Search Results (36)

The experiments in this study investigated the toxicity of naphthenic acids (NAs) on the algal culture Spirulina platensis. The tests monitored the progression of the algal suspension in media contaminated with various concentrations of naphthenic acids. The evolution of the algal culture during the metabolism of NAs was investigated. The monitoring also included the determination of the values of some parameters during the biodegradation process (pH, conductivity, cell viability, dissolved oxygen). Optical density measurements (OD₆₀₀) were used to quantify the growth of Spirulina platensis, alongside the determination of the sedimentation index (IS). Cell viability was assessed microscopically using TEM and optical microscopy. The results facilitated the estimation of the percentage of cell growth inhibition and the inhibitory concentration value, determined by estimating ECb50 (concentration of NAs corresponding to 50% inhibition). The chemical quantification of naphthenic acids in the samples analyzed was performed by calculating the acidity value (AV) and characterizing the naphthenic acids through FTIR analysis. The graphical representation of ECb50 was established by extrapolating to a concentration of 110 mg/mL of naphthenic acids. We have demonstrated that pollution caused by NAs can be mitigated by the algae Spirulina platensis, which can metabolize these compounds and thus biodegrade them. Full article

Previous coreflooding results and wettability analyses in our group show that injection of naphthenic-acid-enriched water can improve oil recovery over traditional waterflooding. This observation is still a subject of research efforts without a definitive explanation. Naphthenic acids (NA) have been reported to drive wettability alteration and increase the water–oil interface elasticity. These alterations depend on the NA carbon number and aqueous-phase salinity, among other conditions, as reported in the literature. Smart-water flooding (SWF) research often links recovery to the initial wettability condition, being higher for initially oil-wet rock. SWF refers to a technique in which the aqueous-phase ion composition or/and salinity are changed to maximize oil recovery. Given NAs’ complex solution behavior, selecting acid combinations that prompt oil recovery is a difficult objective. The aim of this research is to determine the effects of select naphthenic acids on the oil–water interfacial rheology and wettability alteration and how these interfacial effects are associated with oil recovery under spontaneous imbibition. NAs were selected based on their carbon number, molecular structure, and solubility in the saline solution used in this research. We aimed at exploring which NAs should be used to regulate interfacial properties so as to either increase oil recovery or accelerate production. Time-domain nuclear magnetic resonance, interfacial dilatational rheology, and liquid-bridge experiments, i.e., proxy of snap-off, were conducted. A baseline was established using results obtained with a previously tested sulfate-rich aqueous phase, shown to be effective in recovering oil. Results show that NA14 and N18 increase the water–oil interfacial viscoelasticity and induce interfacial healing but led to different recovery factors. N10, while effective at inducing water wetness in oil-wet rock, is ineffective at increasing the recovery factor. We concluded that wettability and oil–water interfacial rheology are not exclusive, and instead they can synergistically favor EOR benefits. Moreover, oil recovery benefits under spontaneous imbibition are shown to depend strongly on the initial wettability conditions. Full article

