Effect of factors on decolorization of azo dye methyl orange by oxone/natural sunlight in aqueous solution

Purpose  

The oxone process for azo dye decolorization has drawbacks such as difficulties with reuse, risks of secondary pollution, and high costs associated with UV irradiation. This study aims to explore the use of oxone for decolorization in the absence of catalyst and under natural sunlight conditions (i.e., oxone/natural sunlight system) and evaluate the impacts of operating parameters (reagent dosage, initial methyl orange (MO) concentration, and initial pH) and coexisting substances (humic acid, NO₃⁻, metal ions) on the system’s decolorization efficiency.     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.     

Assessing the steady-state [·NO<Subscript>2</Subscript>] in environmental samples

Based on available literature data of [NO₂ ⁻], steady-state [·OH], and ·OH generation rate upon nitrate photolysis in environmental aqueous samples under sunlight, the steady-state [·NO₂], could be calculated. Interestingly, one to two orders of magnitude more ·NO₂ would be formed in photochemical processes in atmospheric water droplets compared to transfer from the gas phase. The relative importance of nitrite oxidation compared to nitrate photolysis as an ·NO₂ source would be higher in atmospheric than in surface waters. The calculated levels of ·NO₂ could lead to substantial transformation of phenol into nitrophenols in both atmospheric and surface waters.     

Gamma irradiation-induced decomposition of sulfamethoxazole in aqueous solution: the influence of additives,biological inhibitory,and degradation mechanisms

Sulfamethoxazole (SMX) was decomposed by using gamma irradiation in the presence of different additives such as NO₃ ⁻, NO₂ ⁻, Cr(VI), 2-propanol, and tert-butanol. The results demonstrated that NO₃ ⁻, NO₂ ⁻, 2-propanol, and tert-butanol inhibited SMX radiolytic removal. However, there existed a synergetic effect for radiolytic removal of the mixture containing SMX and Cr(VI). At an absorbed dose of 150 Gy, the removal percentages of SMX and Cr(VI) in the mixture were 73.5 and 84.6%, respectively, which was higher than the removal percentages of 70.6 and 4.1% for the single component of SMX and Cr(VI). This provides us an insight into treating the combined pollution in micro-polluted water. The SMX radiolytic removal followed a pseudo first-order reaction kinetic model, and the rate constant ratios of ·OH, e_aq ⁻, and H· towards SMX radiolysis were 10.4:1:2.9. In addition, 24-h bio-inhibitory to the macroalgae of SMX solution during gamma irradiation reached the maximum of 0.85 at an adsorbed dose of 100 Gy, then gradually decreased with the increasing adsorbed dose. Based on LC-MS analysis and quantum chemical calculation, the degradation intermediates were determined and concluded that SMX radiolytic removal was mainly via ·OH radical attack and direct decomposition of SMX molecule by gamma ray.

     

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Cyclooctane tropospheric degradation initiated by reaction with Cl atoms

