Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

Electrochemical advanced oxidation processes: today and tomorrow. A review

In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical (^?OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which ^?OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which ^?OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.     

Photolysis of atrazine in aqueous solution: role of process variables and reactive oxygen species

Photochemical advanced oxidation processes have been considered for the treatment of water and wastewater containing the herbicide atrazine (ATZ), a possible human carcinogen and endocrine disruptor. In this study, we investigated the effects of the photon emission rate and initial concentration on ATZ photolysis at 254 nm, an issue not usually detailed in literature. Moreover, the role of reactive oxygen species (ROS) is discussed. Photon emission rates in the range 0.87?×?10¹⁸–3.6?×?10¹⁸ photons L^?1 s^?1 and [ATZ]₀?=?5 and 20 mg L^?1 were used. The results showed more than 65 % of ATZ removal after 30 min. ATZ photolysis followed apparent first-order kinetics with k values and percent removals decreasing with increasing herbicide initial concentration. A fivefold linear increase in specific degradation rate constants with photon emission rate was observed. Also, regardless the presence of persistent degradation products, toxicity was efficiently removed after 60-min exposure to UV radiation. Experiments confirmed a noticeable contribution of singlet oxygen and radical species to atrazine degradation during photolysis. These results may help understand the behavior of atrazine in different UV-driven photochemical degradation treatment processes.     

Decomposition of phenylarsonic acid by AOP processes: degradation rate constants and by-products

The paper presents results of the studies photodegradation, photooxidation, and oxidation of phenylarsonic acid (PAA) in aquatic solution. The water solutions, which consist of 2.7 g dm^?3 phenylarsonic acid, were subjected to advance oxidation process (AOP) in UV, UV/H₂O₂, UV/O₃, H₂O₂, and O₃ systems under two pH conditions. Kinetic rate constants and half-life of phenylarsonic acid decomposition reaction are presented. The results from the study indicate that at pH 2 and 7, PAA degradation processes takes place in accordance with the pseudo first order kinetic reaction. The highest rate constants (10.45?×?10^?3 and 20.12?×?10^?3) and degradation efficiencies at pH 2 and 7 were obtained at UV/O₃ processes. In solution, after processes, benzene, phenol, acetophenone, o-hydroxybiphenyl, p-hydroxybiphenyl, benzoic acid, benzaldehyde, and biphenyl were identified.     

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.

     

Enhanced removal of tetracycline via advanced oxidation of sodium persulfate and biochar adsorption

Advanced oxidation of antibiotic tetracycline (TC) is becoming an accessible and efficient technology. The removal of TC from the complex wastewater needs to be lucubrated. In this study, a TC removal system involving degradation and adsorption was established. TC degradation was accomplished by enhanced advanced oxidation via the addition of sodium persulfate (SP) and biochar into simulated wastewater containing Mn²⁺ and TC wastewater. The adsorption of TC and its derivatives was removed by biochar. The results indicate that the optimized reaction parameters were 3.0 g/L of biochar prepared at 600 °C (B600) and 400 mg/L of SP under acidic condition, and the removal percentage of TC was 87.48%, including 74.23% of degradation and 13.28% of adsorption; the anions Cl^?, NO₃^?, and H₂PO₄^? had negligible effects on the removal of TC in this Mn²⁺/B600/SP system. The system also functioned well with an aqueous solution with a high chemical oxygen demand (COD) concentration. Electron paramagnetic resonance (EPR) analysis indicated that ·OH and SO₄^? free radicals were present in the Mn²⁺/B600/SP system. Based on the testing and analysis results, a removal mechanism and potential TC degradation pathway for this system were proposed. TC can be degraded by ·OH and SO₄^? via three degradation pathways. Mn²⁺ can be precipitated as MnO₂, and a part of the TC and its derivatives can be adsorbed on the biochar surface. The Mn²⁺/B600/SP system also performed satisfactorily for a complex aqueous solution with various cations and antibiotics.

