Examining the immunotoxicity of oil sands process affected waters using a human macrophage cell line.

Oil sands process affected water (OSPW) is produced during the surface mining of the oil sands bitumen deposits in Northern Alberta. OSPW contains variable quantities of organic and inorganic components causing toxic effects on living organisms. Advanced Oxidation Processes (AOPs) are widely used to degrade toxic organic components from OSPW including naphthenic acids (NAs). However, there is no established biological procedure to assess the effectiveness of the remediation processes. Our previous study showed that human macrophage cells (THP-1) can be used as a bioindicator system to evaluate the effectiveness of OSPW treatments through examining the proinflammatory gene transcription levels. In the present study, we investigated the immunotoxicological changes in THP-1 cells following exposure to untreated and AOP-treated OSPW. Specifically, using proinflammatory cytokine protein secretion assays we showed that AOP treatment significantly abrogates the ability of OSPW to induce the secretion of IL-1ß, IL-6, IL-8, TNF-α, IL-1Ra and MCP-1. By measuring transcriptional activity as well as surface protein expression levels, we also showed that two select immune cell surface markers, CD40 and CD54, were significantly elevated following OSPW exposure. However, AOP treatments abolished the immunostimulatory properties of OSPW to enhance the surface expression of these immune proteins. Finally, a transcriptome-based approach was used to examine the proinflammatory effects of OSPW as well as the abrogation of immunotoxicity following AOP treatments. Overall, this research shows how a human macrophage cell-based biomonitoring system serves as an effective in vitro tool to study the immunotoxicity of OSPW samples before and after targeted remediation strategies.

Solar-activated zinc oxide photocatalytic treatment of real oil sands process water: Effect of treatment parameters on naphthenic acids, polyaromatic hydrocarbons and acute toxicity removal.

Oil sands process water (OSPW) is an industrial process effluent that contains organic compounds such as naphthenic acids (NAs) and polyaromatic hydrocarbons (PAHs), as well as large quantities of inorganic compounds in its mixture. OSPW requires effective treatment for successful reclamation and water reuse. This study investigated the impact of solar-activated zinc oxide (ZnO) photocatalysis on the degradation and removal of NAs and PAHs in OSPW, as well as the elimination of its acute toxicity. With catalyst particles suspended in the effluent (at 1 g/L) under simulated solar radiation of steady irradiance of ~278 W/m2, more than 99% removal of NAs was achieved after 4 h of treatment, while nearly all PAHs were simultaneously oxidized within the same reaction time. The photocatalytic treatment appeared to selectively convert classical NAs faster than oxidized NAs. Additionally, NAs with higher double-bond equivalents (DBEs) and higher carbon numbers seemed more susceptible to photocatalytic destruction than others. An overall pseudo first-order rate constant of 1.14 × 10-2 min-1, and a fluence-based rate constant of 6.81 × 10-1 m2/MJ were recorded in apparently hydroxyl radicals (OH) and superoxide (O2-) radicals mediated NAs degradation mechanisms. Assessment of the toxicity levels in raw and treated OSPW samples by using Microtox® bioassay indicated that the photocatalytic treatment resulted in ~50% reduction in acute toxicity. Furthermore, we showed that by monitoring the expression levels of key proinflammatory genes using qPCR that treated OSPW significantly reduced the ability of raw OSPW to activate the inflammatory response of immune cells. This indicates that at acute sub-lethal exposure doses, photocatalytic treatment also reduces immunotoxicity. Overall, our results suggest that the ZnO-based photocatalytic degradation of these NAs and PAHs in OSPW could be a significant treatment process aimed at detoxifying OSPW.

Insight into BDD electrochemical oxidation of florfenicol in water: Kinetics, reaction mechanism, and toxicity.

