A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

Comparative studies of the Fe–UV, H2O2–UV, TiO2–UV/vis systems for the decolorization of a textile dye X-3B in water

The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe³⁺, H₂O₂ and TiO₂ components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe²⁺–H₂O₂–UV  Fe²⁺–H₂O₂ > Fe³⁺–H₂O₂–UV > Fe³⁺–H₂O₂ > Fe³⁺–TiO₂–UV > TiO₂–UV > Fe³⁺–UV > TiO₂–visible light (λ  450 nm) > H₂O₂–UV > Fe²⁺–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.     

Simultaneous E. coli inactivation and NOM degradation in river water via photo-Fenton process at natural pH in solar CPC reactor. A new way for enhancing solar disinfection of natural water

Bacteria inactivation and natural organic matter oxidation in river water was simultaneously conducted via photo-Fenton reaction at “natural” pH (6.5) containing 0.6 mg L⁻¹ of Fe³⁺ and 10 mg L⁻¹ of H₂O₂. The experiments were carried out by using a solar compound parabolic collector on river water previously filtered by a slow sand filtration system and voluntarily spiked with Escherichia coli. Fifty five percent of 5.3 mg L⁻¹ of dissolved organic carbon was mineralized whereas total disinfection was observed without re-growth after 24 h in the dark.     

Zero valent iron mediated degradation of the pharmaceutical diazepam

Parameters that influence the zero valent iron mediated degradation of the pharmaceutical diazepam (DZP) were evaluated including the iron concentration and its pre-treatment, the effect of complexation with EDTA and oxic versus anoxic condition. It was observed that acid pre-treatment of iron particles is important for degradation efficiency and that H₂SO₄ is a better choice than HCl, resulting in higher degradation of DZP. Under oxic conditions, the degradation of DZP achieved 96% after 60 min using Fe⁰ (25 g L⁻¹) pre-treated with H₂SO₄ in the presence of EDTA (119 mg L⁻¹), while mineralization achieved around 60% after the same time. Under anoxic conditions, degradation occurred, however at lower extent, achieving 67% after 120 min. The addition of EDTA improved the treatment efficiency in 20% leading to 99% DZP degradation after 120 min. The first intermediates formed during DZP degradation were identified using LC/MS analysis and revealed the formation of mono- and di-hydroxylated products from DZP during Fe⁰/EDTA/O₂ degradation, which evidences that OH was the main oxidizing species formed in this process.     

Degradation of acetic acid with sulfate radical generated by persulfate ions photolysis

The photolysis of was studied for the removal of acetic acid in aqueous solution and compared with the H₂O₂/UV system. The radicals generated from the UV irradiation of ions yield a greater mineralization of acetic acid than the OH radicals. Acetic acid is oxidized by radicals without significant formation of intermediate by-products. Increasing system pH results in the formation of OH radicals from radicals. Maximum acetic acid degradation occurred at pH 5. The results suggest that above this pH, competitive reactions with the carbon mineralized inhibit the reaction of the solute with and also OH radicals. Scavenging effects of two naturally occurring ions were tested; in contrast to ions, the presence of Cl⁻ ions enhances the efficiency of the /UV process towards the acetate removal. It is attributed to the formation of the Cl radical and its great reactivity towards acetate.     

Degradation of 1,4-dioxane in water with heat- and Fe2+-activated persulfate oxidation

This research investigated the 1,4-dioxane (1,4-D) degradation efficiency and rate during persulfate oxidation at different temperatures, with and without Fe²⁺ addition, also considering the effect of pH and persulfate concentration on the oxidation of 1,4-D. Degradation pathways for 1,4-D have also been proposed based on the decomposition intermediates and by-products. The results indicate that 1,4-D was completely degraded with heat-activated persulfate oxidation within 3–80 h. The kinetics of the 1,4-D degradation process fitted well to a pseudo-first-order reaction model. Temperature was identified as the most important factor influencing the 1,4-D degradation rate during the oxidation process. As the temperature increased from 40 to 60 °C, the degradation rate improved significantly. At 40 °C, the addition of Fe²⁺ also increased the 1,4-D degradation rate. Interestingly, at 50 and 60 °C, the 1,4-D degradation rate decreased slightly with the addition of Fe²⁺. This reduced degradation rate may be attributed to the rapid conversion of Fe²⁺ to Fe³⁺ and the production of an Fe(OH)₃ precipitate which limited the ultimate oxidizing capability of persulfate with Fe²⁺ under higher temperatures. Higher persulfate concentrations led to higher 1,4-D degradation rates, but pH adjustment had no significant effect on the 1,4-D degradation rate. The identification of intermediates and by-products in the aqueous and gas phases showed that acetaldehyde, acetic acid, glycolaldehyde, glycolic acid, carbon dioxide, and hydrogen ion were generated during the persulfate oxidation process. A carbon balance analysis showed that 96 and 93 % of the carbon from the 1,4-D degradation were recovered as by-products with and without Fe²⁺ addition, respectively. Overall, persulfate oxidation of 1,4-D is promising as an economical and highly efficient technology for treatment of 1,4-D-contaminated water.     

