Tris(2-chloroethyl) phosphate (TCEP), a typical chlorinated organophosphate
ester (OPE), is an emerging contaminant of global concern because
of its frequent occurrence, potential toxic effects, and persistence
in the environment. In this study, we investigated the microbial TCEP
biotransformation and the development of microbial communities in
sediment microcosms with repeated TCEP amendments. The TCEP degradation
fitted pseudo-zero-order kinetics, with reaction rates of 0.068 mg/(L
h) after the first spike of 5 mg/L and 1.85 mg/(L h) after the second
spike of 50 mg/L. TCEP was mainly degraded via phosphoester bond hydrolysis,
evidenced by the production of bis(2-chloroethyl) phosphate (BCEP)
and mono-chloroethyl phosphate (MCEP). Bis(2-chloroethyl) 2-hydroxyethyl
phosphate (TCEP-OH), phosphoric bis(2-chloroethyl) (2-oxoethyl) ester
(TCEP-CHO), phosphoric acid bis(2-chloroethyl)(carboxymethyl) ester
(TCEP-COOH), and 2-chloroethyl 2-hydroxyethyl hydrogen phosphate (BCEP-OH)
were also identified as microbial TCEP transformation products, indicating
that TCEP degradation may follow hydrolytic dechlorination and oxidation
pathways. Microbial community compositions in TCEP-amended microcosms
shifted away from control microcosms after the second TCEP spike.
Burkholderiales and Rhizobiales were two prevalent bacterial guilds
enriched in TCEP-amended microcosms and were linked to the higher
abundances of alkaline and acid phosphatase genes and genes involved
in the metabolism of 2-chloroethanol, a side product of TCEP hydrolysis,
indicating their importance in degrading TCEP and its metabolites.