Environmentally Safe Photodynamic Control of Aedes aegypti Using Sunlight-Activated Synthetic Curcumin: Photodegradation, Aquatic Ecotoxicity, and Field Trial.

This study reports curcumin as an efficient photolarvicide against Aedes aegypti larvae under natural light illumination. Larval mortality and pupal formation were monitored daily for 21 days under simulated field conditions. In a sucrose-containing formulation, a lethal time 50 (LT50) of 3 days was found using curcumin at 4.6 mg L-1. This formulation promoted no larval toxicity in the absence of illumination, and sucrose alone did not induce larval phototoxicity. The photodegradation byproducts (intermediates) of curcumin were determined and the photodegradation mechanisms proposed. Intermediates with m/z 194, 278, and 370 were found and characterized using LC-MS. The ecotoxicity of the byproducts on non-target organisms (Daphnia, fish, and green algae) indicates that the intermediates do not exhibit any destructive potential for aquatic organisms. The results of photodegradation and ecotoxicity suggest that curcumin is environmentally safe for non-target organisms and, therefore, can be considered for population control of Ae. aegypti.

Influence of electrolysis conditions on the treatment of herbicide bentazon using artificial UVA radiation and sunlight. Identification of oxidation products.

The main objective of this work is to demonstrate the viability of solar photoelectro-Fenton (SPEF) process to degrade pesticides in urban wastewater matrix, selecting the herbicide bentazon as a model molecule. In order to provide a correct assessment of the role of the different oxidants and catalysts involved, bentazon was comparatively treated by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and UVA-assisted EF (i.e., PEF) processes as well, either in sulfate or chloride media. Trials were made in a stirred tank reactor with an air-diffusion cathode and a boron-doped diamond (BDD), RuO2-based or Pt anode. In chlorinated matrices, the herbicide disappeared more rapidly using a RuO2-based anode because of the generated active chlorine. The best mineralization performance was always obtained using BDD due to its higher oxidation power, which allowed the complete destruction of refractory chloroderivatives. A concentration of 0.50 mM Fe2+ was found optimal to catalyze Fenton's reaction, largely enhancing the mineralization process under the action of OH. Among photo-assisted treatments, sunlight was proven superior to a UVA lamp to promote the photolysis of intermediates, owing to its greater UV irradiance and contribution of visible photons, although PEF also allowed achieving a large mineralization. In all cases, bentazon decay obeyed a pseudo-first-order kinetics. SPEF treatment in urban wastewater using BDD at only 16.6 mA cm-2 yielded 63.2% mineralization. A thorough, original reaction pathway for bentazon degradation is proposed, including seven non-chlorinated aromatics, sixteen chloroaromatics and two chloroaliphatics identified by GC-MS, most of them not previously reported in literature. Ion-exclusion HPLC allowed the detection of seven short-chain linear carboxylic acids.

Kinetic studies of the reaction between pesticides and hydroxyl radical generated by laser flash photolysis.

BACKGROUND: Due to contamination of the environment by pesticides and their mishandling, there is the need for treatment of contaminated sites and correct disposal of materials containing them. Thus, studies with advanced oxidation processes are expanding and can determine the rate constant of the hydroxyl radical with organic compounds of great importance in environmental contamination. In this context, the use of laser flash photolysis has been shown to be viable for the determination of these constants. RESULTS: The reaction rate constants of different pesticides with HO(•) in degassed acetonitrile have been determined. They were 1.6 × 10(9) M(-1) s(-1), 0.6 × 10(9) M(-1) s(-1), 1.2 × 10(9) M(-1) s(-1), 2.4 × 10(9) M(-1) s(-1) and 2.2 × 10(9) M(-1) s(-1) for the pesticides carbaryl, propoxur, fenoxycarb, ethoxysulfuron and chlorimuron-ethyl, respectively. These values are about an order of magnitude smaller than the diffusion controlled rate and correlate with the relative rates of disappearance of the pesticides in the photo-Fenton reaction in water. CONCLUSION: The correlation of the relative rate constants determined by laser flash photolysis with the relative rates of photo-Fenton degradation of the pesticides is compelling evidence for the participation of the hydroxyl radical in the degradation of these pesticides in the latter system.

Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration.

A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2,4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe(2+) ([Fe(2+)](0)) from 1.0 up to 2.5 mM, the rate in mmol of H(2)O(2) fed into the system (FH(2)O(2);in) from 3.67 up to 7.33 mmol of H(2)O(2)/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes.

Antituberculosis drug isoniazid degraded by electro-Fenton and photoelectro-Fenton processes using a boron-doped diamond anode and a carbon-PTFE air-diffusion cathode.

Solutions with 0.65 mM of the antituberculosis drug isoniazid (INH) in 0.050 M Na2SO4 at pH 3.0 were treated by electro-Fenton (EF) and UVA photoelectro-Fenton (PEF) processes using a cell with a BDD anode and a carbon-PTFE air-diffusion cathode. The influence of current density on degradation, mineralization rate, and current efficiency has been thoroughly evaluated in EF. The effect of the metallic catalyst (Fe2+ or Fe3+) and the formation of products like short-chain linear aliphatic carboxylic acids were assessed in PEF. Two consecutive pseudo-first-order kinetic regions were found using Fe2+ as catalyst. In the first region, at short time, the drug was rapidly oxidized by ●OH, whereas in the second region, at longer time, a resulting Fe(III)-INH complex was much more slowly removed by oxidants. INH disappeared completely at 300 min by EF, attaining 88 and 94% mineralization at 66.6 and 100 mA cm-2, respectively. Isonicotinamide and its hydroxylated derivative were identified as aromatic products of INH by GC-MS and oxalic, oxamic, and formic acids were quantified by ion-exclusion HPLC. The PEF treatment of a real wastewater polluted with the drug led to slower INH and TOC abatements because of the parallel destruction of its natural organic matter content.

Influence of chelation on the Fenton-based electrochemical degradation of herbicide tebuthiuron.

This study describes the performance of electro-Fenton (EF) and photoelectro-Fenton (PEF) processes to degrade the herbicide tebuthiuron (TBH) in 0.050 M Na2SO4 at pH = 3.0. Experiments were performed in an undivided cell equipped with a boron-doped diamond (BDD) or Pt anode and an air-diffusion cathode that produces H2O2. Physisorbed hydroxyl radicals (M(OH)) generated from water oxidation at the anode and/or free OH formed from Fenton's reaction acted as main oxidants. All processes became much more effective using a BDD anode because of the higher oxidation power of BDD(OH). Sulfate and nitrate were the predominant ions released during TBH destruction. In both, EF and PEF treatments, two distinct kinetic regimes were observed, the first one corresponding to the oxidation of free TBH by OH and the second one to that of the Fe(III)-TBH complex by M(OH). The effect of Fe2+ and TBH concentrations on the kinetics of both regions has been examined. Moreover, a poor mineralization was reached with Pt anode, whereas almost total mineralization was attained by EF and PEF with BDD. Both processes showed analogous mineralization rates because the intermediates produced could not be photodegraded by UVA light. Gas chromatography-mass spectrometry analysis of electrolyzed solutions revealed the generation of eight heteroaromatics along with 1,3-dimethylurea, which have been included in a reaction pathway proposed for the initial degradation of TBH.

Degradation of 4-aminoantipyrine by electro-oxidation with a boron-doped diamond anode: Optimization by central composite design, oxidation products and toxicity.

