Ultrasound/chlorine sono-hybrid-advanced oxidation process: Impact of dissolved organic matter and mineral constituents

Abstract

In this work, after exploring the first report on the synergism of combining ultrasound (US: 600 kHz) and chlorine toward the degradation of Allura Red AC (ARAC) textile dye, as a contaminant model, the impact of various mineral water constituents (Cl^-, SO₄^2-, NO₃^-, HCO₃^- and NO₂^-) and natural organic matter, i.e., humic acid (HA), on the performance of the US/chlorine sono-hybrid process was assessed for the first time. Additionally, the process effectiveness was evaluated in a real natural mineral water (NMW) of a known composition. Firstly, it was found that the combination of ultrasound and chlorine (0.25 mM) at pH 5.5 in cylindrical standing wave ultrasonic reactor (f = 600 kHz and P_e = 120 W, equivalent to P_A ∼ 2.3 atm) enhanced in a drastic manner the degradation rate of ARAC; the removal rate being 320% much higher than the arithmetic sum of the two separated processes. The source of the synergistic effect was attributed to the effective implication of reactive chlorine species (RCS: Cl, ClO and Cl₂^-) in the degradation process. Radical probe technique using nitrobenzene (NB) as a specific quencher of the acoustically generated hydroxyl radical confirmed the dominant implication of RCS in the overall degradation rate of ARAC by US/chlorine system. Overall, the presence of humic acid and mineral anions decreased the efficiency of the sono-hybrid process; however, the inhibition degrees depend on the type and the concentration of the selected additives. The reaction of these additives with the generated RCS is presumably the reason for the finding results. The inhibiting effect of Cl^-, SO₄^2-, NO₃^- and NO₂^- was more pronounced in US/chlorine process as compared to US alone, whereas the inverse scenario was remarked for the effect of HA. These outcomes were associated to the difference in the reactivity of HA and mineral anions toward RCS and OH oxidizing species, in addition to the more selective character of RCS than hydroxyl radical. The displacement of the reaction zone with increasing the additive concentration may also be another influencing factor that favors competition reactions, which subsequently reduce the available reactive species in the reacting medium. The NMW exerted reductions of 43% and 10% in the process efficiency at pH 5.5 and 8, respectively, thereby confirming the RCS-quenching mechanism by the water matrix constituents. Hence, this work provided a precise understanding of the overall mechanism of chlorine activation by ultrasound to promote organic compounds degradation in water.

Keywords: Mineral anions; Natural organic matter; Reactive chlorine species (RCS); Synergy; Ultrasound/chlorine process.

Graphical abstract

Fig. 1

ARAC chlorination kinetics for different solution pH (a) and diverse chlorine dosages (b) (conditions: C₀ = 5 mg L⁻¹ (10 µM), [chlorine]₀ = 0.25 mM for (a) and 0.05–0.3 mM for (b), pH 3–10 for (a) and pH 5.5 for (b), V = 150 mL, temperature: 25 ± 1 °C, stirring speed: 300 rpm).

Fig. 2

ARAC degradation kinetics (a), and corresponding pseudo-first order rate constant (b), obtained under different oxidation systems, i.e., chlorine, ultrasound (US), US/chlorine, US/NB, and US/chlorine/NB (conditions: frequency: 600 kHz, power: 120 W, C₀ = 5 mg L⁻¹ (10 µM), [chlorine]₀ = 0.25 mM, [NB]₀ = 1 mM, 25 ± 1 °C, pH 5.5). NB: nitrobenzene.

Fig. 3

H₂O₂ evolution during the sonolysis of pure water and 5 mg L⁻¹ of ARAC solution (conditions: V = 150 mL, temperature: 25 ± 1 °C, frequency: 600 kHz, power: 120 W). Accumulation rates: 5.6 µM min⁻¹ in pure water and 4.17 µM min⁻¹ in ARAC solution (ARAC induced reduction of in the accumulation rate of H₂O₂, confirming the ^•OH pathway at the bubble/solution interface for the sonolytic degradation of ARAC).

Fig. 4

Effect of HA concentration on ARAC degradation kinetics (a), and corresponding effect of [HA] on the pseudo-first order rate constant (k) for US and US/chlorine treatment of ARAC (b) (conditions: frequency: 600 kHz, power: 120 W, C₀ = 5 mg L⁻¹ (10 µM), [chlorine]₀ = 0.25 mM, [HA]₀ = 0–15 mg L⁻¹, 25 ± 1 °C, pH 5.5). HA: Humic acid.

Fig. 5

Effect of mineral anions on ARAC degradation rate constant (k) for US and US/chlorine treatments (conditions: frequency: 600 kHz, power: 120 W, C₀ = 5 mg L⁻¹ (10 µM), [chlorine]₀ = 0.25 mM, [anions]₀ = 0–10 mM, 25 ± 1 °C, pH 5.5, except for HCO₃⁻ (pH 8)).

Fig. 6

Effect of water matrices on ARAC degradation rate constant (k) for US and US/chlorine treatments (conditions: frequency: 600 kHz, power: 120 W, C₀ = 5 mg L⁻¹ (10 µM), [chlorine]₀ = 0.25 mM, 25 ± 1 °C, pH 5.5 and 8). DW: deionized water, NMW: natural mineral water.