Altered body condition and diminished growth in wildlife in the Alberta Oil Sands Region (AOSR) are prompting investigations into the impact of oil sands industrial activity on wildlife in the region. Chemical constituents from bitumen-influenced waters, including oil sands process-affected water (OSPW), can disrupt endocrine signaling, leading to aberrant lipid accumulation and altered glycemic control in mammals. This study aimed to investigate the effects of naphthenic acid fraction components (NAFCs), derived from OSPW, on energy homeostasis using the McA-RH7777 rat hepatocyte model. Cells were exposed to NAFCs at nominal concentrations of 0, 0.73, 14.7, and 73.4 mg/L for 24 and 48 h. We assessed gene expression related to lipid and glucose metabolism and measured triglyceride accumulation, glucose, and fatty acid uptake. NAFC exposure (14.7 and 73.4 mg/L) reduced triglyceride levels and glucose uptake and increased fatty acid uptake and the expression of beta-oxidation genes, suggesting a metabolic switch from glucose to fatty acid oxidation. This switch in substrate availability signifies a shift in cellular energy dynamics, potentially linked to altered mitochondrial function. To investigate this, we conducted adenosine triphosphate (ATP), mitochondrial membrane potential, and terminal deoxynucleotidyl transferase dUTP nick-end labeling (TUNEL) assays to measure cellular ATP levels, mitochondrial membrane potential, and apoptosis, respectively. At both time points, 73.4 mg/L NAFC exposure resulted in increased ATP levels, induced mitochondrial membrane hyperpolarization, and increased apoptosis. These results suggest that mitochondrial efficiency is compromised, necessitating metabolic adaptations to maintain energy homeostasis. Given that cells exhibit metabolic flexibility that allows them to dynamically respond to changes in substrate availability, we further demonstrated that the kynurenine–tryptophan ratio (KTR) serves as a marker for a shift in energy metabolism under these stress conditions. This work provides a mechanistic framework for understanding how bitumen-derived organic contaminants may disrupt metabolic function in wildlife living in the AOSR. These findings further support the use of molecular markers like KTR to evaluate sub-lethal metabolic stress in environmental health monitoring. Full article

Oil sand tailings from bitumen extraction contain various contaminants, including polycyclic aromatic hydrocarbons, BTEX, and naphthenic acids, which can leak into surrounding environments, threatening aquatic ecosystems and human health. These tailings also contribute to environmental issues such as habitat disruption and greenhouse gas emissions. Despite these challenges, oil sand tailings hold significant potential for waste-to-resource recovery as they contain valuable minerals like rare earth elements (REEs), titanium, nickel, and vanadium. Traditional metal extraction methods are environmentally damaging, requiring high energy inputs and generating dust and harmful emissions. Furthermore, the coating of hydrocarbons on mineral surfaces presents an additional challenge, as it can inhibit the efficiency of metal extraction processes by blocking access to the minerals. This highlights the need for alternative, eco-friendly approaches. Bioleaching, which uses microorganisms to extract metals, emerges as a sustainable solution to unlock the valuable metals within oil sand tailings. This review discusses the minerals found in oil sand tailings, the challenges associated with their extraction, methods from hydrocarbon removal from minerals, and bioleaching as a potential metal recovery method. Full article

Responding to global standards and legislative updates in Canada, including Bill S-5 (2023), toxicity testing is shifting towards more ethical, in vitro methods. Traditional two-dimensional (2D) monolayer cell cultures, limited in replicating the complex in vivo environment, have prompted the development of more relevant three-dimensional (3D) spheroidal hepatocyte cultures. This study introduces the first 3D spheroid model for McA-RH7777 cells, assessing xenobiotic receptor activation, cellular signaling, and toxicity against dexamethasone and naphthenic acid (NA)-fraction components; NAFCs. Our findings reveal that 3D McA-RH7777 spheroids demonstrate enhanced sensitivity and more uniform dose–response patterns in gene expression related to xenobiotic metabolism (AhR and PPAR) for both single compounds and complex mixtures. Specifically, 3D cultures showed significant gene expression changes upon dexamethasone exposure and exhibited varying degrees of sensitivity and resistance to the apoptotic effects induced by NAFCs, in comparison to 2D cultures. The optimization of 3D culture conditions enhances the model’s physiological relevance and enables the identification of genomic signatures under varied exposures. This study highlights the potential of 3D spheroid cultures in providing a more accurate representation of the liver’s microenvironment and advancing our understanding of cellular mechanisms in toxicity testing. Full article