Electro-oxidation with electrogenerated H2O2 (EO-H2O2) was applied to treat acidic aqueous solutions of 4-aminoantipyrine (4-AA), a persistent drug metabolite of dipyrone, in sulfate medium. Trials were made using a boron-doped diamond anode in the presence of H2O2 electrogenerated on site. A 24 central composite design (CCD) was employed to evaluate the effect of four independent variables, namely current density (j), pH, 4-AA concentration and electrolysis time, on the percentages of degradation and mineralization, as well as on mineralization current efficiency (MCE). Predicted responses agreed with observed values, showing linear trendlines with good R2 and R2adj values. The degradation was optimum at j=77.5mAcm-2, pH3.5 and 62.5mgL-1 4-AA, leading to 63% and 99% removal after 3 and 7min, respectively. For those solutions, the largest mineralization was found at j=77.5mAcm-2, attaining 45% abatement at 175min. Low MCE values were obtained in all electrolyses. An initial route for 4-AA degradation is proposed based on one dimer and eleven aromatic and aliphatic intermediates detected in the treated solutions at pH3.5 by LC-MS. The initial 62.5mgL-1 solution at pH3.5 presented acute toxicity on Artemia salina larvae, with LC50=13.6mgL-1, being substantially reduced after 3 and 7min of EO-H2O2 at j=77.5mAcm-2 due to the formation of less toxic derivatives.

Optimization of nimesulide oxidation via a UV-ABC/H2O2 treatment process: Degradation products, ecotoxicological effects, and their dependence on the water matrix.

Nimesulide (Nim) degradation in ultrapure water (UW) and municipal sewage (MS) via UV-ABC/H2O2 was investigated. The variables included in the experimental design were time, initial Nim, and initial H2O2 concentrations. Resulting decreases in Nim concentration (monitored by high performance liquid chromatography (HPLC) using a photodiode array detector operating at a maximum UV absorbance of 300 nm), mineralization (from total organic carbon (TOC) measurements), and ecotoxicity (assays employing the bioindicators Daphnia similis, Artemia salina, and Allium cepa) were also studied. Degradation rates of 90% or higher were found for 15-20 min reaction times, employing combinations of [H2O2] = 50-150 mg L-1 and [Nim] = 8.5-15 mg L-1 prepared with MS. Mineralization rates of 70% and higher were attained within 60 min of reaction for [Nim] = 15 mg L-1 prepared in MS with [H2O2] = 100 mg L-1. Nim by-products were detected and possible degradation pathways proposed. Ecotoxicity evaluation using A. salina, D. similis, and A. cepa revealed that the treated samples had significantly lower toxicity. Exposure to treated samples resulted in survival rates of 79% for A. salina and over 90% for D. similis. No root growth inhibition was observed in A. cepa exposed to treated samples, whereas exposure to untreated samples inhibited root growth by 60%. Statistical analysis revealed elimination of cytotoxicity and reduction of genotoxicity against A. cepa. The results showed that the UV-ABC/H2O2 process can be employed as a pre- or post-treatment method to remove Nim from contaminated wastewater.

Mineralization of humic acids (HAs) by a solar photo-Fenton reaction mediated by ferrioxalate complexes: commercial HAs vs extracted from leachates.

The mineralization of bio-recalcitrant humic acids (HAs) by a solar photo-Fenton (SPF) process was investigated in aqueous system, in order to understand its abatement in real high-HA content matrices, such as sanitary landfill leachates. SPF reactions were performed in tubular photoreactors with CPCs at lab-scale (simulated solar light) and pilot-scale (natural sunlight). Considering the experimental conditions selected for this work, the formation of insoluble HA-Fe3+ complexes was observed. Thus, to avoid HA precipitation, oxalic acid (Ox) was added, since Fe3+-Ox complexes present a higher stability constant. The effect of different process variables on the performance of SPF reaction mediated by ferrioxalate complexes (SPFF) was assessed with excess of H2O2 (50-250 mg L-1), at lab-scale: (i) pH (2.8-4.0); (ii) initial iron concentration (20-60 mg Fe3+ L-1); (iii) iron-oxalate molar ratio (Fe3+-Ox of 1:3 and 1:6); (iv) temperature (20-40 °C); (v) UV irradiance (21-58 WUV m-2); and (vi) commercial-HA concentration (50-200 mg C L-1). At the best lab conditions (40 mg Fe3+ L-1, pH 2.8, 30 °C, 1.6 Fe3+-Ox molar ratio, 41 WUV m-2), commercial HAs' mineralization profile was also compared with HAs extracted from a sanitary landfill leachate, achieving 88 and 91% of dissolved organic carbon removal, respectively, after 3-h irradiation (8.7 kJUV L-1). Both reactions followed the same trend, although a 2.1-fold increase in the reaction rate was observed for the leachate-HA experiment, due to its lower humification degree. At pilot-scale, under natural sunlight, 95% HA mineralization was obtained, consuming 42 mM of H2O2 and 5.9 kJUV L-1 of accumulated UV energy. However, a pre-oxidation during 2.8 kJUV L-1 (12 mM H2O2) was enough to obtain a biodegradability index of 89%, showing the strong feasibility to couple the SPFF process to a downstream biological oxidation, with low chemicals and energetic demands. Graphical abstract ᅟ.

