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Naphthenic acids (NA) are organic compounds commonly found in crude oil and produced water, known for their recalcitrance and toxicity. This study introduces a new adsorbent, a polymer derived from spent coffee grounds (SCGs), through a straightforward cross-linking method for removing cyclohexane carboxylic acid as representative NA. The adsorption kinetics followed a pseudo-second-order model for the data (0.007 g min-1 mg-1), while the equilibrium data fitted the Sips model ( q m = 140.55 mg g-1). The process's thermodynamics indicated that the target NA's adsorption was spontaneous and exothermic. The localized sterical and energetic aspects were investigated through statistical physical modeling, which corroborated that the adsorption occurred indeed in monolayer, as suggested by the Sips model, but revealed the contribution of two energies per site ( n 1 ; n 2 ). The number of molecules adsorbed per site ( n ) was highly influenced by the temperature as n 1 decreased with increasing temperature and n 2 increased. These results were experimentally demonstrated within the pH range between 4 and 6, where both C6H11COO-(aq.) and C6H11COOH(aq.) species coexisted and were adsorbed by different energy sites. The polymer produced was naturally porous and amorphous, with a low surface area of 20 to 30 m2 g-1 that presented more energetically accessible sites than other adsorbents with much higher surface areas. Thus, this study shows that the relation between surface area and high adsorption efficiency depends on the compatibility between the energetic states of the receptor sites, the speciation of the adsorbate molecules, and the temperature range studied.

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Considerable amount of produced water discharged by the oil industry contributes to an environmental imbalance due to the presence of several components potentially harmful to the ecosystem. We investigated the factors influencing the adsorption capacity of Zinc Imidazolate Framework-8 (ZIF-8) in finite bath systems for crude oil removal from petroleum extraction in synthetic produced water. ZIF-8, experimentally obtained by solvothermal method, was characterized by XRD, FTIR, TGA, BET and its point of zero charge (pHpcz) was determined. Synthesized material showed high crystallinity, with surface area equal to 1558 m2 g-1 and thermal stability equivalent to 400 °C. Adsorption tests revealed, based on the Sips model, that the process takes place in a heterogeneous system. Additionally, intraparticle diffusion model exhibited multilinearity characteristics during adsorption process. Thermodynamic investigation demonstrated that adsorption process is spontaneous and exothermic, indicating a physisorption phenomenon. These properties enable the use of ZIF-8 in oil adsorption, which presented an adsorption capacity equal to 452.9 mg g-1. Adsorption mechanism was based on hydrophobic interactions, through apolar groups present on ZIF-8 structure and oil hydrocarbons, and electrostatic interactions, through the difference in charges between positive surface of adsorbent and negatively charged oil droplets.

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This study has the novel aim of experimentally examining the efficiency of a pilot-scale treatment plant, composed of a multi-tube type falling-film distillation column equipped with a biphasic thermosiphon, for treating a real sample of high-salinity produced water (electrical conductivity of 20,700 µS cm-1). It investigates the influence of operational parameters, including feed temperature and steam chamber temperature of the biphasic thermosiphon, on distillate flow rate and reduction of conductivity. All experimental conditions tested achieved a reduction greater than 98% in terms of electrical conductivity. The production of treated water increased with increasing feed temperature; the flow rate increased from 20.8 L h-1 to 28.2 L h-1 as the feed temperature was increased from 80 °C to 90 °C, when the steam chamber temperature was fixed at 119 °C. Within the temperature range of the steam chamber, the specific energy consumption during the treatment process, with respect to the biphasic thermosiphon, remained practically unchanged between 0.58 kWh L-1 and 0.60 kWh L-1, when the feed temperature was 90 °C. The results proved the potential of the falling-film distillation technology assisted by heat pipes to be a promising proposal for removing salinity from produced water from oil extraction operations.