     

Degradation of anti-inflammatory drug ketoprofen by electro-oxidation: comparison of electro-Fenton and anodic oxidation processes

The electrochemical degradation of the nonsteroidal anti-inflammatory drug ketoprofen in tap water has been studied using electro-Fenton (EF) and anodic oxidation (AO) processes with platinium (Pt) and boron-doped diamond (BDD) anodes and carbon felt cathode. Fast degradation of the parent drug molecule and its degradation intermediates leading to complete mineralization was achieved by BDD/carbon felt, Pt/carbon felt, and AO with BDD anode. The obtained results showed that oxidative degradation rate of ketoprofen and mineralization of its aqueous solution increased by increasing applied current. Degradation kinetics fitted well to a pseudo-first-order reaction. Absolute rate constant of the oxidation of ketoprofen by electrochemically generated hydroxyl radicals was determined to be (2.8?±?0.1)?×?10⁹ M^?1 s^?1 by using competition kinetic method. Several reaction intermediates such as 3-hydroxybenzoic acid, pyrogallol, catechol, benzophenone, benzoic acid, and hydroquinone were identified by high-performance liquid chromatography (HPLC) analyses. The formation, identification, and evolution of short-chain aliphatic carboxylic acids like formic, acetic, oxalic, glycolic, and glyoxylic acids were monitored with ion exclusion chromatography. Based on the identified aromatic/cyclic intermediates and carboxylic acids as end products before mineralization, a plausible mineralization pathway was proposed. The evolution of the toxicity during treatments was also monitored using Microtox method, showing a faster detoxification with higher applied current values.     

Kinetics of the oxidation of sucralose and related carbohydrates by ferrate(VI)

The kinetics of the oxidation of sucralose, an emerging contaminant, and related monosaccharides and disaccharides by ferrate(VI) (Fe(VI)) were studied as a function of pH (6.5-10.1) at 25°C. Reducing sugars (glucose, fructose, and maltose) reacted faster with Fe(VI) than did the non-reducing sugar sucrose or its chlorinated derivative, sucralose. Second-order rate constants of the reactions of Fe(VI) with sucralose and disaccharides decreased with an increase in pH. The pH dependence was modeled by considering the reactivity of species of Fe(VI), (HFeO(4)(-) and FeO(4)(2-)) with the studied substrates. Second-order rate constants for the reaction of Fe(VI) with monosaccharides displayed an unusual variation with pH and were explained by considering the involvement of hydroxide in catalyzing the ring opening of the cyclic form of the carbohydrate at increased pH. The rate constants for the reactions of carbohydrates with Fe(VI) were compared with those for other oxidant species used in water treatment and were briefly discussed.     

Efficient removal of insecticide “imidacloprid” from water by electrochemical advanced oxidation processes

The oxidative degradation of imidacloprid (ICP) has been carried out by electrochemical advanced oxidation processes (EAOPs), anodic oxidation, and electro-Fenton, in which hydroxyl radicals are generated electrocatalytically. Carbon-felt cathode and platinum or boron-doped diamond (BDD) anodes were used in electrolysis cell. To determine optimum operating conditions, the effects of applied current and catalyst concentration were investigated. The decay of ICP during the oxidative degradation was well fitted to pseudo-first-order reaction kinetics and absolute rate constant of the oxidation of ICP by hydroxyl radicals was found to be k _abs(ICP)?=?1.23?×?10⁹ L mol^?1 s^?1. The results showed that both anodic oxidation and electro-Fenton process with BDD anode exhibited high mineralization efficiency reaching 91 and 94 % total organic carbon (TOC) removal at 2 h, respectively. For Pt-EF process, mineralization efficiency was also obtained as 71 %. The degradation products of ICP were identified and a plausible general oxidation mechanism was proposed. Some of the main reaction intermediates such as 6-chloronicotinic acid, 6-chloronicotinaldehyde, and 6-hydroxynicotinic acid were determined by GC-MS analysis. Before complete mineralization, formic, acetic, oxalic, and glyoxylic acids were identified as end-products. The initial chlorine and organic nitrogen present in ICP were found to be converted to inorganic anions Cl^?, NO₃ ^?, and NH₄ ⁺.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

Degradation of chlordecone and beta-hexachlorocyclohexane by photolysis, (photo-)fenton oxidation and ozonation

Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants – chlordecone (CLD) and beta-hexachlorocyclohexane (β-HCH) in 1 mg L^?1 synthetic aqueous solutions by means of photolysis, (photo-) Fenton oxidation and ozonation processes. Fenton oxidation is not efficient for CLD and yields less than 15% reduction of β-HCH concentration in 5 h. Conversely, both molecules can be quantitatively converted under UV-Vis irradiation reaching 100% of degradation in 5 h, while combination with hydrogen peroxide and ferrous iron does not show any significant improvement except in high wavelength range (>280 nm). Ozonation exhibits comparable but lower degradation rates than UV processes. Preliminary identification of degradation products indicated that hydrochlordecone was formed during photo-Fenton oxidation of CLD, while for β-HCH the major product peak exhibited C₃H₃Cl₂ as most abundant fragment.     