Oxidative properties of ambient PM2.5 and elemental composition: Heterogeneous associations in 19 European cities

We assessed the extent to which constituents of PM_2.5 (transition metals, sodium, chloride) contribute to the ability to generate hydroxyl radicals (OH) in vitro in PM_2.5 sampled at 20 locations in 19 European centres participating in the European Community Respiratory Health Survey. PM_2.5 samples (n = 716) were collected on filters over one year and the oxidative activity of particle suspensions obtained from these filters was then assessed by measuring their ability to generate OH in the presence of hydrogen peroxide. Associations between OH formation and the studied PM constituents were heterogeneous. The total explained variance ranged from 85% in Norwich to only 6% in Albacete. Among the 20 centres, 15 showed positive correlations between one or more of the measured transition metals (copper, iron, manganese, lead, vanadium and titanium) and OH formation. In 9 of 20 centres OH formation was negatively associated with chloride, and in 3 centres with sodium. Across 19 European cities, elements which explained the largest variations in OH formation were chloride, iron and sodium.     

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.     

Chemical degradation of chlorophenols with Fenton's reagent (Fe + H2O2)

Aqueous solutions of Fenton's reagent (Fe²⁺ + H₂O₂) have been used to effect the total decomposition of the chlorophenols: 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 3,4-dichlorophenol and 2,4,5-trichlorophenol. The mineralization of these chlorinated aromatic substrates to CO₂ and free Cl⁻ has been studied as a function of [Fe²⁺] and [HClO₄]. Increasing the concentration of Fe²⁺ enhances the decomposition process, while an increase in the concentration of HClO₄, inhibits the reaction. The presence of Fe³⁺ alone (without any Fe²⁺) with H₂O₂ has no effect on the degradation of the chlorophenols. In all cases, the stoichiometric quantity of free Cl⁻ was obtained at the completion of the decomposition reaction; but the rates of disappaearance of the chlorophenol and of the formation of the Cl⁻ are not similar. This suggests that some chlorinated aliphatic species may be formed as possible intemediates.     

Parathion degradation and its intermediate formation by Fenton process in neutral environment

The purpose of this study is to investigate parathion degradation by Fenton process in neutral environment. The initial parathion concentration for all the degradation experiments was 20 ppm. For hydrogen ion effect on Fenton degradation, the pH varied from 2 to 8 at the [H₂O₂] to [Fe²⁺] ratio of 2-2 mM, and the result showed pH 3 as the most effective environment for parathion degradation by Fenton process. Apparent degradation was also observed at pH 7. The subsequent analysis for parathion degradation was conducted at pH 7 because most environmental parathion exists in the neutral environment. Comparing the parathion degradation results at various Fenton dosages revealed that at Fe²⁺ concentrations of 0.5, 1.0 and 1.5 mM, the Fenton reagent ratio ([H₂O₂]/[Fe²⁺]) for best-removing performance were found as 4, 3, and 2, resulting in the removal efficiencies of 19%, 48% and 36%, respectively. Further increase in Fe²⁺ concentration did not cause any increase of the optimum Fenton reagent ratio for the best parathion removal. The result from LC-MS also indicated that hydroxyl radicals might attack the PS double bond, the single bonds connecting nitro-group, nitrophenol, or the single bond within ethyl groups of parathion molecules forming paraoxons, nitrophenols, nitrate/nitrite, thiophosphates, and other smaller molecules. Lastly, the parathion degradation by Fenton process at the presence of humic acids was investigated, and the results showed that the presence of 10 mg L⁻¹ of humic acids in the aqueous solution enhanced the parathion removal by Fenton process twice as much as that without the presence of humic acids.     