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Produced water (PW) generated by oil companies is a highly impacting waste that contains chemicals such as metals and organic and inorganic compounds. Given its polluting potential, PW requires effective treatment before being discharged into the environment. Conventional treatments have limited efficiency in removing PW toxicity, so alternative approaches must be developed and standardized. In this context, treatment with adsorbent materials like magnetized vermiculite (VMT-mag) is highlighted. This work aimed to evaluate the efficiency of treatment with VMT-mag in reducing PW toxicity to aquatic biota. For this purpose, three aquatic species (the midge Chironomus riparius, the planarian Girardia tigrina, and the crustacean Daphnia magna) were exposed to untreated PW and to PW treated with VMT-mag at laboratory conditions. The assessed endpoints included mortality, growth, emergence, and developmental time of C. riparius; mortality, locomotion, feeding, and head regeneration of G. tigrina; and intrinsic population growth rate (r) and reproductive output of D. magna. The results showed that all the species exposed to raw PW were impaired: C. riparius had delayed development, G. tigrina had reduced locomotor activity and delayed head regeneration, and D. magna had reduced reproduction and delayed intrinsic population growth rate (r). Most of the analyzed parameters showed that treatment with VMT-mag diminished PW toxicity. Therefore, using VMT-mag to treat PW may be the key to reducing the PW effects on aquatic organisms.

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Microbiologically influenced corrosion (MIC) or biocorrosion is a complex biological and physicochemical process, Strategies for monitoring MIC are frequently based on microbial cultivation methods, while microbiological molecular methods (MMM) are not well-established in the oil industry in Brazil. Thus, there is a high demand for the development of effective protocols for monitoring biocorrosion with MMM. The main aim of our study was to analyze the physico-chemi- cal features of microbial communities occurring in produced water (PW) and in enrichment cultures in oil pipelines of the petroleum industry. In order to obtain strictly comparable results, the same samples were used for both culturing and metabarcoding. PW samples displayed higher phylogenetic diversity of bacteria and archaea whereas PW enrichments cultures showed higher dominance of bacterial MIC-associated genera. All samples had a core community composed of 19 distinct genera, with MIC-associated Desulfovibrio as the dominant genus. We observed significant associations between the PW and cultured PW samples, with a greater number of associations found between the cultured sulfate-reducing bacteria (SRB) samples and the uncultured PW samples. When evaluating the correlation between the physicochemical characteristics of the environment and the microbiota of the uncultivated samples, we suggest that the occurrence of anaerobic digestion metabolism can be characterized by well-defined phases. Therefore, the detection of microorganisms in uncultured PW by metabarcoding, along with physi-cochemical characterization, can be a more efficient method compared to the culturing method, as it is a less laborious and cost-effective method for monitoring MIC microbial agents in oil industry facilities.

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An Eu(III) ß-diketonate complex was produced and employed as a photoluminescent probe to determine methylmercury (CH3Hg+). To establish its molecular structure, the Eu(III) complex was characterized by elemental (CHNS) and thermogravimetric analyses and infrared spectroscopy. After establishing robust conditions to use the Eu(III) complex as an analytical probe, it was employed for the analysis of produced water (PW) samples with the analytical response based on the luminescence suppression proportional to the concentration of CH3Hg+ (a linear model after normalization of the response within the concentration range from 0.2 µg L-1 up to 2.0 µg L-1). Selectivity was guaranteed by a simple liquid-liquid extraction of the analyte in dichloromethane, which also allowed a 50 times pre-concentration factor. The instrumental limit of quantification of 0.2 µg L-1 is equal to the limit established in Brazilian resolution for total mercury content in waters, but pre-concentration (50 times factor) improved the overall method limit of quantification down to 4 ng L-1. Recovery results agreed with the ones achieved using cold vapor atomic absorption spectrometry.

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Produced water (PW) and crude glycerin (CG) are compounds overproduced by the oil and biodiesel industry and significant scientific efforts are being applied for properly recycling them. The aim of this research is to combine such industrial byproducts for sustaining the production of xanthan by Xanthomonas campestris. Xanthan yields and viscosity on distinct PW ratios (0, 10, 15, 25, 50, 100) and on 100% dialyzed PW (DPW) in shaker batch testing identified DPW treatment as the best approach for further bioreactor experiments. Such experiments showed a xanthan yield of 17.3 g/L within 54 h and a viscosity of 512 mPa s. Physical-chemical characterization (energy dispersive X-ray spectroscopy, scanning electron microscopy and Raman spectroscopy) showed similarities between the produced gum and the experimental control. This research shows a clear alternative for upcycling high salinity PW and CG for the generation of a valued bioproduct for the oil industry.