Goal, Scope and Background Within the non-methane hydrocarbons, alkanes constitute the largest fraction of the anthropogenic emissions of volatile organic compounds. For the case of cyclic alkanes, tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atom reaction rate constants are generally one order of magnitude larger than those of OH. In the present work, the reaction of cyclooctane with Cl atoms has been studied within the temperature range of 279–333 K. Methods The kinetic study has been carried out using the fast flow tube technique coupled to mass spectrometry detection. The reaction has been studied under low pressure conditions, p=1 Torr, with helium as the carrier gas. Results The measured room temperature rate constant is very high, k=(2.63±0.54)×10⁻¹⁰ cm³molecule⁻¹s⁻¹, around 20 times larger than that for the corresponding OH reaction. We also report the results of the rate coefficients obtained at different temperatures: k = (3.5±1.2)×10⁻¹⁰ exp[(−79±110)/T] cm³ molecule⁻¹ s⁻¹ within the range of 279–333 K. This reaction shows an activation energy value close to zero. Discussion Quantitative formation of HCl has been observed, confirming the mechanism through H-atom abstraction. The reactivity of cyclic alkanes towards Cl atoms is clearly dependent on the number of CH₂ groups in the molecule, as is shown by the increase in the rate constant when the length of the organic chain increases. This increase is very high for the small cyclic alkanes and it seems that the reactions are approaching the collision-controlled limit for cyclohexane and cyclooctane. Conclusions These results show that gas-phase reaction with Cl in marine or coastal areas is an efficient sink (competing with the gas phase, OH initiated degradation) for the Earth’s emissions of cyclooctane, with a Cl-based lifetime ranging from 11 to 2000 hours, depending on the location and time of day. Recommendations and Perspectives Cl and OH fast reactions with cyclooctane are expected to define the lifetime of cyclooctane emissions to the atmosphere. The degradation of cyclooctane occurs in a short period of time and consequently (under conditions of low atmospheric mass transport), close to the emission sources enabling a significant contribution to local effects, like the formation of photochemical smog. ESS-Submission Editor: Prof. Dr. Gerhard Lammel (lammel@recetox.muni.cz)     

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO<Subscript>2</Subscript> suspensions

Background, aim and scope  

Photocatalytic oxidation using UV irradiation of TiO₂ has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e ⁻ _cb) with electron holes (h_vb⁺) on the irradiated TiO₂ surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO₄²⁻) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO₂ photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e ⁻ _cb and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate.     

铈离子光催化降解茜素绿的性能和机理简

主要研究了简单铈离子（Ce³⁺）在紫外光（UV）的作用下对蒽醌染料茜素绿（AG）的光催化降解效果和反应机理。结果表明,UV/Ce³⁺体系能够有效降解AG,初始反应速率随AG浓度的倒数值和Ce³⁺浓度的增加而线性增加,随初始溶液pH的增加先降低后增加,在酸性条件下有很高的TOC去除率。荧光探针实验表明,反应过程中可以产生·OH自由基。UV/Ce³⁺体系对其他类型染料和对硝基苯酚都有较好的降解效果。     

Accelerated photo-transformation of 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB 153) in water by dissolved organic matter

The ubiquitous dissolved organic matter (DOM) has an important influence on transformation of organic contaminants through the production of reactive substances, such as ^?OH, ¹O₂, and ³DOM*. The photolysis of a higher chlorinated polychlorinated biphenyl (PCB) congener (2,2′,4,4′,5,5′-hexachlorobiphenyl, PCB 153) under simulated sunlight in presence of humic acid (HA) was investigated. Degradation of PCB 153 was accelerated significantly by the addition of HA, with a rate constant of 0.0214, 0.0413, and 0.0358 h^?1 in the initial 18 h of irradiation in presence of 1, 5, and 20 mg/L HA, respectively. The main photodegradation products analyzed by gas chromatography mass spectrometry were 4-hydroxy-2,2′,4′,5,5′-pentaCB and 2,4,5-trichlorobenzoic acid. Main reactive species involved were determined by the electron spin-resonance spectroscopy, including ¹O₂ and ^?OH. Special scavengers were added to elucidate the photolysis mechanisms. By using the specific scavengers, it turned out that ^?OH accounted for 29.3 % of the degradation, and the intra-DOM reactive species (¹O₂, ^?OH, and ³DOM*) accounted for 59.6 % of the degradation. Photo-transformation sensitized by DOM, which involves both aqueous and intra-DOM reactions of PCBs with reactive species, may be one of the most important mechanisms for natural attenuation of PCBs.     

