Critical review on the mechanistic photolytic and photocatalytic degradation of triclosan.

The environmentally extended presence of triclosan, TCS, component of many pharmaceutical and personal care products, and its known persistent character have awoke the scientific and social concern leading to the study of effective remediation techniques. Advanced oxidation techniques stand out for the effectiveness in degrading many persistent compounds, and as a result, they have been addressed by many researchers. However, the powerful oxidation media might lead to the formation of undesirable by-products, concern that has also been widely addressed. With regard to the presence of TCS, photolytic and photocatalytic processes provide a very effective degradation yield and rate, with a large number of reports addressing its removal from different environmental matrices. But currently, there is no clear understanding of the mechanisms involved and the routes responsible for the formation of degradation products. Thus, this work presents an exhaustive and critical analysis of the state of the art related to the photo-degradation of TCS, with special focus on the formation of oxidation by-products, on the phenomena responsible and on the influence of operation variables. This report aims at offering valuable information to researchers dealing with this environmentally relevant problem.

PCDD/Fs traceability during triclosan electrochemical oxidation.

5-Chloro-2-(2,4-dichlorophenoxy)phenol (TCS) is a persistent organic pollutant (POP) widely used in different consumer goods. Its recalcitrant nature demands the application of effective remediation technologies in order to avoid the negative environmental impact associated to the discharge of contaminated waters. Although advanced oxidation technologies have been considered the best alternative to destroy bio-recalcitrant compounds, the likely formation of high toxicity byproducts must be analysed before large-scale deployment. In this work, we aim to trace the presence of chlorinated compounds during the electro-oxidation of aqueous TCS samples. First, we analyze the influence of the initial concentration of TCS on the toxicity of the oxidation medium expressed by the International-Toxicity Equivalency Factor (I-TEF); second, we have detected the formation of intermediate organo-chlorinated compounds by GC-MS supported by HPLC and finally, we have quantified the concentration of highly-polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) by HRGC-HRMS within the oxidation treatment. In those samples where TCS had been completely degraded the concentration of PCDD/Fs showed a high increase, especially when NaCl was used as electrolyte, with the initial concentration of TCS. Under these conditions the I-TEF achieved values up to 3.8 × 102 pg L-1.

Fate and hazard of the electrochemical oxidation of triclosan. Evaluation of polychlorodibenzo­p­dioxins and polychlorodibenzofurans (PCDD/Fs) formation.

Triclosan (TCS) is widely used as antiseptic or preservative in many personal care products (PCPs), such as cosmetics, hand wash, toothpaste and deodorant soaps, among others. It is characterized by acute toxicity, resistance to biodegradation, environmental persistence and relatively high lipophilicity. In order to protect the environment and natural resources from the negative effects of the discharge of polluted wastewater with TCS, the application of efficient remediation technologies able to degrade the pollutant to harmless levels becomes crucial. Electrochemical oxidation, among all advanced oxidation processes (AOPs), has been reported as very effective in the complete degradation of a number of persistent pollutants; therefore, its performance using boron-doped diamond (BDD) anodes, and response to operation variables, has been studied in this work. As expected, complete degradation of TCS was achieved in all the studied conditions; however, going a step further and knowing that TCS is a precursor of polychlorinated dibenzo­p­dioxins and dibenzofurans (PCDD/Fs), their quantitative presence in the oxidation media has been assessed. Results showed the dominance of dichlorinated (DCDD) and trichlorinated (TrCDD/Fs) in the homologue profile of total PCDD/Fs, reaching values up to 1.48 × 105 pg L-1 in samples with initial concentration of TCS of 100 mg L-1 and NaCl as electrolyte. Under these conditions, the International Toxicity Equivalency Factor (I-TEF) achieved values up to 2.76 × 102 pg L-1. Nevertheless, the presence of copper in the oxidation medium tends to reduce I-TEF values. Finally, considering the information reported in literature, a mechanism describing the formation of low chlorinated PCDD/Fs from TCS oxidation reactions is proposed.

Theoretical and experimental formation of low chlorinated dibenzo-p-dioxins and dibenzofurans in the Fenton oxidation of chlorophenol solutions.

