates <1 s⁻¹. Instead, the PCDD-β-OH adducts will react with O₂ through hydrogen abstraction at rates <50 s⁻¹, forming PCDD-β-ol, and the PCDD-γ-OH adducts will decompose to the substituted phenoxy radicals by fused-ring C-O bond cleavage at rates of 10³ ∼ 10⁵ s⁻¹. The reaction mechanisms of PCDDs are drastically different from the peroxy mechanism for the atmospheric oxidations of benzene and dibenzofuran.     

A novel application of H2O2-Fe(II) process for arsenate removal from synthetic acid mine drainage (AMD) water

Batch experiments were carried out to investigate the influences of H₂O₂/Fe(II) molar ratio, pH, sequence of pH adjustment, initial As(V) concentration, and interfering ions on As(V) removal in H₂O₂-Fe(II) process from synthetic acid mine drainage (AMD). The optimum H₂O₂/Fe(II) molar ratio was one for arsenate removal over the pH range of 4-7. Arsenate removal at pH 3 was poor even at high Fe(II) dosage due to the high solubility of Fe(III) formed in situ. With the increase of Fe(II) dosage, arsenate removal increased progressively before a plateau was reached at pH 5 as arsenate concentration varied from 0.05 to 2.0 mg L⁻¹. However, arsenate removal was negligible at Fe/As molar ratio <3 and then experienced a striking increase before a plateau was reached at pH 7 and arsenate concentration ≥1.0 mg L⁻¹. The co-occurring ions exerted no significant effect on arsenate removal at pH 5. The experimental results with synthetic AMD revealed that this method is highly selective for arsenate removal and the co-occurring ions either improved arsenate removal or slightly depressed arsenate removal at pH 5-7. The extended X-ray absorption fine structure (EXAFS) derived As-Fe length, 3.27-3.30 Å, indicated that arsenate was removed by forming bidentate-binuclear complexes with FeO(OH) octahydra. The economic analysis revealed that the cost of the H₂O₂-Fe(II) process was only 17-32% of that of conventional Fe(III) coagulation process to achieve arsenate concentration below 10 μg L⁻¹ in treated solution. The results suggested that the H₂O₂-Fe(II) process is an efficient, economical, selective and practical method for arsenate removal from AMD.     

Effect of 3 years' free-air exposure to elevated ozone on mature Norway spruce (Picea abies (L.) Karst.) needle epicuticular wax physicochemical characteristics

We examined the effect of ozone (O₃) on Norway spruce (Picea abies) needle epicuticular wax over three seasons at the Kranzberg Ozone Fumigation Experiment. Exposure to 2× ambient O₃ ranged from 64.5 to 74.2 μl O₃ l⁻¹ h AOT40, and 117.1 to 123.2 nl O₃ l⁻¹ 4th highest daily maximum 8-h average O₃ concentration. The proportion of current-year needle surface covered by wax tubes, tube aggregates, and plates decreased (P = 0.011) under 2× O₃. Epistomatal chambers had increased deposits of amorphous wax. Proportion of secondary alcohols varied due to year (P = 0.004) and O₃ treatment (P = 0.029). Secondary alcohols were reduced by 9.1% under 2× O₃. Exposure to 2× O₃ increased (P = 0.037) proportions of fatty acids by 29%. Opposing trends in secondary alcohols and fatty acids indicate a direct action of O₃ on wax biosynthesis. These results demonstrate O₃-induced changes in biologically important needle surface characteristics of 50-year-old field-grown trees.     

Atmospheric oxidation mechanisms of polychlorinated dibenzo-p-dioxins are different from those of benzene and dibenzofuran: a theoretical prediction

The reaction mechanisms of dibenzo-p-dioxin (DD) and 2,3,7,8-TCDD with OH radical have been studied using density functional theory calculations. Under the atmospheric conditions, ca 42% of DD + OH reaction proceeds as formation of DD − OH-β adduct, which will react with O₂ slowly; while the rest will proceed as formation of DD − OH-γ adduct, which will decompose to the substituted phenoxy radical P1 by the fused-ring C-O bond cleavage. For 2,3,7,8-TCDD + OH, the reaction will predominantly form the substituted phenoxy radical P2. The reaction mechanisms are drastically different from the peroxy mechanism for the atmospheric oxidations of benzene and dibenzofuran.     