污泥基活性炭催化臭氧氧化对氯苯甲酸效能

以城市污水处理厂剩余污泥和玉米芯为原料,用氯化锌活化法制备出污泥基活性炭(SCAC),研究了其催化臭氧氧化去除水中对氯苯甲酸(p-CBA)的效能和机理,同时,考察了臭氧浓度、SCAC投量、p-CBA初始浓度以及自由基抑制剂叔丁醇的加入对SCAC催化活性的影响。实验结果表明,SCAC的加入可以显著提高臭氧对p-CBA的氧化去除效果,在反应初期尤为明显,反应1.0 min时p-CBA的去除率由单独臭氧氧化的26.1%提高到SCAC催化臭氧氧化的60.2%。SCAC催化臭氧氧化对p-CBA的去除率随臭氧浓度的增加和p-CBA初始浓度的减小而增加。此外,在一定范围内增加催化剂的投量可以增加p-CBA的去除率。叔丁醇的加入显著减弱了SCAC催化臭氧氧化降解p-CBA的效能,表明SCAC催化臭氧氧化反应的主要活性物种为羟基自由基(·OH)。     

Hydroxyl radical concentration profile in photo-Fenton oxidation process: generation and consumption of hydroxyl radicals during the discoloration of azo-dye Orange II

Dynamic behaviors of hydroxyl (OH) radical generation and consumption in photo-Fenton oxidation process were investigated by measuring OH radical concentration during the discoloration of azo-dye Orange II. The effects of operating parameters for photo-Fenton discoloration, i.e. dosages of H₂O₂ and Fe, initial dye concentration, solution pH and UV irradiation, on the generation and consumption of OH radicals playing the main role in advanced oxidation processes were extensively studied. The scavenger probe or trapping technique in which coumarin is scavenger of OH radical was applied to estimate OH radical concentration in the photoreactor during the photo-Fenton discoloration process. The OH radical generation was enhanced with increasing the dosages of Fenton regents, H₂O₂ and Fe. At the initial stage of photo-Fenton discoloration of Orange II, the OH radical concentration rapidly increased (Phase-I) and the OH radical concentration decreased after reaching of OH radical concentration at maximum value (Phase-II). The decrease in OH radical concentration started when the complete discoloration of Orange II was nearly achieved and the H₂O₂ concentration became rather low. The dynamic behavior of OH radical concentration during the discoloration of Orange II was found to be strongly linked with the change in H₂O₂ concentration. The generation of OH radical was maximum at solution pH of 3.0 and decreased with an increase of solution pH. The OH radical generation rate in the Fenton Process was rather slower than that in the photo-Fenton process.     

Atrazin Atmospheric deposition and air-borne concentrations

Am Beispiel des Wirkstoffes Atrazin wird die atmosph?rische Verbreitung und der atmosph?rische Eintrag von Pflanzenschutzmitteln mit einer geringen Flüchtigkeit aufgezeigt. Immissions-Konzentrationen lagen zwischen weniger als 0.005 ng·m⁻³ und maximal 0.32 ng·m⁻³ Atrazin wird fast ausschlie?lich in der Partikelphase, offensichtlich im Ungleichgewicht mit der Gasphase, verfrachtet. Dies verz?gert wahrscheinlich den photochemischen Abbau in der Atmosph?re. Die Konzentrationen im Flüssigwasser aufliegender Wolken erreichten zu den Applikationsterminen nahezu 1.6 μg·1⁻¹. Die Eintr?ge über die Atmosph?re betrugen in exponierter Lage im Fichtelgebirge mit 0.13 mg·m⁻²·a⁻¹ ca. 0.4% der Aufwandmengen in 3j?hrigen Maisfruchtfolgen. Im Alpenraum wurden mit 0.012 mg·m⁻²·a⁻¹ deutlich niedrigere Frachten gemessen als im Fichtelgebirge.Das Umweltrisiko durch die atmosph?rische Verbreitung und Deposition von Atrazin und anderen Pflanzenschutzmitteln mit vergleichbaren physikalisch-chemischen Eigenschaften ist als ?u?erst gering einzustufen. Atmospheric occurrence and deposition of atrazine are measured. During the application of atrazine, highest concentrations reached 1.6 μg·1⁻¹ in liquid water of lowlying clouds touching mountain tops. Atmospheric deposition, however, hardly amounts to 0.4% of the flux on crop land by direct spraying. Airborne concentrations ranged from less than 0.005 ng·m⁻³ to 0.32 ng·m⁻³. Contrary to theoretical expectations, almost all atrazine was found in the particulate matter, indicating nonequilibrium with the gas phase. This may inhibit a rapid photochemical decomposition. Human health concerns and environmental risks due to the atmospheric occurrence and deposition of atrazine are judged as minor. This conclusion can be applied to many other, physicochemically related pesticides.     

