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[Display omitted] • PDS and PMS were successfully activated by UVA LED light to treat real OSPW. • Over 90 % of classical NAs were removed by UVA LED/PDS (1 mM) or /PMS (2 mM) • The UVA LED/PDS (1 mM) was the most cost-effective system to treat OSPW. • Pre-existing immunotoxic and cytotoxic effects were markedly reduced in treated OSPW. • Treated OSPW could potentially be considered for reuse applications. This study investigated for the first time the synergistic effect of coupling persulfate (PDS) and peroxymonosulfate (PMS) with UVA LED light for the treatment of real oil sands process water (OSPW). The performance of the UVA LED/PDS and UVA LED/PMS processes was studied at different oxidant concentrations to remove fluorophore organic compounds and naphthenic acids (NAs), commonly considered significant contributors to the toxicity of raw OSPW. Both systems were highly efficient in eliminating fluorophore organic contaminants and classical NAs (O 2 -NAs) from the matrix; however, concentrations of 1 and 2 mM of PDS and PMS, respectively, were the most suitable conditions to achieve one order of magnitude removal of O 2 -NAs (i.e., 90 %). In addition, oxidized NAs (O 3 - and O 4 -NAs) were moderately degraded under these conditions. Considering economic factors, the UVA LED/PDS (1 mM) system proved to be more cost-effective than the UVA LED/PMS (2 mM) process and a viable alternative to other advanced treatments for OSPW remediation. Moreover, the pre-existing toxic effect of raw OSPW was markedly mitigated after treatment with UVA LED/PDS (1 mM), reducing by 80 % the ability of the matrix to induce pro-inflammatory cytokines in human leukemic monocytic and without significantly affecting the viability of the Staphylococcus epidermidis bacteria. Specifically for the microbial viability assay, the exposure period of the microorganism was exceptionally more extended than those considered in standard bioassays, reinforcing the scientific relevance of the obtained results. Finally, these results suggest a high environmental compatibility of the treated OSPW, making its reuse in further applications safe. [ABSTRACT FROM AUTHOR]