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A comprehensive dynamic kinetic model for the UVC/H2O2 process: application to zinc bacitracin degradation in wastewater as a case study

  • Advanced Oxidation/Reduction Technologies: An Perspective from Iberoamerican Countries
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Abstract

A dynamic kinetic model is presented for the UVC/H2O2-driven process. The model comprises 103 reactions, including background species, such as HCO3–/CO32–, NO2–, NO3–, SO42−, Cl−, and H2PO4−/HPO42/PO43– anions, and effluent organic matter (EfOM) was validated based on experimental data obtained for the photooxidation of the nonribosomal peptide antibiotic zinc bacitracin (Zn-Bc, 34 μmol L−1). The set of ordinary differential equations for 38 species was combined with the molar balances describing the recirculating tubular photoreactor used. Predictions for the photolytic and UVC/H2O2 processes confirmed the good agreement with experimental data, enabling the estimation of fundamental kinetic parameters, such as the direct photolysis quantum yield (Ф254 nm, Zn-Bc = 0.0143 mol Einstein−1) and the second-order rate constants for the reactions of Zn-Bc with HO•, HO2•, and O2•− radicals (2.64 × 109, 1.63 × 103, and 1.49 × 104 L mol−1 s−1, respectively). The predicted optimum process conditions correspond to [H2O2]0 = 6.8 mmol L−1 and a specific photon emission rate of 11.1 × 10−6 Einstein L−1 s−1. Zn-Bc photooxidation was significantly impacted by wastewater constituents, particularly EfOM and HCO3–/CO32– (i.e., alkalinity), resulting in a degradation rate about 32% lower compared to that obtained in deionized water. In particular, EfOM acts as a strong radical scavenger and inner filter. In addition, simulations pointed out the continuous tubular photochemical reactor as the best configuration for treating Zn-Bc-containing wastewater. This study hence provides a comprehensive modeling approach, especially useful for predicting the effect of complex water matrices on the performance of the UVC/H2O2 treatment process.

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All data generated or analyzed during this study are included in this published article.

Abbreviations

AOT:

advanced oxidation technologies

CSTR:

continuous stirred-tank reactor

EfOM:

wastewater effluent organic matter

FVM:

finite volume method

NRP:

nonribosomal peptides

ODE:

ordinary differential equation

PFR:

plug flow reactor

PROD1:

dissolved organic products generated from Zn-Bc degradation

PROD2:

dissolved organic products generated from EfOM degradation

RTD:

residence time distribution

SUVA:

specific UV absorption

TOC:

total organic carbon

UVC:

ultraviolet radiation (254 nm)

WWTP:

wastewater treatment plant

Zn-Bc:

zinc bacitracin

Abs254 nm :

total absorbance of the solution at 254 nm

[C]:

molar concentration of the species C (mol L−1)

[C]0 :

initial molar concentration of the species C (mol L−1)

E P,0 :

specific photon emission rate (μmol photons L−1 s−1)

k :

reaction rate constant (L mol−1 s−1 or s−1)

ka:

acid-base equilibrium constant

k global :

global reaction rate constant (s−1)

k Zn-Bc, HO • :

second-order reaction rate constant of Zn-Bc with hydroxyl radical (L mol−1 s−1)

\( {k}_{\mathrm{Zn}-\mathrm{Bc},\kern0.75em \mathrm{H}{\mathrm{O}}_2^{\bullet }} \) :

second-order reaction rate constant of Zn-Bc with hydroperoxyl radical (L mol−1 s−1)

\( {k}_{\mathrm{Zn}-\mathrm{Bc},\kern0.75em {\mathrm{O}}_2^{\bullet -}} \) :

second-order reaction rate constants of Zn-Bc with superoxide radical anion (L mol−1 s−1)

l reactor :

reactor path length (m)

n :

number of the compartment where the reaction occurs: 1 (CSTR 2) and 2 (PFR)

r :

reaction rate term (mol L−1 s−1)

t :

time (s)

UVA254 :

decadic UV absorption coefficient at 254 nm (cm−1)

UVA310 :

decadic UV absorption coefficient at 310 nm (cm−1)

V :

volume (L)

V T :

volume of the recirculating tank (L)

V r :

volume of the annular tubular photoreactor (L)

v :

flow rate (L s−1)

ε :

molar absorption coefficient (L mol−1 m−1)

Ф :

photolysis quantum yield (mol Einstein−1)

τ :

residence time (s)

ε :

molar absorption coefficient (L mol−1 m−1)

Ф :

photolysis quantum yield (mol Einstein−1)

τ :

residence time (s)

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Funding

This study was funded by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) - Finance Code 001 and National Council for Scientific and Technological Development (CNPq) (grant # 131210/2016-5).

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Authors and Affiliations

  1. Research Group in Advanced Oxidation Processes (AdOx), Chemical Systems Engineering Center − Department of Chemical Engineering, University of São Paulo, Av. Prof. Luciano Gualberto, 380, tv 3, São Paulo, 05508-900, Brazil

    Patrícia Metolina & Antonio Carlos Silva Costa Teixeira

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  1. Patrícia Metolina
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  2. Antonio Carlos Silva Costa Teixeira
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Contributions

P.M.: conceptualization, formal analysis, investigation, methodology, software, validation, visualization, writing—original draft, writing—review and editing. A.C.S.C.T.: conceptualization, formal analysis, validation, resources, writing—original draft, writing—review and editing, supervision, funding acquisition. All authors read and approved the final manuscript.

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Correspondence to Patrícia Metolina.

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Metolina, P., Teixeira, A.C.S.C. A comprehensive dynamic kinetic model for the UVC/H2O2 process: application to zinc bacitracin degradation in wastewater as a case study. Environ Sci Pollut Res 28, 24150–24166 (2021). https://doi.org/10.1007/s11356-021-12437-4

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