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Deterministic and probabilistic ecological risk assessments were performed for the boron present in coastal waters in the region of the São Sebastião channel (coast of São Paulo State, Brazil) surrounding the outfall of the São Sebastião waterway terminal (TEBAR) and in reference areas far from the outfall. A set of ecotoxicity tests with 9 marine organisms (Lytechinus variegatus, Arbacia lixula, Skeletonema costatum, Asterionellopsis glacialis, Parablenius pilicornis, Artemia salina, Megabalanus coccopoma, Mysidopsis juniae and Hypnea musciformes) was performed in the laboratory. Ecotoxicity tests confirmed that boron presents low ecotoxicity, with Lytechinus variegatus being the most sensitive species studied, with an EC50 of 14.6 mg L-1 and a no-observed effect concentration (NOEC) of 6.75 mg L-1. According to the deterministic ecological risk assessment, no significant environmental impact is expected if we consider the most sensitive of the organisms tested and the highest concentration of boron found in the coastal waters (5.82 mg L-1).

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Produced water, a mixture of inorganic and organic components, comprises the largest effluent stream from oil and gas activities. The removal of contaminants from this wastewater is receiving special attention of the researchers since most of them are persistent and difficult to remove with simple techniques. Several technologies from conventional to advanced oxidation processes have been employed to treat produced water. However, the achievement of greater efficiency may be conditioned to a combination of different wastewater treatment techniques. Hereupon, the present paper discusses three important aspects regarding produced water treatment: analytical methods used for characterization, relevant aspects regarding photochemical systems used for advanced oxidation processes, and combined techniques for treating oil field wastewaters. Analytical methods employed for the quantification of the main species contained in produced water are presented for a proper characterization. Photochemical aspects of the reaction systems such as operating conditions, types of irradiation sources, and technical details of reactors are also addressed. Finally, research papers concerning combined treatment techniques are discussed focusing on the essential contributions. Thus, this manuscript aims to assist in the development of novel techniques and the improvement of produced water treatment to obtain a high-quality treated effluent and reduce environmental impacts.

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The water produced (PW) by the petroleum industry is a potential contaminant to aquatic biota, due to its complex mixture that may contain polycyclic aromatic hydrocarbons (PAHs), organic chemical compounds, including benzene, toluene, ethylbenzene and xylene (BTEX), metals and other components that are known to be toxic. The aim of this investigation was to examine the acute toxicity produced by a PW sample in aquatic organisms Vibrio fischeri and Daphnia similis prior to and after 4 treatments using advanced oxidative processes such as photocatalysis, photoelectrocatalysis, ozonation and photoelectrocatalytic ozonation. Data demonstrated that exposure to PW was toxic to both organisms, as evidenced by reduced luminescence in bacterium Vibrio fischeri and induced immobility in Daphnia similis. After treatment of PW with 4 different techniques, the PW remained toxic for both tested organisms. However, photoelectrocatalysis was more efficient in decreasing toxicity attributed to PW sample. Therefore, data demonstrate the importance of treating PW for later disposal in the environment in order to mitigate ecotoxicological impacts. Further photoelectrocatalysis appeared to be a promising tool for treating PW samples prior to disposal and exposure of aquatic ecosystems.