Antibiotics in the environment provoke serious consequences on living beings and can be effectively remediated by prominent advanced oxidation process. In this study, electrochemical advanced oxidation treatment in a lab-scale reactor for the degradation of florfenicol (FLO) was studied with the aid of boron-doped diamond anode (BDD). The results exhibited that the FLO degradation follows pseudo-first-order kinetics. As the current intensity rose from 60 mA to 250 mA, the FLO removal efficiency increased and the corresponding reaction rate constant increased from 0.0213 to 0.0343 min-1, which was likely due to the more efficient participation of free hydroxyl radical (•OH) generated at the BDD anode. Faster degradation and higher mineralization of electrolyzed FLO solution were achieved at higher current intensity as well as in higher SO42- concentration medium, as a consequence of catalytic participation of oxidants (free •OH as well as sulfate radical (SO4•-) and persulfate (S2O82-)). The increase in FLO concentration from 30 to 50 mg L-1 resulted in a reaction rate constant decrease (from 0.0235 to 0.0178 min-1). Eight transformation by-products (m/z = 372.99, 359.8, 338.0, 324.04, 199.00, 185.02, 168.99 and 78.989) and three inorganic ions (NO3-, Cl- and F-) were analyzed by UPLC‒Q‒TOF‒MS/MS and Ion‒chromatography, respectively. The Vibrio fischeri bioluminescence inhibition revealed an increase of toxicity during the electrochemical oxidation that could be attributed mostly to the generated organic chlorinated by-products (m/z = 372.99, 359.8) and inorganic species (ClO2- and ClO3-).

Solar photocatalytic treatment of model and real oil sands process water naphthenic acids by bismuth tungstate: Effect of catalyst morphology and cations on the degradation kinetics and pathways.

Bitumen extraction from oil sands produces large quantities of oil sands process water (OSPW), which contains recalcitrant naphthenic acids (NAs). In this study, three different morphologies of bismuth tungstate (Bi2WO6) photocatalysts were prepared by hydrothermal method. The prepared catalyst was characterized to obtain its structural, textural and chemical properties and tested for the degradation of model NAs and real OSPW under simulated solar irradiation. Nanoplate, flower-like and swirl-like Bi2WO6 were prepared and the results showed that the flower-like structure exhibited the highest specific surface area and total pore volume. The highest photocatalytic activity for the degradation of NAs was also demonstrated by the flower-like Bi2WO6, achieving complete degradation of cyclohexanoic acid (CHA) at fluence-based rate constant of 0.0929 cm2/J. Superoxide radicals (O2•-) and holes were identified as the major reactive species generated during the photocatalytic process. The effect of metallic ions on the degradation rates of S-containing and N-containing NAs differed and the heteroatom was found to be the main reactive site. The by-products of heteroatomic NAs were identified and degradation pathways were reported for the first time. The concentration changes of each byproduct were further estimated by mass balance. This research provides valuable information for the treatment of NAs by engineered passive solar-based approaches.

Coagulation-flocculation followed by catalytic ozonation processes for enhanced primary treatment during wet weather conditions.

Combined sewer overflows (CSO), generated during the wet weather flow from the combination of the inflow and stormwater runoff in sewer system, result in an overflow of untreated wastewater from sewer system, which might ultimately contain different micropollutants (MPs). In this study, a coagulation-flocculation-sedimentation (CFS) pretreated CSO spiked with MPs was treated by catalytic ozonation using carbon, iron, and peroxide-based catalysts. The catalysts were characterized and their activity on MPs removal was studied at two different ozone (O3) doses (5 and 10 mg L-1). The effect of the treatment on the spiked CSO effluent was also assessed from the acute toxicity of the effluent using Microtox®, Yeast, and Macrophage cell-line toxicity assay tests. All the carbon-based catalysts showed large surface area, which was strongly influenced by the activation technique in the preparation of the catalysts. The CFS treatment strongly reduced the turbidity (≥60%) but had marginal effect on the UV254, dissolved organic carbon (DOC), and pH. Sludge Based Carbon (SBC) showed strong adsorption capacity (≥60% removal efficiency) for all MPs studied compared to other carbon and iron-based catalysts. Ozonation alone was effective for the degradation of easily oxidizable MPs (sulfamethoxazole, mecoprop, and 2,4-dichlorophenoxyl acetic acid), achieving more than 80% degradation efficiency at 10 mg L-1 of ozone, but not effective for atrazine (≤60% degradation efficiency) at similar O3 dose. Catalytic ozonation (at 10 mg L-1 O3 dose) improved the degradation of the MPs at low catalyst dosage but higher dosage strongly inhibited their degradation. In all cases, the effluents showed negligible acute toxicity, indicating the suitability of the process for the treatment of CSO.