The formation of chlorinated and non-chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) has been experimentally investigated after the Fenton oxidation of 2-chlorophenol (2-CP, 15.56 mM) aqueous solutions by assessing the influence of iron concentration (0.09-2.88 mM), hydrogen peroxide dose (40.44-202.20 mM), temperature (20-70 °C) and chloride concentration (0-56.35 mM). The presence of chloride in the medium together with room temperature and substoichiometric Fenton conditions (40.44 mM H2O2) led to an increase in total PCDD/Fs concentration from less than 1 ng L(-1) to 2 µg L(-1). Results showed a dominance of the dichlorinated species (DCDD/Fs) in the homologue profile of total PCDD/Fs reaching values up to 1.5 µg L(-1). Furthermore, the products distribution exhibited a gradual decrease in the homologue concentration as the chlorination degree increased from di-to octachloro-substituted positions. Considering the characteristics of the reaction medium, the experimental results, and the information gathered in bibliography with regard to the generation of active radicals from 2-chlorophenol, a mechanism describing the formation of low chlorinated PCDD/Fs in a Fenton oxidizing aqueous system has been proposed.

Assessment of PCDD/Fs formation in the Fenton oxidation of 2-chlorophenol: Influence of the iron dose applied.

Toxic polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) may be formed during remediation of chlorinated phenols via Fenton oxidation. To highlight the need for monitoring the production of toxic byproducts in these reactions, this work assessed the influence of iron dose (0.09-0.36 mM) on the Fenton oxidation of 2-chlorophenol (2-CP, 15.56 mM), a potential precursor of PCDD/Fs, by quantifying 2-CP removal and mineralization rates as well as byproducts yields, including PCDD/Fs. Although the increase in the iron dose showed positive contribution to 2-CP oxidation, under the operating conditions of the current study (H2O2 at 20% of the stoichiometric dose and 20 °C), there was no effect on the mineralization rate, and TOC and chlorine balances were far to be closed, depicting the presence of chlorinated organic byproducts in the reaction medium. After 4 h of treatment, the total PCDD/Fs concentrations increased by 14.5-39 times related to the untreated sample when the iron doses tested decreased from 0.36 to 0.09 mM, with preferential formation of PCDFs over PCDDs and dominance of lower chlorinated congeners such as tetra and penta-PCDD/Fs. The treatment with the highest iron dose (0.36 mM) exhibited the lowest PCDD/Fs yields and was thus most successful at mitigating toxic byproducts of the Fenton oxidation, leading to lower sample toxic equivalence (TEQ) value.

The critical role of the operating conditions on the Fenton oxidation of 2-chlorophenol: assessment of PCDD/Fs formation.

This work assesses the influence of the operating conditions H2O2 dose (20 or 100% of the stoichiometric amount), temperature (20 or 70°C), and the presence of chloride in the oxidation medium in the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) during Fenton treatment of aqueous samples of 2-chlorophenol, 2-CP, one of the strongest precursor of PCDD/Fs. After 4h of oxidation in the experiments carried out with 20% H2O2 chlorinated phenoxyphenols and biphenyls, which are intermediates in PCDD/Fs formation, as well as PCDD/Fs were observed, resulting in concentrations 11 times higher than in the untreated sample. Additionally, when NaCl was also present in the reaction medium, PCDD/Fs were formed at higher extent, with a total concentration 74.4 times higher than in the untreated 2-CP solution. Results depicted a preferential formation of PCDFs over PCDDs, with dominance of lower chlorinated PCDD/Fs (tetra and penta-PCDD/Fs). Besides, the formation of the most toxic PCDD/Fs congeners (2,3,7,8-PCDD/Fs) was not favored under the operating conditions used in this work.

Quantitative assessment of the formation of polychlorinated derivatives, PCDD/Fs, in the electrochemical oxidation of 2-chlorophenol as function of the electrolyte type.

The electrochemical degradation of 2-chlorophenol (2-CP) on boron-doped diamond (BDD) anodes was carried out using two electrolytes, NaCl and Na2SO4. Both electrolytes supported complete mineralization of 2-CP, but faster rates of degradation were observed in NaCl. After 4 h of oxidation, the total organic carbon (TOC) balance neared 100% with Na2SO4 for identifiable compounds, whereas 4 mM of TOC remained unidentified with NaCl. Since chlorophenols are known to be precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), a rigorous assessment of intermediate products was carried out. When near complete mineralization was achieved, the use of NaCl resulted in the concentration of total PCDD/Fs increasing 2.68 × 10(4) times compared to the untreated sample, and to toxicity values several times higher than the maximum level established by U.S. Environmental Protection Agency for water ingestion. When Na2SO4 was used, the increase in total PCDD/Fs concentration was 134 times lower than with NaCl and there was no significant 2,3,7,8-PCDD/Fs formation. Thus, we emphasize the importance of electrolyte selection in electro-oxidation processes, especially when PCDD/Fs precursors are initially present or may be formed in the treated water samples.