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Wastewater from the oil industry can be considered a dangerous contaminant for the environment and needs to be treated before disposal or re-use. Currently, membrane separation is one of the most used technologies for the treatment of produced water. Therefore, the present work aims to study the process of separating oily water in a module equipped with a ceramic membrane, based on the Eulerian-Eulerian approach and the Shear-Stress Transport (SST k-ω) turbulence model, using the Ansys Fluent® 15.0. The hydrodynamic behavior of the water/oil mixture in the filtration module was evaluated under different conditions of the mass flow rate of the fluid mixture and oil concentration at the entrance, the diameter of the oil particles, and membrane permeability and porosity. It was found that an increase in the feed mass flow rate from 0.5 to 1.5 kg/s significantly influenced transmembrane pressure, that varied from 33.00 to 221.32 kPa. Besides, it was observed that the particle diameter and porosity of the membranes did not influence the performance of the filtration module; it was also verified that increasing the permeability of the membranes, from 3 × 10-15 to 3 × 10-13 m2, caused transmembrane pressure reduction of 22.77%. The greater the average oil concentration at the permeate (from 0.021 to 0.037 kg/m3) and concentrate (from 1.00 to 1.154 kg/m3) outlets, the higher the average flow rate of oil at the permeate outlets. These results showed that the filter separator has good potential for water/oil separation.

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The objective of this study was to compare the potential of mono-rhamnolipids (mono-RML) and di-rhamnolipids (di-RML) against biofilm formation on carbon steel coupons submitted to oil produced water for 14 days. The antibiofilm effect of the RML on the coupons was analyzed by scanning electron microscopy (SEM) and by epifluorescence microscopy, and the contact angle was measured using a goniometer. SEM analysis results showed that all RML congeners had effective antibiofilm action, as well as preliminary anticorrosion evaluation confirmed that all RML congeners prevented the metal deterioration. In more detail, epifluorescence microscopy showed that mono-RML were the most efficient congeners in preventing microorganism's adherence on the carbon steel metal. Image analyses indicate the presence of 15.9%, 3.4%, and <0.1% of viable particles in di-RML, mono/di-RML and mono-RML pretreatments, respectively, in comparison to control samples. Contact angle results showed that the crude carbon steel coupon presented hydrophobic character favoring hydrophobic molecules adhesion. We calculated the theoretical polarity of the RML congeners and verified that mono-RML (log P = 3.63) presented the most hydrophobic character. This had perfect correspondence to contact angle results, since mono-RML conditioning (58.2°) more significantly changed the contact angle compared with the conditioning with one of the most common surfactants used on oil industry (29.4°). Based on the results, it was concluded that rhamnolipids are efficient molecules to be used to avoid biofilm on carbon steel metal when submitted to oil produced water and that a higher proportion of mono-rhamnolipids is more indicated for this application.

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Chemometric tools are powerful strategies to efficiently optimize many processes. These tools were employed to optimize a fast-solid phase microextraction procedure, which was used for the analysis of polycyclic aromatic hydrocarbons (PAHs) in oil-based produced water using a Headspace-Solid Phase Microextraction technique (HS-SPME/GC-MS). This optimization was achieved with a 24 factorial design approach, where the final conditions for this extraction procedure were 10 µg L-1, 1 h, 92 °C (at headspace), and 0.62 mol L-1 for PAHs concentration, fiber exposition to headspace, temperature, and NaCl concentration, respectively. The limit of detection (LOD) in this protocol ranged from 0.2 to 41.4 ng L-1, while recovery values from 67.65 to 113.10%. Besides that, relative standard deviation (RSD) were lower than 8.39% considering high molecular weight compounds. Moreover, the proposed methodology in this work does not require any previous treatment of the sample and allows to quantify a higher number of PAHs. Notably, naphthalene was the major PAHs compound quantified in all samples of the produced water at 99.99 µg L-1. Altogether, these results supported this methodology as a suitable analytical strategy for fast determination of PAHs in produced water from oil-based industry.

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This study evaluated the acute effects of nine different production chemicals typically employed in oil exploration on the toxicity of a synthetic produced water (PW). Bioassays with the Microtox® System were performed to monitor changes in the level of light emission of the marine luminescent bacteria Vibrio fischeri during exposure to the samples. The results show that synthetic PW is moderately toxic to these organisms, and the addition of oilfield chemicals significantly increases its toxicity. For most of the additives tested, the toxicity of the aqueous phase following partitioning against crude oil was not strongly altered by the presence of these chemicals. Synergistic effects occurred in the three different mixtures investigated. Among the additives studied, biocide, corrosion inhibitor, H2S scavenger, and surfactant were the most toxic for V. fischeri. Furthermore, the surfactant has been identified as the possible source of the acute toxicity observed.

