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This study investigated the application of materials peat-mineral mix (PT) and Pleistocene fluvial sands from different location (PF-1 and PF-2) obtained from surface mining of oil sands as sorbents of naphthenic acids (NAs) from oil sands process water (OSPW). To understand the sorption properties and mechanisms of NAs in the materials, sorption and desorption studies were performed using decanoic acid (DA) and 5-phenylvaleric acid (PVA). Additionally, the removal efficiency was evaluated using real OSPW to understand the effect of NA structure on sorption. Equilibrium of DA and PVA was reached at 2 days for PT, and 3 and 6 days for PF materials, respectively. Langmuir isotherm best fitted the equilibrium data. Maximum sorption capacities for DA and PVA were, respectively, 16.8 × 103 and 104 mg/kg for PT, 142.9 and 81.3 mg/kg for PF-1, and 600 and 476.2 mg/kg for PF-2. Hydrophobic interactions, hydrogen bonding, and π−π interaction were the main sorption mechanisms. Desorption of model compounds from post-sorption materials was not observed for 14 days. The removal of NAs from real OSPW ranged from 20 to 54%. PT is the most promising sorbent of NAs from OSPW because it partially removed NAs with a wide range of molecular weights and structures at very low dosage. Sorption of NAs was affected by the total organic carbon of the materials, emphasizing the hydrophobic interaction as an important sorption mechanism. The results suggest that some mobility of NAs is expected to take place if the reclamation materials come in contact with OSPW, which might occur in an oil sands reclamation landscape. [Display omitted] • Three materials were studied as sorbents of model NA compounds and NAs from OSPW. • Sorption mechanisms included hydrogen bonding, hydrophobic and π−π interactions. • No desorption of model NAs from materials was observed up to 14 days of contact time. • Removal of NAs with different molecular weights and structures ranged from 9.9 to 68.3%. • TOC was the main characteristic of materials that affected the sorption of NAs from OSPW. [ABSTRACT FROM AUTHOR]

Due to their recalcitrance, naphthenic acids (NAs) are one of the constituents of interest in oil sands process water (OSPW). In this study, peroxymonosulfate (PMS) activated by ozone was employed to degrade NA model compounds in buffer solutions. At an ozone/PMS ratio of 2:1, a removal of 85 % was observed for a model diamondoid NA compound (1-adamantanecarboxylic acid; ACA) after 45 s of reaction. Compared with ozone alone, the degradation of ACA was accelerated in the presence of ozone/PMS, with an overall pseudo-first order rate constant (k obs) increasing from 8.02 × 10−4 s−1 during ozone treatment to 6.74 × 10−2 s−1 in the ozone/PMS system. Although ozone/hydrogen peroxide (H 2 O 2) showed high degradation for ACA, the ozone/PMS system showed a higher k obs of 5.44 × 10−2 s−1at a PMS dose of 0.042 mM, while at the same dose of H 2 O 2 , k obs was equal to 3.62 × 10−2 s−1 for ozone/H 2 O 2. This result showed the synergetic effect of ozone and PMS on the degradation of ACA. Relative kinetics studies using mixtures of model NA compounds showed better performance for ozone/PMS to degrade aromatic NAs compared to ozone/H 2 O 2. Hydroxyl radicals and sulfate radicals were found to be responsible for the removal of ACA, with limited effect of molecular ozone. The proposed degradation pathways for ACA included hydroxylation, carboxylation, and polymerization under ozone/PMS, while hydroxylation and carboxylation were the main degradation pathways under ozone/H 2 O 2. The results of this study emphasize the potential of ozone/PMS process to treat OSPW by accelerating the degradation of recalcitrant organic compounds. [Display omitted] • PMS was successfully activated by ozone to degrade naphthenic acids model compounds. • The degradation of ACA was accelerated in the presence of ozone/PMS. • Hydroxyl radicals and sulfate radicals were responsible for the removal of ACA. • Limited effect of molecular ozone was observed for the oxidation of model NAs. • Ozone/PMS produced intermediates via hydroxylation, carboxylation and polymerization. [ABSTRACT FROM AUTHOR]

[Display omitted] • ZnCl 2 -activated biochar from sludge successfully adsorbed total NAs in raw OSPW. • Pore filling, hydrogen bonding, and π − π interactions were the adsorption mechanisms. • Biochar had selectivity for NAs with hydrophobic and higher cyclicity characteristics. • Microtox® assay indicated 66% reduction in acute toxicity after biochar treatment. • 91% reduction of bioavailability of organics was observed in OSPW treated with sludge biochar. Large volumes of oil sands process water (OSPW) containing naphthenic acids (NAs) and other contaminants are generated by oil sands operations. For the first time, pristine and zinc chloride-activated biochars from sludge from a municipal wastewater treatment plant are studied in the adsorption of NAs in real OSPW. By using activated biochar instead of pristine biochar, the adsorption capacity (q t) for total NAs (classical and oxidized NAs) increased from 2.3 to 26.6 mg/g. The increase in q t for activated biochar was related to the improvement of surface area from 7.9 to 513 m2/g, the abundance of mesopores (89% of pore volume), and the oxygen-containing surface groups. Equilibrium was reached at 2 h of contact time. Considering the thousands of structures of NAs in the OSPW, the activated biochar presented higher affinity for NAs with higher carbon and double bond equivalency numbers, therefore, NAs with more hydrophobic and higher cyclicity characteristics. Pore-filling, hydrogen bonding, and π-π interactions are the adsorption mechanisms. Thermal regeneration of spent activated biochar was studied, and in the fifth cycle of regeneration, the regenerated biochar had q t of 7.1 mg/g, which was 5 times higher than the adsorption capacity of fresh pristine biochar. Adsorption treatment of OSPW using activated biochar decreased the following parameters: metals Mg (7%), Ca (21%), Sr (27%), and Ba (60%), organic matter by means of DOC (63%) and COD (66%), acute toxicity towards V. fischeri (66%) and bioavailability of organics (91%). These findings promote circular economy as it presents an efficient adsorbent for NAs in OSPW developed from sludge, reducing the environmental impact associated with sludge disposal and allowing the efficient reclamation and reuse of OSPW. [ABSTRACT FROM AUTHOR]

