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


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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Data availability

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



advanced oxidation technologies


continuous stirred-tank reactor


wastewater effluent organic matter


finite volume method


nonribosomal peptides


ordinary differential equation


plug flow reactor


dissolved organic products generated from Zn-Bc degradation


dissolved organic products generated from EfOM degradation


residence time distribution


specific UV absorption


total organic carbon


ultraviolet radiation (254 nm)


wastewater treatment plant


zinc bacitracin

Abs254 nm :

total absorbance of the solution at 254 nm


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)


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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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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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 (2021). https://doi.org/10.1007/s11356-021-12437-4

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  • Zinc bacitracin
  • Antibiotics
  • Dynamic kinetic modeling
  • Tubular photoreactor
  • Transient continuous flow reactor
  • Effluent organic matter
  • Pharmaceutical wastewater treatment
  • UVC/H2O2 process