Effect of Pumice and Sand on the Sustainability of Granular Iron Beds for the Aqueous Removal of CuII,NiII, and ZnII

Current knowledge of the basic principles underlying the design of Fe⁰ beds is weak. The volumetric expansive nature of iron corrosion was identified as the major factor determining the sustainability of Fe⁰ beds. This work attempts to systematically verify developed concepts. Pumice and sand were admixed to 200 g of Fe⁰ in column studies (50:50 volumetric proportion). Reference systems containing 100% of each material have been also investigated. The mean grain size of the used materials (in mm) were 0.28 (sand), 0.30 (pumice), and 0.50 (Fe⁰). The five studied systems were characterized (i) by the time dependent evolution of their hydraulic conductivity (permeability) and (ii) for their efficiency for aqueous removal of Cu^II, Ni^II, and Zn^II (about 0.3 mM of each). Results showed unequivocally that (i) quantitative contaminant removal was coupled to the presence of Fe⁰, (ii) additive admixture lengthened the service life of Fe⁰ beds, and (iii) pumice was the best admixing agent for sustaining permeability while the Fe⁰/sand column was the most efficient for contaminant removal. The evolution of the permeability was well‐fitted by the approach that the inflowing solution contained dissolved O₂. The achieved results are regarded as starting point for a systematic research to optimize/support Fe⁰ filter design.     

Enhancing the Sustainability of Household Fe0/Sand Filters by Using Bimetallics and MnO2

Filtration systems containing metallic iron as reactive medium (Fe⁰ beds) have been intensively used for water treatment during the last two decades. The sustainability of Fe⁰ beds is severely confined by two major factors: (i) reactivity loss as result of the formation of an oxide scale on Fe⁰ and (ii) permeability loss due to pore filling by generated iron corrosion products. Both factors are inherent to iron corrosion at pH > 4.5 and are common during the lifespan of a Fe⁰ bed. It is of great practical significance to improve the performance of Fe⁰ beds by properly addressing these key factors. Recent studies have shown that both reactivity loss and permeability loss could be addressed by mixing Fe⁰ and inert materials. For a non‐porous additive like quartz, the threshold value for the Fe⁰ volumetric proportion is 51%. Using the Fe⁰/quartz system as reference, this study theoretically discusses the possibility of (i) replacing Fe⁰ by bimetallic systems (e.g., Fe⁰/Cu⁰), or (ii) partially replacing quartz by a reactive metal oxide (MnO₂ or TiO₂) to improve the efficiency of Fe⁰ beds. Results confirmed the suitability of both tools for sustaining Fe⁰ bed performance. It is shown that using a Fe⁰:MnO₂ system with the volumetric proportion 51:49 will yield a filter with 40% residual porosity at Fe⁰ depletion (MnO₂ porosity 62%). This study improves Fe⁰ bed design and can be considered as a basis for further refinement and detailed research for efficient Fe⁰ filters.     

Bench‐Scaled Nano‐Fe0 Permeable Reactive Barrier for Nitrate Removal

There are many fundamental problems with the injection of nano‐zero‐valent iron (NZVI) particles to create permeable reactive barrier (PRB) treatment zone. Among them the loss of medium porosity or pore blocking over time can be considered which leads to reduction of permeability and bypass of the flow and contaminant plume up‐gradient of the PRB. Present study provides a solution for such problems by confining the target zone for injection to the gate in a funnel‐and‐gate configuration. A laboratory‐scale experimental setup is used in this work. In the designed PRB gate, no additional material from porous media exists. NZVI (d₅₀ = 52 ± 5 nm) particles are synthesized in water mixed with ethanol solvent system. A steady‐state condition is considered for the design of PRB size based on the concept of required contact time to obtain optimum width of PRB gate. Batch experiment is carried out and the results are used in the design of PRB gate width (~50 mm). Effect of high initial NO₃^–‐N concentration, NZVI concentration, and pore velocity of water in the range of laminar groundwater flow through porous media are evaluated on nitrate‐N reduction in PRB system. Results of PRB indicate that increasing the initial NO₃^–‐N concentration and pore velocity has inhibitor effect—against the effect of NZVI concentration—on the process of NO₃^–‐N removal. Settlement velocity (S.V.) of injected NZVI with different concentrations in the PRB is also investigated. Results indicate that the proposed PRB can solve the low permeability of medium in down‐gradient but increasing of the S.V. especially at higher concentration is one of the problems with this system that needs further investigations.     