[Display omitted] • BC/ZnO composites were successfully synthesized from wood wastes. • The BC/30 %ZnO composite showed enhanced photocatalytic performance than pure ZnO. • The composite presented good reusability and stability after 4 cycles of use. • First study applied BC/ZnO composite for NAs mixture photocatalytic degradation. • Over 95 % of NAs in mixture were degraded by BC/30 %ZnO after 6 h solar irradiation. Naphthenic acids (NAs) present in oil sands process water (OSPW) have brought increasing environmental concerns due to their potential risk to aquatic and mammalian species. In this study, sustainable biochar zinc oxide (BC/ZnO) composites were synthesized using wood waste with different ZnO content and applied under simulated solar light for the photocatalytic degradation of different NAs for the first time. The best experimental conditions were determined as 0.5 g/L BC/30%ZnO and 4 h of simulated solar irradiation time, achieving 93.7 % degradation of cyclohexanecarboxylic acid (CHA) following the pseudo-first order kinetics. BC, with a porous structure and roughened surface, acted as an excellent platform for ZnO particles and an electron reservoir to inhibit the recombination of photogenerated electron-hole pairs. Hydroxyl radicals (•OH) were identified to play the dominant role in CHA degradation, and the enhanced photocatalytic performance of the BC/30%ZnO composite was proved by more •OH species detected compared to synthesized ZnO. The composite showed good reusability and stability after 4 successive cycles of use, still achieving 92.9 % degradation of CHA. Moreover, this is the first study applying BC/30%ZnO composite for the simultaneous degradation of a complex mixture of eight NAs with significantly different chemical structures. The competition kinetics were observed among different NAs in the mixture, resulted in over 95 % degradation of total NAs after 6 h treatment. By applying wood waste-based BC/ZnO composite with excellent photocatalytic performance in combination with solar light as green energy source, this research highlights a promising sustainable approach for real OSPW remediation. [ABSTRACT FROM AUTHOR]

A novel photocatalyst, Bi 2 WO 6 /NiO/Ag, with hierarchical flower-like Z-scheme heterojunction, which exhibited excellent stability and photocatalytic activity over a wide light spectrum, was firstly synthesized and used in the remediation of real oil sands process water (OSPW) and achieved complete removal of aromatics, classical naphthenic acids (NAs), and heteroatomic NAs after 6 h of photocatalytic treatment. The acute toxicity of OSPW was completely eliminated after only 2 h of treatment. h+ and ∙OH were found to be the major oxidative species in the photocatalytic system. The enhanced photocatalytic efficiency is the result of the unique Z-scheme electron transfer among electron mediators Ag, NiO, and Bi 2 WO 6 , which was supported by the in-situ irradiated XPS. The study benefits the design of engineered passive treatment approach for OSPW remediation through solar light-driven catalyst. [Display omitted] • 3D flower-like Z scheme photocatalyst Bi 2 WO 6 /NiO/Ag was synthesized. • Bi 2 WO 6 /NiO/Ag effectively treated OSPW with 90% degradation of O 2 -NAs within 3 hrs. • Aromatics with three fused rings were more prone to degradation than single and two-ring aromatics. • NAs with different carbon number and DBE showed different degradation behaviors. • Z-scheme structure enhanced the photocatalytic activity and was verified by in-situ irradiated XPS. [ABSTRACT FROM AUTHOR]

[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]

• The photochemical reactions of ferric citrate were used to treat OSPW. • NAs could be effectively degraded by ferric citrate under visible light irradiation. • Photocatalytic activity of ferric citrate was greatly affected by the initial pH of OSPW. • Hydroxyl radical was the dominant reactive species in the process. • The photochemical reactions of ferric citrate could produce both Fe2+ and H 2 O 2 in situ. An environmental-friendly treatment method based on photochemical reactions of ferricarboxylate complexes was developed for the treatment of oil sands process water (OSPW). Without using H 2 O 2 , the classical naphthenic acids (NAs), one of the organic compounds present in OSPW, can be effectively degraded by ferric citrate under visible light irradiation. Photochemical reaction activity of ferric citrate was greatly affected by the initial pH of OSPW. In acidic conditions, ferric citrate exhibited an extremely high degradation ratio of classical NAs, 98.3% (initial pH 3) and 96.8% (initial pH 5). Once initial pH exceeded 5, the degradation ratio of classical NAs in OSPW decreased quickly, and the degradation ratio of classical NAs could reach 65.7% (initial pH 7) and 42.4% (without adjusting pH, initial pH 8.9), respectively. It was found that the structure of NAs had little impact on the removal efficiency of NAs. It was also confirmed through scavenger experiments and reaction mechanism study that hydroxyl radical was the dominant reactive species in the process. The study demonstrated that ferric citrate possesses excellent visible light absorption ability and the photochemical reactions of ferric citrate can produce both Fe2+ and H 2 O 2 in situ , Fenton reagent, which non-selectively degrade NAs of OSPW. [ABSTRACT FROM AUTHOR]