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Petroleum has been extracted from oil reservoirs using different techniques. This activity is accompanied for a large amount of water and sometimes mixed with gas. This produced water has a high oil concentration and other toxic chemical compounds, thus, it must be treated to be reused or released to environment according to environmental protection regulations. Currently, ceramic membrane technology has been employed in the wastewater treatment, due to its high benefit-cost ratio. In this sense, this work aims to study the oil-water mixture separation process using a new configuration of tubular ceramic membrane module by computational fluid dynamic (ANSYS Fluent software). The proposed model is composed of mass and linear momentum conservation equations coupled to Darcy's law and SST k-ω turbulence model. Results of the volumetric fraction, pressure, and velocity distribution of the oil and water phases are presented and discussed. The results indicated that the proposed model and new device both have great potential to be used on the water/oil separation process and that the transmembrane pressure remains constant in the axial direction and decreases radially through the membranes, indicating an efficient system that favors the transport of clean water and oil retention.

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A novel method based on relational analysis is presented for assessing the performance of conventional oil exploitation and its environmental implications, with a focus on the energy-water nexus. It considers the energy system as a metabolic network and integrates various factors relevant for technical, economic and environmental processes, thus avoiding some of the simplifications inherent in conventional approaches to the assessment of primary resource quality, such as economic cost-benefit analysis (CBA) and the energy return on investment (EROI). Relational analysis distinguishes between functional (notional) and structural (tangible) elements in the metabolic network, which allows a simultaneous characterization and geo-localization of the exploitation process across different scales and dimensions of analysis. Key aspects of the approach are illustrated with data from the Ecuadorian oil sector spanning the period 1972-2018. It is shown that by establishing a relation among the characteristics of the exploited oil fields (oil typology, age of field) and those of the exploitation process (requirement of energy carriers, labor, freshwater and power capacity and generation of greenhouse gases and oil-produced water), changes in the performance and environmental implications of the oil extraction system can be characterized at different points in space and time.

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Produced water (PW) is a by-product generated throughout oil exploration. Geological formation and geographical location of the reservoir influence its physical, chemical and biological characteristics. Xanthan gum (XG), an exopolysaccharide (EPS) produced by Xanthomonas campestris, has been widely used in enhanced oil recovery (EOR) technology because of its high viscosity, pseudoplastic behavior, stability in function of salinity, temperature and alkaline conditions. The production of XG may be affected by the composition of the PW, where the acetyl and pyruvyl radicals may be present in the mannoses. The aim of this study was to evaluate the composition of XG produced by X. campestris, particularly the amount of Xanthan, acetyl and pyruvyl groups, in culture mediums containing distilled (DW) or produced (PW) water in different concentrations, by means of dispersive Raman spectroscopy (1064 nm). The spectra of XG showed peaks referred to the main constituents of the Xanthan (glucose, mannose and glucuronic acid). Spectral features assigned to pyruvyl were seen in all samples mainly at ~1010 cm-1, with higher intensity when using DW and 25% PW. PCA loadings showed that the peaks assigned to pyruvyl are consistent to presence of sodium pyruvate (~1040/~1050 and ~ 1432 cm-1) and were higher in the samples obtained in 25% PW. ANOVA GLM applied to Raman peaks of interest (~1010 and ~ 1090 cm-1) and to PCA scores (Score 1 to Score 3) showed that both were influenced by the type of water used in the culture medium, where the XG were strongly reduced in the groups PW compared to DW while the pyruvyl content increased proportionally with the concentration of PW. The results suggest that the composition of the water used in the bacteria's culture medium influenced the composition of XG, including the amount of Xanthan and particularly the pyruvyl content, and therefore needs to be considered when using this approach of injecting XG in oil fields as pyruvyl content affects viscosity.