溴酸钾对二茂铁(Fc)非均相Fenton效能的影响

研究了KBrO3对二茂铁(Fc)非均相Fenton效能的影响,深入考察了KBrO3对体系中Fc溶解、H2O2分解和羟基自由基(·OH)生成的影响。结果表明,KBrO3的加入对不同反应阶段Fc/Fenton体系的效能均有明显的促进作用,初始阶段主要是由于KBrO3对·OH产生的促进作用所致,后期主要是由于KBrO3促进了体系中Fc的溶解,使得体系中溶解态的Fc催化的均相Fenton反应的比例增加,体系中H2O2的分解加快,·OH的表观生成率增加,进而促进了反应的进行。无KBrO3添加,pH=4,MB初始浓度为10 mg/L,Fc的量为1.6×10-3mol/L,[H2O2]/[MB]=3.14时,45 min时,MB的剩余率为9.1%,105 min时为0。当KBrO3的用量为3×10-4mol/L时,反应45 min后MB的去除率即可达到100%。随着KBrO3浓度的增加,其对Fc/Fenton效能的促进作用增强。     

Effects of climate change on surface-water photochemistry: a review

Information concerning the link between surface-water photochemistry and climate is presently very scarce as only a few studies have been dedicated to the subject. On the basis of the limited knowledge that is currently available, the present inferences can be made as follows: (1) Warming can cause enhanced leaching of ionic solutes from the catchments to surface waters, including cations and more biologically labile anions such as sulphate. Preferential sulphate biodegradation followed by removal as organic sulphides in sediment could increase alkalinity, favouring the generation of the carbonate radical, CO₃ ^·?. However, this phenomenon would be easily offset by fluctuations of the dissolved organic carbon (DOC), which is strongly anticorrelated with CO₃ ^·?. Therefore, obtaining insight into DOC evolution is a key issue in understanding the link between photochemistry and climate. (2) Climate change could exacerbate water scarcity in the dry season in some regions. Fluctuations in the water column could deeply alter photochemistry that is usually favoured in shallower waters. However, the way water is lost would strongly affect the prevailing photoinduced processes. Water outflow without important changes in solute concentration would mostly favour reactions induced by the hydroxyl and carbonate radicals (·OH and CO₃ ^·?). In contrast, evaporative concentration would enhance reactions mediated by singlet oxygen (¹O₂) and by the triplet states of chromophoric dissolved organic matter (³CDOM*). (3) In a warmer climate, the summer stratification period of lakes would last longer, thereby enhancing photochemical reactions in the epilimnion but at the same time keeping the hypolimnion water in the dark for longer periods.     

Nitrate and natural organic matter in aqueous solutions irradiated by simulated sunlight

