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Stoichiometric excesses of H2O2 as dosimetry strategy: proof of concept for UVC-H2O2, dark-Fenton, and UVC-Fenton

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Abstract

Hydrochlorothiazide (HCT) is a pharmaceutical micropollutant highly toxic to the environment, being absolutely necessary to oxidize it completely to CO2. Here, the variables stoichiometric H2O2 excess for (a) degradation and (b) mineralization are defined and used as metric to quantify the dosimetry of the H2O2. So that, dose of H2O2 qualifies being under- and over-dose respectively for values below and above such standards. In this work, these concepts have been elucidated across AOPs regarding the H2O2 degradation excess, whereas only UVC-Fenton was used regarding the H2O2 mineralization excess. At a H2O2 mineralization excess of 0.68 (equivalent to degradation excess of 36.74), oxidation via UVC-H2O2 enables absolute (100%) HCT degradation within 60 min; however, the mineralization of HCT demonstrated limited optimization for all AOPs employed in the beaker-like reactor of this work, being the underlying reasons investigated hereby. At best, 26.70% HCT mineralization was observed within 60 min of UVC photo-Fenton using an initial 2.00 H2O2 mineralization excess. Such mineralization of 26.7% is unexpectedly low considering that, in addition, the residual H2O2 concentration almost fully depletes within 30 min of UVC-Fenton oxidation. Taken all that together, the loss of H2O2 due its decomposition induced by the risen temperature from 28 to 70ºC very likely were the underlying reason preventing better mineralization performance. We successfully demonstrated 18% of mean efficiency of radical •OH consumption signals that the overheating is indeed a designer problem with the photo-reactor since a well-refrigerated photo-reactor shows a mean efficiency of 38% for the same H2O2 excess.

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Funding

Graduate Program in Chemical Engineering of the Federal University of Rio Grande do Norte (UFRN) has funding the consumables; National Program for Academic Cooperation (PROCAD-CAPES, # 403230/2013–6) provide financial support to the scientists travel between the universities, and National Council of Research and Development (CNPq, #155046/2018–7) has support an individual scholarship.

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Authors and Affiliations

  1. Department of Chemical Engineering, Federal University of Rio Grande Do Norte (UFRN), Av. Sen. Salgado Filho 3000, Natal, RN, Brazil

    Fernando José Vieira Cunha-Filho & Osvaldo Chiavone-Filho

  2. School of Science and Technology, Federal University of Rio Grande Do Norte (UFRN), Av. Sen. Salgado Filho 3000, Natal, RN, Brazil

    Douglas do Nascimento Silva

  3. Departamento de Engenharia Química - Escola Politécnica, Universidade de São Paulo (USP), Cidade Universitária, São Paulo, SP, 05508-900, Brazil

    Claudio Augusto Oller do Nascimento & Andressa Mota-Lima

Authors
  1. Fernando José Vieira Cunha-Filho
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  2. Douglas do Nascimento Silva
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  3. Claudio Augusto Oller do Nascimento
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  4. Osvaldo Chiavone-Filho
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  5. Andressa Mota-Lima
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Contributions

C.A.O.N. acquired funds; O. C-F administrated the project; A.M-L planned the experiments and conceptualized the methodology for data analysis; F.J.V.C-F employed different experimental techniques and methodologies to execute all the experiments; D.N.D. reproduced part of the experiments and confirmed the temperature elevation of the aqueous solution; A.M-L, D.N.S and F.J.V.C-F analyzed the data. A.M-L wrote the manuscript. C.A.O.N. revised the manuscript. All authors discussed the main results.

Corresponding author

Correspondence to Andressa Mota-Lima.

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Competing interests

A.M-L, O. C-F, and F.J.V.C-F have no financial interests. Non-financial interests: Claudio A. Oller do Nascimento has served on advisory board Research Centre for Greenhouse Gas Innovation-RCGI.

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Cunha-Filho, F.J.V., do Nascimento Silva, D., do Nascimento, C.A.O. et al. Stoichiometric excesses of H2O2 as dosimetry strategy: proof of concept for UVC-H2O2, dark-Fenton, and UVC-Fenton. Environ Sci Pollut Res 30, 14860–14872 (2023). https://doi.org/10.1007/s11356-022-22968-z

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