Degradation of diethyl phthalate (DEP) by vacuum ultraviolet process: influencing factors,oxidation products,and toxicity assessment

The vacuum ultraviolet (VUV) process, which can directly produce hydroxyl radical from water, is considered to be a promising oxidation process in degrading contaminants of emerging concern, because of no need for extra reagents. In this study, the influencing factors and mechanism for degradation of diethyl phthalate (DEP) by the VUV process were investigated. The effects of irradiation intensity, inorganic anions, natural organic matter (NOM), and H₂O₂ dosage on the performance of VUV process were evaluated. The results showed that DEP could be more efficiently degraded by the VUV process compared with ultraviolet (UV)-254-nm irradiation. The presence of HCO₃^?, NO₃^? and NOM in the aqueous solutions inhibited the degradation of DEP to a different degree, mainly by competing hydroxyl radicals (HO^?) with DEP. Degradation rate and removal efficiency of DEP by VUV process significantly enhanced with the addition of H₂O₂, while excess H₂O₂ dosage could inhibit the DEP degradation. Moreover, based on the identified seven oxidation byproducts and their time-dependent evolution profiles, a possible pathway for DEP degradation during the VUV process was proposed. Finally, the ecotoxicity of DEP and its oxidation byproducts reduced overall according to the calculated results from Ecological Structure Activity Relationships (ECOSAR) program. The electrical energy per order (EE/O) was also assessed to analysis the energy cost of the DEP degradation in the VUV process. Our work showed the VUV process could be an alternative and environmental friendly technology for removing contaminants in water.

     

Sonochemical degradation of a pharmaceutical waste,atenolol, in aqueous medium

Atenolol is a β-blocker drug and an identified emerging pollutant. Advanced oxidation processes (AOPs) utilise the reaction of a highly oxidising species (hydroxyl radicals, ^?OH) for the mineralisation of emerging pollutants since conventional treatment methodologies generally fail to degrade these compounds. In the present work, degradation of atenolol was carried out using ultrasound with frequencies ranging from 200 kHz to 1 MHz as a source of hydroxyl radical. The degradation was monitored by HPLC, total organic carbon (TOC) and chemical oxygen demand (COD) reduction and ion chromatography (IC). Nearly 90 % of degradation of atenolol was observed with ultrasound having 350 kHz. Both frequency and power of ultrasound affect the efficiency of degradation. Nearly 100 % degradation was obtained at a pH of 4. Presence of various additives such as sodium dodecyl sulphate, chloride, sulphate, nitrate, phosphate and bicarbonate was found to reduce the efficiency of degradation. Although nearly 100 % degradation of atenolol was observed under various experimental conditions, only about 62 % mineralisation (from TOC and COD measurements) was obtained. Nearly eight intermediate products were identified using high-resolution mass spectrometry (LC-Q-TOF). These products were understood as the results of hydroxyl radical addition to atenolol. The degradation studies were also carried out in river water which also showed a similar degradation profile. A mechanism of degradation and mineralisation is presented.     

Assessing the transformation kinetics of 2- and 4-nitrophenol in the atmospheric aqueous phase. Implications for the distribution of both nitroisomers in the atmosphere

Different transformation processes for nitrophenols in the atmospheric aqueous phase were considered to assess their relative importance, and their ability to account for the higher occurrence of 4-nitrophenol (4NP) compared to 2-nitrophenol (2NP) in the atmosphere. The importance of the different processes was in the order ^?OH > ^?NO₃ > direct photolysis > nitration to 2,4-dinitrophenol. 2NP is more reactive than 4NP with the hydroxyl radical, but the difference is low. Accordingly, such a process could account for the higher atmospheric occurrence of 4NP only if the observed atmospheric nitrophenols were what was left of an almost complete degradation by ^?OH. This would imply the unlikely scenario that the known nitrophenol sources to the atmosphere were only a limited fraction of the actual ones. A more likely, tentative possibility would be connected with the higher occurrence of 4NP on particles. If the reactivity order of nitrophenols in the atmospheric compartments was water droplets > gas phase > particles, particulate matter could act as a reservoir of 4NP. 2NP would undergo degradation in gas phase or solution at a higher rate than 4NP on particles, which could decrease the atmospheric levels of 2NP below those of 4NP.     