By means of simulated sunlight, the influence of natural organic matter (NOM) on the photochemical degradation of halogenated pesticides in the absence and presence of nitrate as a precursor of the highly reactive OH radicals in aqueous solutions and freshwater was investigated. Solutions of dichlorprop or terbutylazine (a) in phosphate-buffered demineralized water containing nitrate and/or NOM and (b) in natural freshwaters were irradiated by a 1000-W Xe short-arc lamp. The collimated beam was filtered using a combination of optical filters (WG 320 and WG 295) to simulate the solar spectrum under summer midday conditions. In the absence of nitrate and NOM, the pesticides were degraded photolytically by simulated sunlight. The degradation rates depended on the absorption spectrum in the UVB range and the quantum yield of the degradation. The photochemical degradation of the pesticides was faster in the presence of nitrate due to the sunlight-induced formation of OH radicals. In the absence of nitrate, low concentrations of NOM of a brownwater lake accelerated the degradation due to the formation of reactive species by NOM. At higher concentrations of NOM, the inner filter effect of NOM lowered the degradation rates. In the presence of 50 mg l−1 nitrate, NOM decreased the degradation rate significantly. In case the natural water samples were used as a matrix for the experiments (nitrate concentrations between 2 mg l−1 and 15 mg l−1, DOC concentrations below 2.3 mg l−1), NOM acted mainly as a radiation filter and as a scavenger of OH radicals. As a consequence, in most freshwater systems, the accelerating effect of NOM by the formation of reactive species is of minor importance compared to the inner filter effect and to radical scavenging.     

Degradation of tris(1-chloro-2-propanyl) phosphate by the synergistic effect of persulfate and zero-valent iron during a mechanochemical process

This study revealed a dual pathway for the degradation of tris(1-chloro-2-propanyl) phosphate (TCPP) by zero-valent iron (ZVI) and persulfate as co-milling agents in a mechanochemical (MC) process. Persulfate was activated with ZVI to degrade TCPP in a planetary ball mill. After milling for 2 h, 96.5% of the TCPP was degraded with the release of 63.16, 50.39, and 42.01% of the Cl^?, SO₄^2?, and PO₄^3?, respectively. In the first degradation pathway, persulfate was activated with ZVI to produce hydroxyl (·OH) radicals, and ZVI is oxidized to Fe(II) and Fe(III). A substitution reaction occurred as a result of the attack of ·OH on the P–O–C bonds, leading to the successive breakage of the three P–O–C bonds in TCPP to produce PO₄^3?. In the second pathway, a C–Cl bond in part of the TCPP molecule was oxidized by SO₄·^? to carbonyl and carboxyl groups. The P–O–C bonds continued to react with ·OH to produce PO₄^3?. Finally, the intermediate organochloride products were further reductively dechlorinated by ZVI. However, the synergistic effect of the oxidation (·OH and SO₄·^?) and the reduction reaction (ZVI) did not completely degrade TCPP to CO₂, resulting in a low mineralization rate (35.87%). Moreover, the intermediate products still showed the toxicities in LD₅₀ and developmental toxicant. In addition, the method was applied for the degradation of TCPP in soil, and high degradations (>?83.83%) were achieved in different types of soils.

     

Photo-sensitized oxidation in natural water via OH radicals

A method is presented for determining production and consumption rates of ^.OH radicals produced photochemically in natural surface waters. It is based on the determination of the kinetics by which the concentration of a specified trace compound decreases during irradiation. In samples from Lake Greifensee (Switzerland) low production rates for ^.OH limit its possible effects. In addition, fast consumptions by the natural dissolved organic solutes and by the bicarbonate protect organic micropollutants from oxidation by ^.OH. Neither direct nor indirect H₂O₂ photolysis was a significant source of ^.OH in the lakewater studied lacking iron, whereas nitrate photolysis could have been a source. Comparison with reaction kinetic formulations allows generalizations for other types of waters.     