Tracer Method to Determine Residence Time in a Permeable Reactive Barrier

A method is presented to evaluate ground water residence time in a zero‐valent iron (ZVI) permeable reactive barrier (PRB) using radon‐222 (²²²Rn) as a radioactive tracer. Residence time is a useful indicator of PRB hydraulic performance, with application to estimating the volumetric rate of ground water flow through a PRB, identifying flow heterogeneity, and characterizing flow conditions over time as a PRB matures. The tracer method relies on monitoring the decay of naturally occurring aqueous ²²²Rn as ground water flows through a PRB. Application of the method at a PRB site near Monticello, Utah, shows that after 8 years of operation, residence times in the ZVI range from 80 to 486 h and correlate well with chemical parameters (pH, Ca, SO₄, and Fe) that indicate the relative residence time. Residence times in this case study are determined directly from the first‐order decay equation because we show no significant emanation of ²²²Rn within the PRB and no measurable loss of ²²²Rn other than by radioactive decay.     

Metallic Iron for Water Treatment: A Critical Review

Water treatment with metallic iron (Fe⁰) is still based on the premise that Fe⁰ is a reducing agent. An alternative concept stipulates that contaminants are removed by adsorption, co‐precipitation, and size‐exclusion in a reactive filtration process. This article underlines the universal validity of the alternative concept. It is shown that admixing non‐expansive material to Fe⁰ as a pre‐requisite for sustainable Fe⁰‐based filtration systems. Fe⁰‐based filters are demonstrated an affordable, appropriate, and efficient decentralized water treatment technology.     

Extending Service Life of Household Water Filters by Mixing Metallic Iron with Sand

The use of metallic iron filters (Fe⁰ filters) has been discussed as a promising low‐cost option for safe drinking water production at household level. Filter clogging due to the volumetric expansive nature of iron corrosion has been identified as the major problem of Fe⁰ filters. Mixing Fe⁰ and sand (yielding Fe⁰/sand filters) has been proposed as a tool to extent filter service life. However, no systematic discussion rationalizing Fe⁰/sand mixtures is yet available. This communication theoretically discussed suitable Fe⁰/sand proportions for efficient filters. Results suggested that Fe⁰/sand filters should not contain more that 50 vol% Fe⁰ (25 wt% when Fe⁰ is mixed with quartz). The actual Fe⁰ percentage in a filter will depend on its intrinsic reactivity.     

An Injectable Apatite Permeable Reactive Barrier for In Situ 90Sr Immobilization

An injectable permeable reactive barrier (PRB) technology was developed to sequester ⁹⁰Sr in groundwater through the in situ formation of calcium‐phosphate mineral phases, specifically apatite that incorporates ⁹⁰Sr into the chemical structure. This injectable barrier technology extends the PRB concept to sites where groundwater contaminants are too deep or where site conditions otherwise preclude the application of more traditional trench‐emplaced barriers. An integrated, multiscale development and testing approach was used that included laboratory bench‐scale experiments, an initial pilot‐scale field test, and the emplacement and evaluation of a 300‐feet‐long treatability‐test‐scale PRB. The apatite amendment formulation uses two separate precursor solutions, one containing a Ca‐citrate complex and the other a Na‐phosphate solution, to form apatite precipitate in situ. Citrate is needed to keep calcium in solution long enough to achieve a more uniform and areally extensive distribution of precipitate formation. In the summer of 2008, the apatite PRB technology was applied as a 91‐m‐long (300 feet) PRB on the downgradient edge of a ⁹⁰Sr plume beneath the Hanford Site in Washington State. The technology was deployed to reduce ⁹⁰Sr flux discharging to the Columbia River. Performance assessment monitoring data collected to date indicate that the barrier is meeting treatment objectives (i.e., 90% reduction in ⁹⁰Sr concentration). The average reduction in ⁹⁰Sr concentrations at four downgradient compliance monitoring locations was 95% relative to the high end of the baseline range approximately 1 year after treatment, and continues to meet remedial objectives more than 4 years after treatment.     