Coupling of Anodic Oxidation and Soil Remediation Processes: A Review.

In recent years, due to industrial modernization and agricultural mechanization, several environmental consequences have been observed, which make sustainable development difficult. Soil, as an important component of ecosystem and a key resource for the survival of human and animals, has been under constant contamination from different human activities. Contaminated soils and sites require remediation not only because of the hazardous threat it possess to the environment but also due to the shortage of fresh land for both agriculture and urbanization. Combined or coupled remediation technologies are one of the efficient processes for the treatment of contaminated soils. In these technologies, two or more soil remediation techniques are applied simultaneously or sequentially, in which one technique complements the other, making the treatment very efficient. Coupling anodic oxidation (AO) and soil remediation for the treatment of soil contaminated with organics has been studied via two configurations: (i) soil remediation, ex situ AO, where AO is used as a post-treatment stage for the treatment of effluents from soil remediation process and (ii) soil remediation, in situ AO, where both processes are applied simultaneously. The former is the most widely investigated configuration of the combined processes, while the latter is less common due to the greater diffusion dependency of AO as an electrode process. In this review, the concept of soil washing (SW)/soil flushing (SF) and electrokinetic as soil remediation techniques are briefly explained followed by a discussion of different configurations of combined AO and soil remediation.

Electrochemical advanced oxidation processes (EAOPs) as alternative treatment techniques for carwash wastewater reclamation.

Electrochemical advanced oxidation processes such as electrooxidation (EO), electrooxidation with hydrogen peroxide generation (EO-H2O2) and electro-Fenton process (EF) have been investigated as alternative treatment techniques for complete removal of anionic surfactants and organic matters from real carwash wastewater. The electrochemical processes were performed with acidified real carwash wastewater using boron doped anode and carbon felt cathode. In all cases, the chemical oxygen demand (COD) removal efficiency was always increased with rise in applied current and complete organic matter decay was achieved at applied current of 500 mA or above after 6 h of electrolysis. Faster and higher COD decay was observed with EF compared to either EO or EO-H2O2 treatment, at all currents and electrolysis time. Besides, complete degradation of anionic surfactants - the major organic content of the wastewater could be achieved at all applied currents studied irrespective of the process used, indicating the efficacy of processes for total remediation of real carwash wastewater. The short-chain carboxylic acids formed as the final organic byproducts were identified and quantified by ion-exclusion chromatography. More so, lower energy consumption and higher current efficiency were achieved with EF compared to EO-H2O2. Electrochemical treatment was found to be a powerful technology for the complete abatement of organic matter in carwash wastewater for possible reuse.

Sub-stoichiometric titanium oxide (Ti4O7) as a suitable ceramic anode for electrooxidation of organic pollutants: A case study of kinetics, mineralization and toxicity assessment of amoxicillin.

Electrochemical degradation of aqueous solutions containing antibiotic amoxicillin (AMX) has been extensively studied in an undivided electrolytic cell using a sub-stoichiometric titanium oxide (Ti4O7) anode, elaborated by plasma deposition. Oxidative degradation of AMX by hydroxyl radicals was assessed as a function of applied current and was found to follow pseudo-first order kinetics. The use of carbon-felt cathode enhanced oxidation capacity of the process due to the generation of H2O2. Comparative studies at low current intensity using dimensional stable anode (DSA) and Pt anodes led to the lower mineralization efficiencies compared to Ti4O7 anode: 36 and 41% TOC removal for DSA and Pt respectively compared to 69% for Ti4O7 anode. Besides, the use of boron doped diamond (BDD) anode under similar operating conditions allowed reaching higher mineralization (94%) efficiency. Although Ti4O7 anode provides a lesser mineralization rate compared to BDD, it exhibits better performance compared to the classical anodes Pt and DSA and can constitutes an alternative to BDD anode for a cost effective electro-oxidation process. Moreover several aromatic and aliphatic oxidation reaction intermediates and inorganic end-products were identified and a plausible mineralization pathway of AMX involving these intermediates was proposed.