Advanced oxidation of alkylphenol ethoxylates in aqueous systems

Alkylphenols and alkylphenol ethoxylates are ubiquitous wastewater contaminants. In this study the oxidation of nonylphenol ethoxylates (NPEO) and octylphenol ethoxylates (OPEO) by oxidant systems generating hydroxide radicals was evaluated. The reaction of each oxidant with a technical mixture of NPEO (Tergitol™) and OPEO (Triton X-100™) in ultrapure laboratory water and four aqueous environmental matrices was carried out in order to develop an understanding of reaction kinetics. The oxidation of APEOs was evaluated by hydroxyl radical generated by (1) hydrogen peroxide in the presence of ultraviolet light, (2) Fenton’s reagent, and (3) a photo-Fenton’s process. The second order kinetic rate constant for both NPEO and OPEO with hydroxyl radical was calculated to be 1.1 × 10¹⁰ M⁻¹ s⁻¹. The efficacy of the AOPs within an aqueous environmental matrix was dependent on the rate of formation of hydroxyl radical and the scavenging capacity of the matrix. A model based on the hydroxyl radical formation, scavenging capacity and the kinetic rate constant of target APEO was developed from the existing literature and applied to predict the concentration of APEOs in solution during advanced oxidation in different aqueous environmental matrices.     

Bioaccumulation and depuration of anthracene in Penaeus monodon (Fibricius) through food ingestion

Understanding on the bioaccumulation and depuration of PAHs (polycyclic aromatic hydrocarbons) in Penaeus monodon is important in seafood safety because it is one of the most popular seafood consumed worldwide. In this study, we used anthracene as the precursor compound for PAHs accumulation and depuration in the shrimp. Commercial feed pellets spiked with anthracene were fed to P. monodon. At 20 mg kg⁻¹ anthracene, P. monodon accumulated 0.1% of the anthracene from the feed. P. monodon deputed the PAH two times faster than its accumulation. The shrimp reduced its feed consumption when anthracene content in the feed exceeded 20 mg kg⁻¹. At 100 mg kg⁻¹ anthracene, P. monodon started to have necrosis tissues on the posterior end of their thorax. The bioaccumulation factor (BAF), uptake rate constant (k₁) and depuration rate constant (k₂) of anthracene in P. monodon were 1.15 × 10⁻³, 6.80 × 10⁻⁴ d⁻¹ and 6.28 × 10⁻¹ d⁻¹, respectively. The depuration rate constant is about thousand times higher than the uptake rate constant and this indicated that this crustacean is efficient in depurating hydrocarbons from their tissue.     

Determination of the dietary biomagnification of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane with the rainbow trout (Oncorhynchus mykiss)

Separate 77-d fish feeding studies were conducted on the cyclic volatile methylsiloxane (cVMS) chemicals octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane with the rainbow trout, Oncorhynchus mykiss, with the determination of biomagnification factor (BMF) and lipid-adjusted BMF (BMF(L)) values as the final experimental metrics. The studies used fish food concentrations of ∼500 μg g⁻¹ for exposure periods of 35 d, followed by a depuration period of 42 d with clean food. The fish tissue concentrations of D4 and D5 achieved empirical steady-state by day 21 in each study. By day 7 of exposure, total ¹⁴C activity of both compounds had moved from the fish gastrointestinal (GI) tract into surrounding tissue. An absence of significant fish growth during the initial depuration phase allowed for measurement of empirical depuration rate constants (k₂) independent of growth dilution for D4 and D5 of 0.035 and 0.040 d⁻¹, respectively, corresponding to elimination half-lives of approximately 20 d. These rate constants indicated that ∼70–75% of steady-state was achieved during exposure in both studies, resulting in empirical steady-state BMF and BMF(L) values of 0.28 and 0.66 for D4, respectively, and 0.32 and 0.85 for D5, respectively. Kinetic modeling using simple first-order uptake and depuration dynamics produced good agreement with experimental data, with D4 and D5 assimilation efficiencies of 40% and 44%, respectively. Growth-corrected depuration rate constants modeled over the entire study data set indicated slower elimination kinetics for D4 (k₂ of 0.007 d⁻¹ or half-life of 100 d) compared to D5 (k₂ of 0.010 d⁻¹ or elimination half-life of 69 d). Kinetic BMF_k values (i.e., k₁/k₂) for D4 and D5 were 1.7 and 1.3, respectively, with lipid-adjusted BMF_k(L) values of 4.0 and 3.4, respectively.     