Photo-Fenton treatment of valproate under UVC, UVA and simulated solar radiation.

The abatement of valproic acid sodium salt (VA) via photo-Fenton process was investigated to evaluate the effect of irradiation type. Three different light sources have been used: UVA (black light blue lamps, BLB reactor), UVC (UVC reactor) and simulated sunlight in a Solarbox (SB). Using the highest concentrations of Fe2+ (10mgL-1) and H2O2 (150mgL-1), 100% of VA degradation was observed in BLB and UVC devices, and 89.7% in Solarbox. Regarding mineralization, 67.4% and 76.4% of TOC conversion were achieved in BLB and UVC, respectively. In Solarbox, mineralization was negligible. Treated solutions under UVA or UVC radiation became biodegradable (BOD5/COD≥0.25), which was not observed in Solarbox where BOD5/COD achieved was only 0.20. Regarding to toxicity (Vibrio Fischeri method), all processes have promoted the overall toxicity reduction of VA solution. Transformation products were identified by a LC-ESI-TOF mass spectrometer, and degradation pathways were proposed. Operating costs and the energy needed by mg of VA removed were estimated and compared, for the different installations, showing that UVA can remove around 3 times more VA than SB and 2 times more VA than UVC, under the same conditions.

Degradation of the insecticide propoxur by electrochemical advanced oxidation processes using a boron-doped diamond/air-diffusion cell.

A solution with 0.38 mM of the pesticide propoxur (PX) at pH 3.0 has been comparatively treated by electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF), and photoelectro-Fenton (PEF). The trials were carried out with a 100-mL boron-doped diamond (BDD)/air-diffusion cell. The EO-H2O2 process had the lowest oxidation ability due to the slow reaction of intermediates with •OH produced from water discharge at the BDD anode. The EF treatment yielded quicker mineralization due to the additional •OH formed between added Fe2+ and electrogenerated H2O2. The PEF process was the most powerful since it led to total mineralization by the combined oxidative action of hydroxyl radicals and UVA irradiation. The PX decay agreed with a pseudo-first-order kinetics in EO-H2O2, whereas in EF and PEF, it obeyed a much faster pseudo-first-order kinetics followed by a much slower one, which are related to the oxidation of its Fe(II) and Fe(III) complexes, respectively. EO-H2O2 showed similar oxidation ability within the pH range 3.0-9.0. The effect of current density and Fe2+ and substrate contents on the performance of the EF process was examined. Two primary aromatic products were identified by LC-MS during PX degradation.

Laser flash photolysis study of the photocatalytic step of the photo-fenton reaction in saline solution.