Evidence of the water-cage effect on the photolysis of NO3− and FeOH2+. Implications of this effect and of H2O2 surface accumulation on photochemistry at the air–water interface of atmospheric droplets

Experiments are conducted to determine the effect of a cage of water molecules on the photolysis quantum yields of nitrate, FeOH²⁺, and H₂O₂. Results suggest that the quantum yields of nitrate and FeOH²⁺ are decreased by the recombination of photo-fragments ( OH +  NO₂ and Fe²⁺ +  OH, respectively) before they leave the surrounding cage of water molecules. However, no evidence is found for an enhanced quantum yield for H₂O₂. Therefore, the photolysis of nitrate and FeOH²⁺ could be enhanced if the cage of the solvent molecules is incomplete, as is the case at the air–water interface of atmospheric droplets. The photolysis rate constant distribution within nitrate, FeOH²⁺, and H₂O₂ aerosols is calculated by combining the expected quantum yield data in the bulk and at the interface with Mie theory calculations of light intensity. The photolysis rate constant of nitrate and FeOH²⁺ would be significantly higher at the surface than in the bulk if quantum yields are enhanced at the surface. In the case of H₂O₂, the photolysis rate constant would be enhanced by surface accumulation. The results concerning the expected rates of photolysis of these photoactive species are applied to the assessment of the reaction between benzene and OH in the presence of OH scavengers in an atmospherically relevant scenario. For a droplet of 1 μm radius, a large fraction of the total OH-benzene reaction (15% for H₂O₂, 20% for nitrate, and 35% for FeOH²⁺) would occur in the surface layer, which accounts for just 0.15% of the droplet volume.     

The OH-induced degradation mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA) with two forms in the water: a DFT comparison

The initial degradation mechanisms of OH and 4-chloro-2-methylphenoxyacetic acid (MCPA) including molecular form and anionic form are studied at the MPWB1K/6-311+G(3df, 2p)//MPWB1K/6-31+G(d, p) level. Possible reaction pathways of H-atom abstraction and OH addition are considered in detail. By result comparison analysis, it is found that the reaction mechanisms for OH and two forms of MCPA are different, and most reactions for anionic MCPA are easier than those for molecular MCPA. For H-atom abstraction reactions, the calculated energies show that OH abstracting H-atom from -CH₃ group of molecular MCPA is the most kinetically favorable process; the potential energy surface for anionic MCPA indicates that H-atom in -CH₂ group is slightly easier to be abstracted than that in -CH₃ group. For OH addition reactions, the addition of OH to the C1 site is the initial step for molecular MCPA and the predominant product is 4-chloro-2-methylphenol (denoted P3), while the C4 site is the most reactive site for anionic MCPA and the primary product results from the hydroxylation of the aromatic ring, which is in good agreement with the experimental observation. In additional, results from PCM calculations show that most reactions in water phase are more kinetically favorable than those in gas phase, though the mechanisms discussed above will not be changed.     

Fe2+活化过硫酸钠降解1,2-二氯苯

以Na2S2O8为氧化剂,柠檬酸螯合Fe2+为活化剂,对水中1,2-二氯苯进行处理。首先研究了Na2S2O8浓度、FeSO4浓度、柠檬酸浓度及初始pH值等因素对1,2-二氯苯降解的影响;然后通过正交实验,发现在Na2S2O8浓度14.28 mmol/L、FeSO4浓度7.14 mmol/L、柠檬酸浓度3.57 mmol/L、初始pH值3.0的条件,1,2-二氯苯降解率达到最大(99.28%)。进一步研究表明,柠檬酸螯合FeSO4活化Na2S2O8降解1,2-二氯苯的过程可分为2个阶段,其中第1阶段为快速反应,第2阶段反应速度较慢并且符合一级反应动力学规律。     