Relevant Reducing Agents in Remediation Fe0/H2O Systems

Metallic iron (Fe⁰) is often reported as a reducing agent for environmental remediation. There is still controversy as to whether Fe⁰ plays any significant direct role in the process of contaminant reductive transformation. The view that Fe⁰ is mostly a generator of reducing agents (e.g. H, H₂ and Fe^II) and Fe oxyhydroxides has been either severely refuted or just tolerated. The tolerance is based on the simplification that, without Fe⁰, no secondary reducing agents could be available. Accordingly, Fe⁰ serves as the original source of electron donors (including H, H₂ and Fe^II). The objective of this communication is to refute the named simplification and establish that quantitative reduction results from secondary reducing agents. For this purpose, reports on aqueous contaminant removal by Al⁰, Fe⁰ and Zn⁰ are comparatively discussed. Results indicated that reduction may be quantitative in aqueous systems containing Fe⁰ and Zn⁰ while no significant reduction is observed in Al⁰/H₂O systems. Given that Al⁰ is a stronger reducing agent than Fe⁰ and Zn⁰, it is concluded that contaminant reduction in Fe⁰/H₂O systems results from synergic interactions between H/H₂ and Fe^II within porous Fe oxyhydroxides. This conclusion corroborates the operating mode of Fe⁰ bimetallics as H/H₂ producing systems for indirect contaminant reduction.     

Effect of SO on 1,1,1‐Trichloroethane Degradation by Fe0 in Aqueous Solution

Sulfate in groundwater has been previously shown to change the reactivity of Fe⁰ in permeable reactive barriers for reducing chlorinated organics. To better understand the effect and mechanism of SO, the degradation of 1,1,1‐trichloroethane (TCA) by Fe⁰ in unbuffered aqueous solutions with and without SO was investigated. In a Fe⁰‐TCA‐H₂O system with initial pH of 2.0 to 10.0, the maximum removal rate of TCA was achieved at the initial pH 6.0 with pseudo‐first‐order constant K_obs 9.0 × 10^?3/min. But in a Fe⁰‐TCA‐Na₂SO₄‐H₂O system, the removal rate of TCA decreased remarkably with a reduction in K_obs to 1.0 × 10^?3/min, and the pH varied from 6.0 to 9.6, indicating an inhibition of TCA dehydrochlorination by SO. Sulfate remarkably inhibited TCA degradation via changing the route of Fe⁰ dissolution. It accelerated the dissolution of Fe⁰ and transformed the intermediate form Fe(OH)_ads to Fe₂(SO₄)_ads, which weakened the affinity between Fe and TCA, and thus depressed the degradation of TCA by Fe⁰.     

Interface Treatment of Petroleum Hydrocarbon‐impacted Lower Permeability Layers by Activated Sodium Persulfate to Reduce Emissions to Groundwater

Nonaqueous phase liquid (NAPL)‐impacted lower permeability layers in heterogeneous media are difficult to fully remediate and can act as persistent sources of groundwater contamination through diffusive emissions to transmissive aquifer zones. This work investigated the benefits of partial remediation involving treatment focused near the high‐low permeability interface, with the performance metric being emissions reduction. A sequential base‐activated persulfate (S₂O₈ ^2?) delivery treatment strategy was studied in this work, involving 13–14 d deliveries of 10% w/w sodium persulfate (Na₂S₂O₈) and 14–28 d deliveries of 19 g/L sodium hydroxide (NaOH). Treatment and control experiments were conducted in 1.2‐m wide × 1.2‐m tall × 5‐cm thick physical model tanks containing two soil layers differing in hydraulic conductivity by three orders of magnitude. The top 10 cm of the lower permeability layers contained 7400–7800 mg‐NAPL/kg‐soil; the NAPL was comprised of benzene, toluene, ethylbenzene, p‐xylene, o‐xylene, n‐propylbenzene, and 1,3,5‐trimethylbenzene (TMB) mixed in octane. Approximately 0.1 g‐Na₂S₂O₈ was delivered per cm²‐interface area over 13–14 d. The S₂O₈ ^2? and SO₄ ^2? concentration profiles suggest higher oxidant reaction rates when NaOH is delivered prior to, rather than after Na₂S₂O₈. After 264 d and two treatments, hydrocarbon emissions from the NAPL source were reduced by 60% to 73% compared to a no‐treatment control tank. The incremental benefit of the second treatment was only about 10% of the effect of the first treatment.     

