Solar photo-Fenton with Fe3+-EDDS and Fe3+-NTA at neutral pH for removal of ibuprofen, diclofenac and their main transformation products in wastewater

IF 5.2 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today Pub Date : 2024-11-19 DOI:10.1016/j.cattod.2024.115139

Marina Aliste , Lixy Olinda León-Morán , Carmen María Martínez-Escudero , Isabel Garrido , Fulgencio Contreras , Pilar Hellín , Pilar Flores , José Fenoll

{"title":"Solar photo-Fenton with Fe3+-EDDS and Fe3+-NTA at neutral pH for removal of ibuprofen, diclofenac and their main transformation products in wastewater","authors":"Marina Aliste , Lixy Olinda León-Morán , Carmen María Martínez-Escudero , Isabel Garrido , Fulgencio Contreras , Pilar Hellín , Pilar Flores , José Fenoll","doi":"10.1016/j.cattod.2024.115139","DOIUrl":null,"url":null,"abstract":"<div><div>In recent years, solar photo-Fenton (SPF) processes have gained interest owing to the use of a cost-free and sustainable radiation source and their effectiveness in removing pharmaceuticals, among other Emerging Pollutants (EPs), from wastewater. Especially, when iron complexes are used to work at neutral pH. The stability and biodegradability characteristics make ethylenediamine-N,N-disuccinic acid (EDDS), and nitrilotriacetic acid (NTA) suitable iron complexing agents. In this work, the removal of diclofenac (DCF) and ibuprofen (IBU), two of the most widely used Non-steroidal Anti-Inflammatory Drug (NSAID) for the treatment of pain, at 200 µg L<sup>−1</sup> was studied in wastewater using SPF at natural pH, comparing EDDS and NTA as chelating agents for the first time. The main transformation products (TPs) were also monitored. For this purpose, a suitable analytical method using liquid chromatography coupled to triple quadrupole tandem mass spectrometry (LC-QqQ-MS/MS) with Electro Spray Ionization negative mode (ESI<sup>-</sup>) was applied to determine the pharmaceutical EPs and their main TPs in wastewater. Next, they were confirmed by LC-QTOF-HRMS. DCF was degraded 44 % faster with NTA (t<sub>1/2</sub> 53 min) than with EDDS (t<sub>1/2</sub> 77 min), although the final removal percentages, including photolysis, were similar (90–93 %). In contrast, IBU removal with EDDS (t<sub>1/2</sub> 116 min) was twice as fast as with NTA (t<sub>1/2</sub> 231 min), whereas photolysis was ineffective. Twenty TPs were monitored, of which only three were detected because of the low concentration used in this study: DCF-2C (<em>m/z</em> 258.0326), DCF-6B (<em>m/z</em> 310.0040), and IBU-4 (<em>m/z</em> 221.1181). Their behaviour followed a formation-elimination profile, but only the complete oxidation of DCF-6 was achieved. This work focuses on the kinetic aspects and TPs formed, which are useful for improving knowledge for the development of efficient processes to abate organic pollutants in real aqueous matrices. Therefore, more EPs should be thoroughly studied to determine the efficiency of EDDS and NTA as iron-chelating agents and the necessity of implementing the SPF process in WWTPs.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"446 ","pages":"Article 115139"},"PeriodicalIF":5.2000,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Catalysis Today","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0920586124006333","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}