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In South America, Colombia is known as an important oil-producing country. However, the environmental impact of crude oil industry has not been studied deeply and few studies have been carried out for evaluating responses of algae and its adaptation under specific conditions. Enzymatic and physiological effects in Chlorella vulgaris and its potential for bioremediation after exposure to produced water (PW) were assessed using different PW concentrations (0, 25, 50, 75 and 100%) and crude oil. Variables such as cell density, growth rate (µ), percentage of growth inhibition (% I), chlorophyll a and b and cell diameter were evaluated during 5 days. Furthermore, enzymatic biomarkers such as superoxide dismutase (SOD) and catalase (CAT) were also measured. Results showed that the treatment with 100% PW had the highest cell density and µ; similarly, 25% PW treatment had a similar behaviour, being these two treatments with the highest growth. A dose-dependent response was seen for chlorophyll a and b and cell diameter, showing significant differences between treatments and the control. Different levels of SOD and CAT were observed in algae exposed to PW. At 24 h, an increase in SOD and CAT activity was observed, probably due to effects caused by xenobiotics. After 72 h, a decrease in the activity of both enzymes was observed. The results evidenced that C. vulgaris can adapt easily to PW, showing an increase on its growth and stabilisation in its antioxidant activity. Additionally, cell diameter results and decrease of hydrocarbons and phenols show the potential of these algae to degrade xenobiotics from PW.

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Production water is the largest byproduct of the oil industry and must be treated before disposal, either by reinjection or shedding processes, with the purpose of eliminating emulsified crude oil and avoiding the operational and toxic problems associated with it. The objective of this work was to immobilize a hydrocarbon-degrading strain on activated carbons, to evaluate the biocomplex's capacity for catalyzing hydrocarbons from Oil in Brine emulsions (O/W) simulating produced waters. Activated carbons were prepared and their chemical and porous properties were estimated by XPS, pHPZC and SEM, N2 adsorption, and mercury porosimetry. Biomaterials were synthesized and hydrocarbon removal tests were performed. The basic and neutral carbons immobilized Pseudomonas stutzeri by physisorption in the macroporous space and electrostatic interactions (108⁻108 UFC∙g-1), while acid materials inhibited bacterial growth. Removal of aromatic hydrocarbons was more efficient using materials (60%⁻93%) and biomaterials (16%⁻84%) than using free P. stutzeri (1%⁻47%), and the removal efficiencies of crude oil were 22%, 48% and 37% for P. stutzeri and two biomaterials, respectively. The presence of minor hydrocarbons only when P. stutzeri was present confirmed the biotransformation process.

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One of the main problems faced by the oil industry is related to the amount of produced water generated during the oil extraction process. For proper disposal of this effluent, treatment processes should be applied to meet the requirements established by environmental agencies. Thus, the present study aimed to evaluate the efficiency of the combination of electroflotation process and down-flow granular filtration in the treatment of wastewater contaminated with oil. To this end, they were studied in a pilot system, to optimize the electroflotation process and combination of processes. The performance of the pilot system was determined by removal of oil and grease content (OG) in the treated effluent. According to the results, the electroflotation process had the best performance with an effluent input rate of 62 m3 m-2 d-1, current density of 80 A m-2 and NaCl concentration of 7900 mg L-1. Under these conditions, the mean removal of OG from synthesized solution after 720 minutes of treatment was 86.64% (59.51 mg L-1) for the electroflotation process and 61.52% (12.91 mg L-1) after down-flow granular filtration. By combining the processes studied, we obtained an initial OG removal (470.55 mg L-1) of over 98% (6.42 mg L-1) in 720 minutes of treatment, with an energy consumption of the electrochemical reactor of 1.47 kWh m-3. ABBREVIATIONS: ANOVA: analysis of variance; CCRD: Central Composite Rotational Delineation; DOC: dissolved organic carbon; DSA: dimensionally stable anodes; LAPOA: Laboratory of Water Potabilization; OG: oil and grease; OPER: operating parameters of the electrochemical reactor; TDS: total dissolved solids; UFSC: Federal University of Santa Catarina.

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