Distinguishing Iron-Reducing from Sulfate-Reducing Conditions

Ground water systems dominated by iron‐ or sulfate‐reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe²⁺) and sulfide (sum of H₂S, HS^?, and S⁼ species and denoted here as “H₂S”). This approach is based on the observation that concentrations of Fe²⁺ and H₂S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe²⁺ concentrations are high, H₂S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe²⁺ with H₂S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron‐ and the sulfate‐reducing microorganisms that catalyze the production of Fe²⁺ and H₂S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe²⁺ and H₂S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H₂) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe²⁺/H₂S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H₂～0.2 to 0.8 nM). Conversely, if the Fe²⁺/H₂S ratio was less than 0.30, consistent sulfate‐reducing (H₂～1 to 5 nM) conditions were observed over time. Concomitantly high Fe²⁺ and H₂S concentrations were associated with H₂ concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron‐ and sulfate‐reducing zones or concomitant iron and sulfate reduction under nonelectron donor–limited conditions. These observations suggest that Fe²⁺/H₂S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems.     

Microstructural Characterization of Granular Cast Iron for Permeable Reactive Barriers

Although intensive research on Fe(0) permeable reactive barriers (PRB) for in situ groundwater remediation has been conducted and multiple applications have been installed in the past two decades, some properties of reactive materials in use have not been fully considered and discussed yet. In the present investigation, a typical granular cast iron has been characterized with different techniques. The grain size distribution not only has an influence on the resulting pore geometry and the surface area but material properties significantly differ between fine and coarse grains. Metallographic analyses revealed large differences in both graphite inclusions and microstructures that likely influence the reactivity. Both graphite and cementite proved to be more resistant toward acidic dissolution compared to Fe⁰. The intrinsic material characteristics described here have not been covered in the existing PRB literature.     

Designing Iron‐Amended Biosand Filters for Decentralized Safe Drinking Water Provision

There are ongoing efforts to render conventional biosand filters (BSF) more efficient for safe drinking water provision. One promising option is to amend BSF with a reactive layer containing metallic iron (Fe⁰). The present communication presents some conceptual options for efficient Fe⁰‐amended BSF in its fourth generation. It is shown that a second fine‐sand layer should be placed downwards from the Fe⁰‐reactive layer to capture dissolved iron. This second fine‐sand layer could advantageously contain adsorbing materials (e.g. activated carbons, wooden charcoals). An approach for sizing the Fe⁰‐reactive layer is suggested based on 3 kg Fe⁰ per filter. Working with the same Fe⁰ load will ease comparison of results with different materials and the scaling up of household BSF to large scale community slow sand filters (SSF).     

Degradation of Phenol in Aqueous Solution by Fenton,Sono‐Fenton and Sono‐photo‐Fenton Methods

The present work focuses on the performance of Fenton, sono‐Fenton, and sono‐photo‐Fenton processes for the oxidation of phenol present in aqueous solution. The effects of H₂O₂ concentration, Fe²⁺ concentration, pH, and initial phenol concentration on the oxidation of phenol were studied. The optimum Fe²⁺ and H₂O₂ concentrations for the Fenton process were 45 and 800 mg/L, respectively. For the sono‐Fenton process, the optimum Fe²⁺ and H₂O₂ concentrations were 30 and 800 mg/L, respectively. The optimal conditions for the sono‐photo‐Fenton process were found to be 20 mg/L of Fe²⁺ and 700 mg/L of H₂O₂. The optimum pH was found to be 3 for the processes investigated in the present study. The analysis of results showed that the sono‐photo‐Fenton method reduced the Fe²⁺ concentration by 30–50% and the H₂O₂ concentration by 12.5%. It was found that the sono‐photo‐Fenton technique showed better performance than the Fenton and sono‐Fenton processes for the oxidation of phenol. A lumped kinetic model was used to predict the chemical oxygen demand reduction and the model was found to fit the data.     