引用次数: 0

Abstract

In recent years, solar photo-Fenton (SPF) processes have gained interest owing to the use of a cost-free and sustainable radiation source and their effectiveness in removing pharmaceuticals, among other Emerging Pollutants (EPs), from wastewater. Especially, when iron complexes are used to work at neutral pH. The stability and biodegradability characteristics make ethylenediamine-N,N-disuccinic acid (EDDS), and nitrilotriacetic acid (NTA) suitable iron complexing agents. In this work, the removal of diclofenac (DCF) and ibuprofen (IBU), two of the most widely used Non-steroidal Anti-Inflammatory Drug (NSAID) for the treatment of pain, at 200 µg L⁻¹ was studied in wastewater using SPF at natural pH, comparing EDDS and NTA as chelating agents for the first time. The main transformation products (TPs) were also monitored. For this purpose, a suitable analytical method using liquid chromatography coupled to triple quadrupole tandem mass spectrometry (LC-QqQ-MS/MS) with Electro Spray Ionization negative mode (ESI^-) was applied to determine the pharmaceutical EPs and their main TPs in wastewater. Next, they were confirmed by LC-QTOF-HRMS. DCF was degraded 44 % faster with NTA (t_1/2 53 min) than with EDDS (t_1/2 77 min), although the final removal percentages, including photolysis, were similar (90–93 %). In contrast, IBU removal with EDDS (t_1/2 116 min) was twice as fast as with NTA (t_1/2 231 min), whereas photolysis was ineffective. Twenty TPs were monitored, of which only three were detected because of the low concentration used in this study: DCF-2C (m/z 258.0326), DCF-6B (m/z 310.0040), and IBU-4 (m/z 221.1181). Their behaviour followed a formation-elimination profile, but only the complete oxidation of DCF-6 was achieved. This work focuses on the kinetic aspects and TPs formed, which are useful for improving knowledge for the development of efficient processes to abate organic pollutants in real aqueous matrices. Therefore, more EPs should be thoroughly studied to determine the efficiency of EDDS and NTA as iron-chelating agents and the necessity of implementing the SPF process in WWTPs.

查看原文本刊更多论文

在中性 pH 条件下使用 Fe3+-EDDS 和 Fe3+-NTA 的太阳能光-芬顿去除废水中的布洛芬、双氯芬酸及其主要转化产物

近年来，太阳能光-芬顿（SPF）工艺越来越受到人们的关注，这是因为它使用了一种无成本、可持续的辐射源，而且能有效去除废水中的药物和其他新出现的污染物（EPs）。特别是当铁络合物在中性 pH 值下工作时。乙二胺-N,N-二丁二酸（EDDS）和氮基三乙酸（NTA）的稳定性和生物降解性使其成为合适的铁络合剂。在这项研究中，首次比较了 EDDS 和 NTA 作为螯合剂对废水中 200 µg L-1 浓度的双氯芬酸 (DCF) 和布洛芬 (IBU) 的去除效果，这两种药物是目前最广泛使用的治疗疼痛的非甾体抗炎药 (NSAID)。此外，还对主要转化产物（TPs）进行了监测。为此，采用了一种合适的分析方法，即液相色谱耦合三重四极杆串联质谱（LC-QqQ-MS/MS）和电喷雾电离负模式（ESI-）来测定废水中的药物 EPs 及其主要 TPs。然后，用 LC-QTOF-HRMS 对其进行了确认。使用 NTA 时，DCF 的降解速度（t1/2 53 分钟）比使用 EDDS 时（t1/2 77 分钟）快 44%，尽管最终去除率（包括光解）相似（90-93%）。相比之下，使用 EDDS（t1/2 116 分钟）去除 IBU 的速度是使用 NTA（t1/2 231 分钟）的两倍，而光解则无效。对 20 种 TPs 进行了监测，由于本研究使用的浓度较低，因此只检测到其中的三种：DCF-2C（m/z 258.0326）、DCF-6B（m/z 310.0040）和 IBU-4（m/z 221.1181）。它们的行为遵循形成-消除曲线，但只有 DCF-6 实现了完全氧化。这项工作的重点是动力学方面和形成的 TPs，这有助于增进知识，以开发有效的工艺来消减实际水基质中的有机污染物。因此，应深入研究更多的 EP，以确定 EDDS 和 NTA 作为铁螯合剂的效率，以及在污水处理厂实施 SPF 工艺的必要性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Catalysis Today 化学-工程：化工

CiteScore

11.50

自引率

3.80%

发文量

573

审稿时长

2.9 months

期刊介绍： Catalysis Today focuses on the rapid publication of original invited papers devoted to currently important topics in catalysis and related subjects. The journal only publishes special issues (Proposing a Catalysis Today Special Issue), each of which is supervised by Guest Editors who recruit individual papers and oversee the peer review process. Catalysis Today offers researchers in the field of catalysis in-depth overviews of topical issues. Both fundamental and applied aspects of catalysis are covered. Subjects such as catalysis of immobilized organometallic and biocatalytic systems are welcome. Subjects related to catalysis such as experimental techniques, adsorption, process technology, synthesis, in situ characterization, computational, theoretical modeling, imaging and others are included if there is a clear relationship to catalysis.