Speciation and persistence of doxycycline in the aquatic environment: Characterization in terms of steady state kinetics

The aim of the present work was to establish the kinetics for the degradation of doxycycline in the aquatic environment with a view to arriving at a kinetic model that can be used to predict the persistence of antibiotic with confidence. The degradation of doxycycline in both water and sediment phases of aquatic microcosm experiments, as well as in distilled water control experiments, was studied over a period of 90 days. An initial 21% loss due to adsorption by the sediment was observed in the microcosm experiment soon after charging. Biphasic zero-order linear rates of degradation, attributed to microbial degradation of the free and sediment or colloidal particle-adsorbed antibiotic, were observed for both water phase (2.3 × 10^?2 and 4.5 × 10^?3 μgg^?1 day^?1) and sediment phase (7.9 × 10^?3 and 1.5 × 10^?3 μgg^?1 day^?1) of the microcosm experiment. The covered distilled water control experiment exhibited a monophasic zero-order linear rate (1.9 × 10^?3 μgg^?1 day^?1) attributed to hydrolysis, while the distilled water experiment exposed to natural light exhibited biphasic liner rates attributed to a combination of hydrolysis and photolysis (2.9 × 10^?3 μgg^?1 day^?1) and to microbial degradation (9.8 × 10^?3 μgg^?1 day^?1). A kinetic model that takes into account hydrolysis, photolysis, microbial degradation as well as sorption/desorption by colloidal and sediment particles is presented to account for the observed zero-order kinetics. The implications of the observed kinetics on the persistence of doxycycline in the aquatic environment are discussed.     

Transformation of sulfaquinoxaline by chlorine and UV light in water: kinetics and by-product identification

Sulfaquinoxaline (SQX) is an antimicrobial of the sulfonamide class, frequently detected at low levels in drinking and surface water as organic micropollutant. The main goal of the present study is the evaluation of SQX reactivity during chlorination and UV irradiations which are two processes mainly used in water treatment plants. The SQX transformation by chlorination and UV lights (254 nm) was investigated in purified water at common conditions used for water disinfection (pH =?7.2, temperature =?25 °C, [chlorine] =?3 mg L^?1). The result shows a slow degradation of SQX during photolysis compared with chlorination process. Kinetic studies that fitted a fluence-based first-order kinetic model were used to determine the kinetic constants of SQX degradation; they were equal to 0.7?×?10^?4 and 0.7?×?10^?2 s^?1corresponding to the half time lives of 162 and 1.64 min during photolysis and chlorination, respectively. In the second step, seven by-products were generated during a chlorination and photo-transformation of SQX and identified using liquid chromatography with electrospray ionization and tandem mass spectrometry (MS-MS). SO₂ extrusion and direct decomposition were the common degradation pathway during photolysis and chlorination. Hydroxylation and isomerization were observed during photodegradation only while electrophilic substitution was observed during chlorination process.     

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.     

Oxygen,carbon, and nutrient exchanges at the sediment–water interface in the Mar Piccolo of Taranto (Ionian Sea,southern Italy)

In the shallow environment, the nutrient and carbon exchanges at the sediment–water interface contribute significantly to determine the trophic status of the whole water column. The intensity of the allochthonous input in a coastal environment subjected to strong anthropogenic pressures determines an increase in the benthic oxygen demand leading to depressed oxygen levels in the bottom waters. Anoxic conditions resulting from organic enrichment can enhance the exchange of nutrients between sediments and the overlying water. In the present study, carbon and nutrient fluxes at the sediment–water interface were measured at two experimental sites, one highly and one moderately contaminated, as reference point. In situ benthic flux measurements of dissolved species (O₂, DIC, DOC, N-NO₃ ^?, N-NO₂ ^?, N-NH₄ ⁺, P-PO₄ ^3?, Si-Si(OH)₄, H₂S) were conducted using benthic chambers. Furthermore, undisturbed sediment cores were collected for analyses of total and organic C, total N, and biopolymeric carbon (carbohydrates, proteins, and lipids) as well as of dissolved species in porewaters and supernatant in order to calculate the diffusive fluxes. The sediments were characterized by suboxic to anoxic conditions with redox values more negative in the highly contaminated site, which was also characterized by higher biopolymeric carbon content (most of all lipids), lower C/N ratios and generally higher diffusive fluxes, which could result in a higher release of contaminants. A great difference was observed between diffusive and in situ benthic fluxes suggesting the enhancing of fluxes by bioturbation and the occurrence of biogeochemically important processes at the sediment–water interface. The multi-contamination of both inorganic and organic pollutants, in the sediments of the Mar Piccolo of Taranto (declared SIN in 1998), potentially transferable to the water column and to the aquatic trophic chain, is of serious concern for its ecological relevance, also considering the widespread fishing and mussel farming activities in the area.     

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.