Linking Triclosan's Structural Features to Its Environmental Fate and Photoproducts.

Triclosan is a high-production volume chemical, which has become widely detected in environmental systems because of its widespread usage. Photodegradation has been identified as a major degradation pathway, but the identified photoproducts are also chemicals of concern. In this study, lower chlorinated derivatives of triclosan were synthesized to investigate the impact the chlorine substituents have on the photodegradation rate and the photoproducts produced. In addition, the photodegradation of two classes of photoproducts-dibenzo-p-dioxins (DDs) and 2,2'-dihydroxylated biphenyls-was also investigated. Degradation of triclosan in near-surface sunlit waters was relatively fast (t1/2 < 5 h). Calculated degradation rates were slower for DDs and faster for dihydroxylated biphenyls in comparison to that for triclosan. In addition, the 2'-Cl substituent was critical for the high quantum yield measured for triclosan and necessary for the photodegradation mechanism that forms DDs and dihydroxylated biphenyls. The 4-Cl substituent was responsible for higher rates of light absorption and the environmentally relevant pKa. Without either of these substituents, the environmental fate of triclosan would be markedly different.

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.