Photochemical generation of reactive intermediates from urban-waste bio-organic substances under UV and solar irradiation

Singlet oxygen (¹O₂), hydroxyl radicals (^•OH), and excited triplet states of organic matter (³OM^*) play a key role in the degradation of pollutants in aquatic environments. The formation rates and quantum yields (Φ) of these reactive intermediates (RI) through photosensitized reactions of dissolved organic matter (DOM) have been reported in the literature for decades. Urban biowaste-derived substances (UW-BOS), a form of organic matter derived from vegetative and urban waste, have recently been shown to be efficient sensitizers in the photo-degradation of different contaminants. Nevertheless, no quantitative measurements of photo-oxidant generation by UW-BOS have been reported. In this study, the formation quantum yields of ¹O₂ and ^•OH, as well as quantum yield coefficients of TMP degradation (indicative of ³OM^* formation), were quantified for two UW-BOS samples, under 254-nm UV radiation or simulated sunlight and compared to a DOM standard from the Suwanee River (SRNOM). Values of Φ for UW-BOS samples ranged from Φ(+¹O₂) = 8.0 to 8.8 × 10⁻³, Φ(+^•OH) = 4.1 to 4.3 × 10⁻⁶, and f _TMP = 1.22 to 1.23 × 10² L Einstein⁻¹ under simulated sunlight and from Φ(+¹O₂) = 1.4 to 2.3 × 10⁻², Φ(+^•OH) = 1.3 to 3.5 × 10⁻³, and f _TMP = 3.3 to 3.9 × 10² L Einstein⁻¹ under UV. Although UW-BOS are not necessarily better than natural DOM regarding photosensitizing properties, they do sensitize the production of RI and could potentially be used in engineered treatment systems.

     

Elimination of diclofenac from water using irradiation technology

The effluents of wastewater treatment plants, usually directly emitted to the environment, often contain the anti-inflammatory drug diclofenac (DCF). The paper investigates DCF elimination using irradiation technology. Hydroxyl radical and hydrated electron reactive intermediates resulting from water radiolysis effectively degrade DCF and strongly reduce the toxicity of the solutions. OH attaches to one of the rings of DCF, and hydroxylated molecules, 2,6-dichloroaniline and quinoid type compounds are the products. Hydrated electron adds to the chlorine atom containing ring, in the reaction quinoid type compounds and 4-chloroacridine form. At a 0.1 mM DCF concentration, a ∼1 kGy absorbed dose is needed for the degradation of DCF molecules, but for mineralization of the products (in presence of O₂) an order of magnitude higher dose is required.For irradiation of wastewater after biological treatment a ∼1 kGy dose is suggested. At this dose DCF and other drugs or metabolites present at μg L⁻¹ level are eliminated together with microorganism deactivation.     

Atmospheric chemistry of 1-methyl-2-pyrrolidinone

Rate constants for the atmospheric reactions of 1-methyl-2-pyrrolidinone with OH radicals, NO₃ radicals and O₃ have been measured at 296±2 K and atmospheric pressure of air, and the products of the OH radical and NO₃ radical reactions investigated. Using relative rate techniques, rate constants for the gas-phase reactions of OH and NO₃ radicals with 1-methyl-2-pyrrolidinone of (2.15±0.36)×10^-11 cm³ molecule^-1 s^-1 and (1.26±0.40)×10^-13 cm³ molecule^-1 s^-1, respectively, were measured, where the indicated errors include the estimated overall uncertainties in the rate constants for the reference compounds. An upper limit to the rate constant for the O₃ reaction of <1×10^-19 cm³ molecule^-1 s^-1 was also determined. These kinetic data lead to a calculated tropospheric lifetime of 1-methyl-2-pyrrolidinone of a few hours, with both the daytime OH radical reaction and the nighttime NO₃ radical reaction being important loss processes. Products of the OH radical and NO₃ radical reactions were analyzed by gas chromatography with flame ionization detection and combined gas chromatography–mass spectrometry. N-methylsuccinimide and (tentatively) 1-formyl-2-pyrrolidinone were identified as products of both of these reactions. The measured formation yields of N-methylsuccinimide and 1-formyl-2-pyrrolidinone were 44±12% and 41±12%, respectively, from the OH radical reaction and 59±16% and ∼4%, respectively, from the NO₃ radical reaction. Reaction mechanisms consistent with formation of these products are presented.