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.

Reductive Outer-Sphere Single Electron Transfer Is an Exception Rather than the Rule in Natural and Engineered Chlorinated Ethene Dehalogenation.

Chlorinated ethenes (CEs) such as perchloroethylene, trichloroethylene and dichloroethylene are notorious groundwater contaminants. Although reductive dehalogenation is key to their environmental and engineered degradation, underlying reaction mechanisms remain elusive. Outer-sphere reductive single electron transfer (OS-SET) has been proposed for such different processes as Vitamin B12-dependent biodegradation and zerovalent metal-mediated dehalogenation. Compound-specific isotope effect (13C/12C, 37Cl/35Cl) analysis offers a new opportunity to test these hypotheses. Defined OS-SET model reactants (CO2 radical anions, S2--doped graphene oxide in water) caused strong carbon (εC = -7.9‰ to -11.9‰), but negligible chlorine isotope effects (εCl = -0.12‰ to 0.04‰) in CEs. Greater chlorine isotope effects were observed in CHCl3 (εC = -7.7‰, εCl = -2.6‰), and in CEs when the exergonicity of C-Cl bond cleavage was reduced in an organic solvent (reaction with arene radical anions in glyme). Together, this points to dissociative OS-SET (SET to a σ* orbital concerted with C-Cl breakage) in alkanes compared to stepwise OS-SET (SET to a π* orbital followed by C-Cl cleavage) in ethenes. The nonexistent chlorine isotope effects of chlorinated ethenes in all aqueous OS-SET experiments contrast strongly with pronounced Cl isotope fractionation in all natural and engineered reductive dehalogenations reported to date suggesting that OS-SET is an exception rather than the rule in environmental transformations of chlorinated ethenes.

Environmental Photochemistry of Altrenogest: Photoisomerization to a Bioactive Product with Increased Environmental Persistence via Reversible Photohydration.

Despite its wide use as a veterinary pharmaceutical, environmental fate data is lacking for altrenogest, a potent synthetic progestin. Here, it is reported that direct photolysis of altrenogest under environmentally relevant conditions was extremely efficient and rapid (half-life ∼25 s). Photolysis rates (observed rate constant kobs = 2.7 ± 0.2 × 10(-2) s(-1)) were unaffected by changes in pH or temperature but were sensitive to oxygen concentrations (N2-saturated kobs = 9.10 ± 0.32 × 10(-2) s(-1); O2-saturated kobs = 1.38 ± 0.11 × 10(-2) s(-1)). The primary photoproduct was identified as an isomer formed via an internal 2 + 2 cycloaddition reaction; the triplet lifetime (8.4 ± 0.2 µs) and rate constant (8 × 10(4) s(-1)) of this reaction were measured using transient absorption spectroscopy. Subsequent characterization determined that this primary cycloaddition photoproduct undergoes photohydration. The resultant photostable secondary photoproducts are subject to thermal dehydration in dark conditions, leading to reversion to the primary cycloaddition photoproduct on a time scale of hours to days, with the photohydration and dehydration repeatable over several light/dark cycles. This dehydration reaction occurs more rapidly at higher temperatures and is also accelerated at both high and low pH values. In vitro androgen receptor (AR)-dependent gene transcriptional activation cell assays and in silico nuclear hormone receptor screening revealed that certain photoproducts retain significant androgenic activity, which has implications for exposure risks associated with the presence and cycling of altrenogest and its photoproducts in the environment.

Experimental and theoretical insights into the involvement of radicals in triclosan phototransformation.

The phototransformation of triclosan has been a matter of longstanding interest due to both its prevalence in the environment and the discovery of 2,8-dichlorodibenzodioxin as a photoproduct. In this study, photolysis of triclosan resulted in several primary photoproducts including the following: 2,8-dichlorodibenzodioxin (4%), 4,5'-dichloro-[1,1'-biphenyl]-2,2'-diol (10%), 5-chloro-2-(4-chlorophenoxy)phenol (0.5%), and 2,4-dichlorophenol (7%). Trapping studies using d8-isopropanol showed deuterium incorporation in 5-chloro-2-(4-chlorophenoxy)phenol, providing strong evidence for the involvement of organic radicals in this reaction. Density functional calculations of the excited states of triclosan support the involvement of a radical intermediate in the mechanisms responsible for the dioxin, biphenyl, and phenoxyphenol photoproducts. The pathways for C-Cl bond cleavage and cyclization reactions are discussed.