催化臭氧氧化染料溶液的研究

采用催化臭氧化技术降解染料废水,以甲基紫溶液为目标污染物,研究了过渡型金属离子的类型,Fe2+的浓度,溶液初始pH值,染料浓度和正丁醇等因素对其降解率的影响。实验结果表明:臭氧氧化甲基紫溶液的过程中,加入一定浓度的过渡型金属离子对甲基紫的去除具有促进作用;当臭氧浓度为16 mg/L,一定浓度范围内,Fe2+催化臭氧化的效果随着浓度的增加而增加,但Fe2+浓度为13 mg/L时,甲基紫的降解率下降;在酸性范围时,pH值增大其降解率会减小;染料浓度增加,甲基紫的降解率减小,但是其绝对降解值会增加;正丁醇的加入抑制氧化反应的进行,甲基紫的降解率下降,说明催化臭氧化过程中有羟基自由基产生。染料降解过程符合一级反应动力学规律。     

Fenton-like degradation of nalidixic acid with Fe3+/H2O2

The Fenton-like degradation of nalidixic acid was studied in this work. The effects of Fe³⁺ concentration and initial H₂O₂ concentration were investigated. Increasing the initial H₂O₂ concentration enhances the degradation and mineralization efficiency for nalidixic acid, while Fe³⁺ shows an optimal concentration of 0.25 mM. A complete removal of nalidixic acid and a TOC removal of 28 % were achieved in 60 min under a reaction condition of [Fe³⁺]?=?0.25 mM, [H₂O₂]?=?10 mM, T?=?35 °C, and pH?=?3. LC–MS analysis technique was used to analyze the possible degradation intermediates. The degradation pathways of nalidixic acid were proposed according to the identified intermediates and the electron density distribution of nalidixic acid. The Fenton-like degradation reaction of nalidixic acid mainly begins with the electrophilic attack of hydroxyl radical towards the C₃ position which results in the ring-opening reaction; meanwhile, hydroxyl radical attacking to the branched alkyl groups of nalidixic acid leads to the oxidation at the branched alkyl groups.     

Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe⁰, Fe/Ni, Fe₃O₄, Fe_3???x Ni _x O₄). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H₂O₂ or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe₃O₄) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe⁰ and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe⁰ and Fe/Ni (18–19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250–500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings may have important practical implications to promote successively reduction and oxidation reactions in soils and understand the impact of soil properties on remediation performance.     

Impact of initial and boundary conditions on preferential flow

Preferential flow in soil is approached by a water-content wave, WCW, that proceeds downward from the ground surface. WCWs were obtained from sprinkler experiments with infiltration rates varying from 5 to 40 mm h^− 1. TDR-probes and tensiometers measured volumetric water contents θ(z,t) at seven depths, and capillary heads, h(z,t) at six depths in a column of an undisturbed soil. The wave is characterized by the velocity of the wetting front, c_W, the amplitude, w_S, and the final water content, θ. We tested with uni-variate and bi-variate linear regressions the impacts of initial volumetric water contents, θ_ini, and input rates, q_S, on c_W, w_S and θ.The test showed that θ_ini influenced θ and w_S and q_S effected c_W. The expected proportionality of w_S ≈ qs^1/3 was weak and c_W ≈ qs^2/3 was strong.     

Factors affecting degradation of dimethyl sulfoxide (DMSO) by fluidized-bed Fenton process

In this study, the target compound is dimethyl sulfoxide (DMSO), which is used as a photoresist stripping solvent in the semiconductor and thin-film transistor liquid crystal display (TFT-LCD) manufacturing processes. The effects of the operating parameters (pH, Fe²⁺ and H₂O₂ concentrations) on the degradation of DMSO in the fluidized-bed Fenton process were examined. This study used the Box-Behnken design (BBD) to investigate the optimum conditions of DMSO degradation. The highest DMSO removal was 98 % for pH 3, when the H₂O₂ to Fe²⁺ molar ratio was 12. At pH 2 and 4, the highest DMSO removal was 82 %, when the H₂O₂ to Fe²⁺ molar ratio was 6.5. The correlation of DMSO removal showed that the effect of the parameters on DMSO removal followed the order Fe²⁺?>?H₂O₂?>?pH. From the BBD prediction, the optimum conditions were pH 3, 5 mM of Fe²⁺, and 60 mM of H₂O₂. The difference between the experimental value (98 %) and the predicted value (96 %) was not significant. The removal efficiencies of DMSO, chemical oxygen demand (COD), total organic carbon (TOC), and iron in the fluidized-bed Fenton process were higher than those in the traditional Fenton process.