The photo-Fenton reaction (Fe2+/Fe3+, H2O2, UV light) is strongly inhibited by high concentrations of added chloride ion. In this work, the effect of added chloride ion on the photocatalytic step that converts Fe(III) back to Fe(II) is studied by nanosecond laser flash photolysis over a wide range of pH (1.0-3.3) and concentrations of Fe(III) (0.1-1.0 mM) and chloride ion (0.05-0.75 M). An explicit mechanistic model based on the preferential formation of the less-reactive Cl2*- radical anion via two routes (competitive photolysis of the iron(III)-chloride complex to chlorine atoms instead of the desired hydroxyl radical and pH-dependent scavenging of the hydroxyl radical by chloride ion) is proposed. This model, which fits the laser flash photolysis data for the production and decay of Cl2*- over the entire range of conditions investigated, suggests that inhibition of the photocatalytic step of the photo-Fenton process in the presence of chloride ion can be circumvented by maintaining the pH of the medium at or slightly above 3.0 throughout the reaction.

Tolfenamic acid degradation by direct photolysis and the UV-ABC/H2O2 process: factorial design, kinetics, identification of intermediates, and toxicity evaluation.

This study employed direct UV-ABC photolysis and the UV-ABC/H2O2 process to investigate the degradation of tolfenamic acid (TA), a common anti-inflammatory drug used in both human and veterinary medicine. A 23 factorial design with added center point was used to evaluate the effect of three independent variables-namely, H2O2 concentration ([H2O2]), TA concentration ([TA]), and experiment time (time)-on TA degradation and H2O2 photolysis during UV-ABC/H2O2 treatment using a high-pressure mercury vapor lamp (photon flux of 2.6307 × 104 J s-1) as the UV irradiation source. The responses yielded similar values, revealing a linear behavior, with correlation coefficients R = 0.9968 and Radj = 0.9921 for TA degradation and R = 0.9828 and Radj = 0.9570 for H2O2 photolysis. The most efficient combination of variables was [H2O2] = 255 mg L-1 and [TA] = 25 mg L-1, resulting in 100% TA degradation and 98.87% H2O2 photolysis by 90 min of treatment. Additionally, the second-order kinetic constant of the reaction between TA and HO● was determined using a competitive kinetic model, employing 2,4-dichlorophenoxyacetic acid (2,4D) as the reference compound. The kinetic constant was 1.9 × 1010 M-1 s-1 in alkaline medium. TA degradation by direct photolysis generated quinone imines as by-products, responsible for the formation of a dark red "internal filter" that increased the value of acute toxicity to Artemia salina. The UV-ABC/H2O2 process did not promote formation of quinone imines by 90 min of treatment and therefore did not increase acute toxicity values. Several by-products generated during TA degradation were identified and possible degradation pathways for the UV-ABC and UV-ABC/H2O2 processes were proposed.

Synthesis and characterization of TiO2 and TiO2/Ag for use in photodegradation of methylviologen, with kinetic study by laser flash photolysis.

This paper reports the synthesis, characterization, and application of TiO2 and TiO2/Ag nanoparticles for use in photocatalysis, employing the herbicide methylviologen (MV) as a substrate for photocatalytic activity testing. At suitable metal to oxide ratios, increases in silver surface coating on TiO2 enhanced the efficiency of heterogeneous photocatalysis by increasing the electron transfer constant. The sol-gel method was used for TiO2 synthesis. P25 TiO2 was the control material. Both oxides were subjected to the same silver incorporation process. The materials were characterized by conventional spectroscopy, SEM micrography, X-ray diffraction, calculation of surface area per mass of catalyst, and thermogravimetry. Also, electron transfers between TiO2 or TiO2/Ag and MV in the absence and presence of sodium formate were investigated using laser flash photolysis. Oxides synthesized with 2.0 % silver exhibited superior photocatalytic activity for MV degradation.

Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation.

In the present study, selected advanced oxidation processes (AOPs)-namely, photo-Fenton (with Fe(2+), Fe(3+), and potassium ferrioxalate-FeOx-as iron sources), solar photo-Fenton, Fenton, and UV/H2O2-were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H2O2 process were most efficient for mineralizing MTX, with 77, 82, and 90% of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe(3+):MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10(4) M(-1), indicating high MTX affinity for Fe(3+). Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H2O2 process is usually slower than the photo-Fenton process, but, in this study, the UV/H2O2 process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H2O2 or by UV/H2O2/FeOx at the concentrations tested.