Reductive dechlorination of TCE by chemical model systems in comparison to dehalogenating bacteria: insights from dual element isotope analysis (13C/12C, 37Cl/35Cl).

Chloroethenes like trichloroethene (TCE) are prevalent environmental contaminants, which may be degraded through reductive dechlorination. Chemical models such as cobalamine (vitamin B12) and its simplified analogue cobaloxime have served to mimic microbial reductive dechlorination. To test whether in vitro and in vivo mechanisms agree, we combined carbon and chlorine isotope measurements of TCE. Degradation-associated enrichment factors ε(carbon) and ε(chlorine) (i.e., molecular-average isotope effects) were -12.2‰ ± 0.5‰ and -3.6‰ ± 0.1‰ with Geobacter lovleyi strain SZ; -9.1‰ ± 0.6‰ and -2.7‰ ± 0.6‰ with Desulfitobacterium hafniense Y51; -16.1‰ ± 0.9‰ and -4.0‰ ± 0.2‰ with the enzymatic cofactor cobalamin; -21.3‰ ± 0.5‰ and -3.5‰ ± 0.1‰ with cobaloxime. Dual element isotope slopes m = Δδ(13)C/ Δδ(37)Cl ≈ ε(carbon)/ε(chlorine) of TCE showed strong agreement between biotransformations (3.4 to 3.8) and cobalamin (3.9), but differed markedly for cobaloxime (6.1). These results (i) suggest a similar biodegradation mechanism despite different microbial strains, (ii) indicate that transformation with isolated cobalamin resembles in vivo transformation and (iii) suggest a different mechanism with cobaloxime. This model reactant should therefore be used with caution. Our results demonstrate the power of two-dimensional isotope analyses to characterize and distinguish between reaction mechanisms in whole cell experiments and in vitro model systems.

Reconciling disparate models of the involvement of vinyl radicals in cobalamin-mediated dechlorination reactions.

Inner-sphere (nonradical) and outer-sphere (radical-based) mechanisms have been suggested for cobalamin-mediated dechlorination of tetrachloroethylene (PCE) and trichloroethylene (TCE). In this study, the role of free vinyl radicals was investigated using deuterated radical traps: d(8)-isopropanol and d(8)-tetrahydrofuran. For both substrates, addition of trap resulted in production of deuterated dechlorination products, and higher concentrations of trap resulted in increased amounts of deuterated products. However, only a finite proportion of the products were trappable: 8% of the PCE-derived products and 86% of the TCE-derived products result from free radicals. The data show that the reaction does not proceed solely by either an inner-sphere or an outer-sphere mechanism and led to the hypothesis that caged radical intermediates were involved in the mechanism. The untrappable fraction of products are hypothesized to result from in-cage reactions. This hypothesis was investigated using d(5)-glycerol as a radical trap and viscogen. Although increased viscosity resulted in decreased formation of free-radical-derived products, consistent with the cage hypothesis, these data were inconclusive. The role of d(8)-isopropanol in enhancing the production of radicals in this system via an acetone ketyl radical chain mechanism was also investigated, and no evidence for such an effect was found.

Dechlorination of chloroethylenes by cob(I)alamin and cobalamin model complexes.

Cobalt-mediated dehalogenation reactions, specifically those that employ cobalamin, have attracted particular attention because these complexes rapidly degrade tetrachloroethylene (PCE) and trichloroethylene (TCE), which are common groundwater contaminants. Although questions remain about the relative importance of several pathways, both radicals and organometallic intermediates, specifically chlorovinyl complexes, play an important role in these processes. This Perspective highlights recent studies focused on elucidating the mechanism of chloroethylene degradation, including experimental studies on PCE and TCE dechlorination, computational studies, preparation of model complexes, and the study of model catalytic systems.