Photocatalytic degradation with immobilised TiO(2) of three selected neonicotinoid insecticides: imidacloprid, thiamethoxam and clothianidin

This research focused on photocatalytic degradation of imidacloprid, thiamethoxam and clothianidin employing a tailor-made photoreactor with six polychromatic fluorescent UVA (broad maximum at 355 nm) lamps and immobilised titanium dioxide (TiO₂) on glass slides. The disappearance was followed by high pressure liquid chromatography (HPLC-DAD) analyses, wherein the efficiency of mineralization was monitored by measurements of total organic carbon (TOC). Within 2 h of photocatalysis, all three neonicotinoids were degraded following first order kinetics with rate constants k = 0.035 ± 0.001 min⁻¹ for imidacloprid, k = 0.019 ± 0.001 min⁻¹ for thiamethoxam and k = 0.021 ± 0.000 min⁻¹ for clothianidin. However, the rate of mineralization was low, i.e. 19.1 ± 0.2% for imidacloprid, 14.4 ± 2.9% for thiamethoxam and 14.1 ± 0.4% for clothianidin. This indicates that several transformation products were formed instead. Some of them were observed within HPLC-DAD analyses and structures were proposed according to the liquid chromatography-electro spray ionization tandem mass spectrometry analyses (LC-ESI-MS/MS). The formation of clothianidin, as thiamethoxam transformation product, was reported for the first time.     

Ozone-enhanced catalytic oxidation of monochlorobenzene over iron oxide catalysts

In this study, we examined the experimental catalytic oxidation of gaseous monochlorobenzene (MCBz) with O₃ over Fe₂O₃ in a packed bed reactor to investigate the feasibility of economical low temperature decomposition at a high space velocity (SV). We investigated the effects of several reaction parameters (temperature, O₃ concentration, and SV) on the MCBz oxidation. At 150 °C, the conversion of MCBz over Fe₂O₃ in the absence of O₃ was only 3%; it increased to 91% over Fe₂O₃ in the presence of 1200 ppm of O₃ at a high SV of 83 s⁻¹. A long-term operation study revealed that the conversion of MCBz was stable for more than 96 h. In the steady state, the carbon and chlorine balances were 88% and 86%, respectively. Applying a Langmuir-Hinshelwood kinetic model, we estimated an activation energy of 16.7 kJ mol⁻¹ for MCBz oxidation over Fe₂O₃ in the presence of O₃.     

Enhanced nitrogen deposition exacerbates the negative effect of increasing background ozone in Dactylis glomerata, but not Ranunculus acris

The combined impacts of simulated increased nitrogen (N) deposition (75 kg N ha⁻¹ yr⁻¹) and increasing background ozone (O₃) were studied using two mesotrophic grassland species (Dactylis glomerata and Ranunculus acris) in solardomes, by means of eight O₃ treatments ranging from 15.5 ppb to 92.7 ppb (24 h average mean). A-C_i curves were constructed for each species to gauge effects on photosynthetic efficiency and capacity, and effects on biomass partitioning were determined after 14 weeks. Increasing the background concentration of O₃ reduced the healthy above ground and root biomass of both species, and increased senesced biomass. N fertilisation increased biomass production in D. glomerata, and a significantly greater than additive effect of O₃ and N on root biomass was evident. In contrast, R. acris biomass was not affected by high N. The study shows the combined effects of these pollutants have differential implications for carbon allocation patterns in common grassland species.     

Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process

This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350 °C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H₂O and CO₂. The Arrhenius law data obtained for the phenol disappearance are the following: k = 1.8 × 10⁶ ± 3.9 × 10⁵ M⁻¹ s⁻¹ (pre-exponential factor) and E_a = 77 ± 8 kJ mol⁻¹ (activation energy).     

Hydrolysis of di-n-butyl phthalate, butylbenzyl phthalate and di(2-ethylhexyl) phthalate in human liver microsomes

Diester phthalates are industrial chemicals used primarily as plasticizers to import flexibility to polyvinylchloride plastics. In this study, we examined the hydrolysis of di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBzP) and di(2-ethylhexyl) phthalate (DEHP) in human liver microsomes. These diester phthalates were hydrolyzed to monoester phthalates (mono-n-butyl phthalate (MBP) from DBP, mono-n-butyl phthalate (MBP) and monobenzyl phthalate (MBzP) from BBzP, and mono(2-ethylhexyl) phthalate (MEHP)) by human liver microsomes. DBP, BBzP and DEHP hydrolysis showed sigmoidal kinetics in V-[S] plots, and the Hill coefficient (n) ranged 1.37-1.96. The S₅₀, V_max and CL_max values for DBP hydrolysis to MBP were 99.7 μM, 17.2 nmol min⁻¹ mg⁻¹ protein and 85.6 μL min⁻¹ mg⁻¹ protein, respectively. In BBzP hydrolysis, the values of S₅₀ (71.7 μM), V_max (13.0 nmol min⁻¹ mg⁻¹ protein) and CL_max (91.3 μL min⁻¹ mg⁻¹ protein) for MBzP formation were comparable to those of DBP hydrolysis. Although the S₅₀ value for MBP formation was comparable to that of MBzP formation, the V_max and CL_max values were markedly lower (<3%) than those for MBzP formation. The S₅₀, V_max and CL_max values for DEHP hydrolysis were 8.40 μM, 0.43 nmol min⁻¹ mg⁻¹ protein and 27.5 μL min⁻¹ mg⁻¹ protein, respectively. The S₅₀ value was about 10% of DBP and BBzP hydrolysis, and the V_max value was also markedly lower (<3%) than those for DBP hydrolysis and MBzP formation for BBzP hydrolysis. The ranking order of CL_max values for monoester phthalate formation in DBP, BBzP and DEHP hydrolysis was BBzP to MBzP ? DBP to MBP > DEHP to MEHP > BBzP to MBP. These findings suggest that the hydrolysis activities of diester phthalates by human liver microsomes depend on the chemical structure, and that the metabolism profile may relate to diester phthalate toxicities, such as hormone disruption and reproductive effects.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Fate of citalopram during water treatment with O3, ClO2, UV and Fenton oxidation

In the present study we investigate the fate of citalopram (CIT) at neutral pH using advanced water treatment technologies that include O₃, ClO₂ oxidation, UV irradiation and Fenton oxidation. The ozonation resulted in 80% reduction after 30 min treatment. Oxidation with ClO₂ removed >90% CIT at a dosage of 0.1 mg L⁻¹. During UV irradiation 85% reduction was achieved after 5 min, while Fenton with addition of 14 mg L⁻¹ (Fe²⁺) resulted in 90% reduction of CIT. During these treatment experiments transformation products (TPs) were formed from CIT, where five compounds were identified by using high resolution and tandem mass spectrometry. Among these desmethyl-citalopram and citalopram N-oxide have been previously identified as human metabolites, while three are novel and published here for the first time. The three TPs are a hydroxylated dimethylamino-side chain derivative, a butyrolactone derivative and a defluorinated derivative of CIT.