A mechanistic kinetic model for phenol degradation by the Fenton process.

The objective of this paper is to develop and validate a mechanistic model for the degradation of phenol by the Fenton process. Experiments were performed in semi-batch operation, in which phenol, catechol and hydroquinone concentrations were measured. Using the methodology described in Pontes and Pinto [R.F.F. Pontes, J.M. Pinto, Analysis of integrated kinetic and flow models for anaerobic digesters, Chemical Engineering Journal 122 (1-2) (2006) 65-80], a stoichiometric model was first developed, with 53 reactions and 26 compounds, followed by the corresponding kinetic model. Sensitivity analysis was performed to determine the most influential kinetic parameters of the model that were estimated with the obtained experimental results. The adjusted model was used to analyze the impact of the initial concentration and flow rate of reactants on the efficiency of the Fenton process to degrade phenol. Moreover, the model was applied to evaluate the treatment cost of wastewater contaminated with phenol in order to meet environmental standards.

Surfactant degradation by a catechol-driven Fenton reaction.

The addition of 0.5mM catechol is shown to accelerate the degradation and mineralization of the anionic surfactant DowFax 2A1 (sodium dodecyldiphenyloxide disulfonate) under conventional Fenton reaction conditions (Fe(II) plus H(2)O(2) at pH 3). The catalytic effect causes a 3-fold increase in the initial rate (up to ca. 20 min) of conversion of the surfactant to oxidation products (apparent first-order rate constants of 0.021 and 0.061 min(-1) in the absence and presence of catechol, respectively). Although this catalytic rate increase persists for a certain amount of time after complete disappearance of catechol itself (ca. 8 min), the reaction rate begins to decline slowly after the initial 20 min towards that observed in the absence of added catechol. Total organic carbon (TOC) measurements of net mineralization and cyclic voltammetric and high performance liquid chromatographic (HPLC) measurements of the initial rate of reaction of catechol and the surfactant provide insight into the role of catechol in promoting the degradation of the surfactant and of degradation products as the eventual inhibitors of the Fenton reaction.

Photolysis of ferric ions in the presence of sulfate or chloride ions: implications for the photo-Fenton process.

The photo-Fenton process (Fe(2+)/Fe(3+), H(2)O(2), UV light) is one of the most efficient and advanced oxidation processes for the mineralization of the organic pollutants of industrial effluents and wastewater. The overall rate of the photo-Fenton process is controlled by the rate of the photolytic step that converts Fe(3+) back to Fe(2+). In this paper, the effect of sulfate or chloride ions on the net yield of Fe(2+) during the photolysis of Fe(3+) has been investigated in aqueous solution at pH 3.0 and 1.0 in the absence of hydrogen peroxide. A kinetic model based on the principal reactions that occur in the system fits the data for formation of Fe(2+) satisfactorily. Both experimental data and model prediction show that the availability of Fe(2+) produced by photolysis of Fe(3+) is inhibited much more in the presence of sulfate ion than in the presence of chloride ion as a function of the irradiation time at pH 3.0.

Abatement of the inhibitory effect of chloride anions on the photo-Fenton process.

The inhibition of the photo-Fenton (Fe2+/Fe3+, H2O2, UV light) degradation of synthetic phenol wastewater solutions by chloride ions is shown to affect primarily the photochemical step of the process, having only a slight effect on the thermal or Fenton step. Kinetic studies of the reactions of oxoiron (IV) (FeO2+) with phenol indicate that, if FeO2+ is formed in the photo-Fenton degradation, its role is probably minor. Finally, it is shown that, for both a synthetic phenol wastewater and an aqueous extract of Brazilian gasoline, the inhibition of the photo-Fenton degradation of the organic material in the presence of chloride ion can be circumvented by maintaining the pH of the medium at or slightly above 3 throughout the process, even in the presence of significant amounts of added chloride ion (0.5 M).