Iron oxidation state in lower mantle mineral assemblages: I. Empirical relations derived from high-pressure experiments

The oxidation state of iron can significantly influence the physical and chemical properties of lower mantle minerals. To improve methods for estimation of Fe³⁺/∑Fe, synthetic assemblages of (Mg,Fe)(Si,Al)O₃ perovskite and (Mg,Fe)O ferropericlase were synthesised from oxide starting mixtures in Re or Fe capsules at 26 GPa and 1650-1850 °C using a multianvil press. (Mg,Fe)(Si,Al)O₃ majorite was also present in some of the run products. Both electron energy loss spectra (EELS) and Mössbauer spectra were measured for each run product, and a robust fitting method was developed for Mössbauer spectra using EELS results as a standard that enabled Fe³⁺/∑Fe of (Mg,Fe)(Si,Al)O₃ perovskite to be determined from Mössbauer spectra of multiphase assemblages. There is a close to linear variation between Fe³⁺/∑Fe and Al concentration in (Mg,Fe)(Si,Al)O₃ perovskite, independent of oxygen fugacity. The concentration of Fe³⁺ in (Mg,Fe)O increases with increasing iron concentration along curves of constant oxygen fugacity, where higher oxygen fugacity stabilises greater Fe³⁺ concentrations. Fe²⁺/Mg partition coefficients calculated from chemical composition data corrected for measured Fe³⁺/∑Fe showed values nearly identical within experimental error for all samples, and independent of Al concentration and oxygen fugacity. Simple empirical relations were derived to calculate Fe³⁺/∑Fe in (Mg,Fe)(Si,Al)O₃ perovskite and (Mg,Fe)O ferropericlase samples for which no Mössbauer or EELS data were available, and tested by applying them to calculation of Fe²⁺/Mg partition coefficients from literature data for (Mg,Fe)(Si,Al)O₃ perovskite-(Mg,Fe)O assemblages where only total iron concentrations had been measured. Results showed Fe²⁺/Mg partition coefficients that were equal to existing values within experimental error, hence confirming the validity of the empirical relations.     

Degradation of Monoazo Pigments Red 53:1 and Red 48:2 by Fenton,Photo‐Fenton and UV/Peroxide Reactions

The degradation reactions of two monoazo pigments, namely, Red 53:1 and Red 48:2, by Fenton, photo‐Fenton and UV/H₂O₂ systems have been studied. The efficiencies of the Fenton reactions increased with temperature, but the formation of solid agglomerates was observed when the reactions were carried out above 50°C indicating a coagulant action of Fe⁺² or Fe⁺³. Photo‐Fenton reactions irradiated by sunlight presented the best rate constants for cleavage of the azo bond and the naphthalene rings. The UV/H₂O₂ system exhibited the highest efficiency with respect to the consumption of H₂O₂. The presence of a carbonyl group in the ortho position of the naphthol ring hampered the oxidation of pigment Red 48:2 by hydroxyl radicals. This finding may be explained in terms of the acceptor character of the COOH group, and suggests the formation of a complex containing two six‐membered rings between Fe⁺³ and the pigment molecule.     

Pretreatment of Olive Oil Mill Wastewater by Two Different Applications of Fenton Oxidation Processes

The removal of chemical oxygen demand (COD) and phenol from olive oil mill wastewaters (OOMW) was investigated experimentally by using conventional Fenton (CFP) and Fenton type processes (FTP) with zero valent iron (ZVI). Different operational parameters such as initial pH, Fe²⁺, Fe⁰, and H₂O₂ concentrations were examined. Kinetic studies in terms of COD and phenol removals for both CFP and FTP were performed. The original pH value (4.6) of OOMW for CFP was found as the optimum pH. The determined optimum conditions are [Fe²⁺] = 1500 mg L^?1, [H₂O₂] = 1750 mg L^?1, and pH = 4.6 for CFP; [Fe⁰] = 2000 mg L^?1, [H₂O₂] = 2000 mg L^?1, and pH = 3 for FTP. 82.4% COD and 62% phenol removals were performed under the optimum conditions by CFP, while 82% COD and 63.4% phenol were removed by FTP. According to the results of kinetic studies, it was observed that COD and phenol were removed by FTP more rapidly, compared to CFP. Consequently, it was determined that both CFP and FTP were effective processes for the pretreatment of OOMW.     

Color Removal from Synthetic Textile Wastewater by Sono‐Fenton Process

In this study, the oxidative decolorization of C.I. reactive yellow 145 (RY 145) from synthetic textile wastewater including RY 145 and polyvinyl alcohol by Fenton and sono‐Fenton processes which are the combination of Fenton process with ultrasound has been carried out. The effects of some operating parameters which are the initial pH of the solution, the initial concentration of Fe²⁺, H₂O₂, and the dye, temperature, and agitation speed on the color and chemical oxygen demand (COD) removals have been investigated. The optimum conditions have been found as [Fe²⁺] = 20 mg/L, [H₂O₂] = 20 mg/L, pH 3 for Fenton process and [Fe²⁺] = 20 mg/L, [H₂O₂] = 15 mg/L, pH 3 for sono‐Fenton process by indirectly sonication at 35 kHz ultrasonic frequency and 80 W ultrasonic power. The color and COD removal efficiencies have been obtained as 91 and 47% by Fenton process, and 95 and 51% by sono‐Fenton processes, respectively. Kinetic studies have been performed for the decolorization of RY 145 under optimum conditions at room temperature. It has been determined that the decolorization has occurred rapidly by sono‐Fenton process, compared to Fenton process.     

High-temperature hysteresis and other magnetic properties of synthetic monodomain titanomagnetites

A suite of synthetic titanomagnetites of composition Fe_2.4?δAl_δTi_0.6O₄ and Fe_2.6?δAl_δTi_0.4O₄ (δ = 0, 0.1 and 0.2 in both cases) have been prepared by a method of partial self-buffering and pulverized in a ball mill to particle size of about 200–500 Å. Magnetic hysteresis parameters-saturation and remanent magnetizations and coercive force were measured between room temperature and the Curie temperatures and other parameters-X-ray cell edge, initial susceptibility and coercive force of remanence were determined at room temperature. The intrinsic magnetic “hardness” increases with increasing content of Al³⁺ and Ti⁴⁺, both probably corresponding to an increase in the concentration of Fe²⁺ ions on the tetrahedral sites of the spinel structure. The room-temperature hysteresis properties were compared with those resulting from monodomain models for the work done to magnetically saturate an assemblage of grains and the approach to saturation, and the separate contributions from coexisting anisotropies of cubic and uniaxial symmetries (assumed present) inferred. The cubic anisotropy energy constants so derived are larger than those determined from multidomain single crystals. The derived cubic constants are also larger than the derived uniaxial anisotropy constants. The latter, however, dominate the behaviour (e.g., coercive force) because of the lower symmetry. The materials appear to be entirely in the stable monodomain state at room temperature.     

Degradation of an Azo Dye with Homogeneous and Heterogeneous Catalysts by Sonophotolysis

This study illustrates the degradation of an azo dye, Reactive Yellow 81 (RY81), by the combined irradiation of UV‐C and ultrasound in the presence of homogeneous (Fe²⁺) and heterogeneous (TiO₂, ZnO) catalysts. The efficiency of homogeneous and heterogeneous oxidation systems was evaluated in regard of the decolorization and mineralization of RY81. Decolorization followed pseudo‐first‐order kinetics with homogeneous and heterogeneous catalysts. Complete color removal was accomplished by homogeneous sonocatalytic and sonophotocatalytic oxidation processes with apparent rate constants of 0.96 × 10^?3 and 46.77 × 10^?3 s^?1, respectively, in the presence of Fe²⁺. However, partial color removal was obtained by heterogeneous sonocatalytic, photocatalytic, and sonophotocatalytic oxidation processes with apparent rate constants of 2.32 × 10^?3, 3.60 × 10^?3, and 3.67 × 10^?3 s^?1, respectively, in the presence of ZnO. TiO₂ had the worst catalytic effect of all of the oxidation processes. The addition of hydrogen peroxide increased the rate constants of the heterogeneous oxidation processes and decreased the rate constants of the homogeneous oxidation processes. RY81 mineralization was 62.8% for the US/UV/Fe²⁺ homogeneous oxidation process, which was the best oxidation process, whereas it was 43.5% for the US/UV/ZnO/H₂O₂ heterogeneous oxidation process within 2 h reaction time.