Naphthenic acid corrosion is a well-recognized factor contributing to corrosion in the construction of offshore industry pipelines. To mitigate the corrosive effects, minor quantities of alloying elements are introduced into the steel. This research specifically explores the corrosion effects arising from immersing low-carbon steel, specifically A333 Grade 6, in a naphthenic acid solution. Various weight percentages of niobium were incorporated, and the resulting properties were observed. It was noted that the addition of 2% niobium in low-carbon steel exhibited the least mass loss and a lower corrosion rate after a 12 h immersion in naphthenic acid. Microstructural analysis using scanning electron microscopy (SEM) revealed small white particles, indicating the presence of oil sediment residue, along with corrosion pits. Following the addition of 2% niobium, the occurrence of corrosion pits markedly decreased, and only minor voids were observed. Additionally, the chemical composition analysis using energy-dispersive X-Ray analysis (EDX) showed that the black spot exhibited the highest percentage of carbon, resembling high corrosion attack. Meanwhile, the whitish regions with low carbon content indicated the lowest corrosion attack. The results demonstrated that the addition of 2% niobium yielded optimal properties for justifying corrosion effects. Therefore, low-carbon steel with a 2% niobium addition can be regarded as a superior corrosion-resistant material for offshore platform pipeline applications. Full article

Oil sands process-affected water (OSPW) contains a diverse mixture of inorganic and organic compounds. Naphthenic acids (NAs) are a subset of the organic naphthenic acid fraction compounds (NAFCs) and are a major contributor of toxicity to aquatic species. Thousands of unique chemical formulae are measured in OSPW by accurate mass spectrometry and high-resolution mass spectrometry (MS) analysis of NAFCs. As no commercial reference standard is available to cover the range of compounds present in NAFCs, quantitation may best be referred to as “semi-quantitative” and is based on the responses of one or more model compounds. Negative mode electrospray ionization (ESI-) is often used for NAFC measurement but is prone to ion suppression in complex matrices. This review discusses aspects of off-line sample preparation techniques and liquid chromatography (LC) separations to help reduce ion suppression effects and improve the comparability of both inter-laboratory and intra-laboratory results. Alternative approaches to the analytical parameters discussed include extraction solvents, salt content of samples, extraction pH, off-line sample cleanup, on-line LC chromatography, calibration standards, MS ionization modes, NAFC compound classes, MS mass resolution, and the use of internal standards. Full article

The authors studied the problem of naphthenate deposits in the oil and gas industry. Currently, there are few ways available to inhibit or dissolve naphthenate deposits in oil facilities. Naphthenate deposits can block pipelines and aggregate in other parts of the installation, i.e., in the separators. In Europe, the issue of deposition on oil rigs is commonly encountered in Norway and the United Kingdom, as well as in some African countries, i.e., Angola and Nigeria. Many tons of chemicals are used to combat naphthenate deposition, usually through inhibition, but also via the dissolution of the scale that precipitates over time. The presented work examines the characteristics of naphthenate fouling, historical ways to inhibit it, and current approaches to the problem, as well as the results of the laboratory testing of naphthenate inhibitors and solvents. The process of the naphthenate creation is as follows. When oil exhibits a high TAN (total acid number) and high content of salty water, naphthenate deposits can emerge via the reaction of naphthenic acids and metal salts (mostly calcium ones). Naphthenates are partially insoluble in water, and they usually float below the oil/water interface. The standard methods of naphthenate inhibition involve lowering the pH of the production water, which can result in serious problems, especially related to corrosion. This study addresses experiments conducted in the laboratory in Poland and on oil rigs in Angola and is based on contemporary knowledge and standards. The objective of this paper was to investigate the most suitable naphthenate inhibitors and solvents, as well as to undertake bottle tests of naphthenate inhibitors with a focus on the main indicators (water clarity, quality of separation surface, and clarity of oil). The use of citric and formic acids in this paper is a novelty, and it is compared with the results obtained with the more commonly used acetic acid, hydrochloric acid, and ABS acid. It was proven that formic acid can effectively inhibit and dissolve naphthenic deposits (99% efficiency of inhibition and 100% efficiency of dissolution). It was found that some acids used in naphthenate inhibition create more deposits than were originally present. Formic acid and ABS acid yielded significantly better results than other types. It is also here hypothesized that there are substances other than acids that can effectively remove naphthenate deposits, and the other novelty of this study is in the use of mutual solvents in the removal of naphthenate salts. Another important outcome is the finding that not only acids but also mutual solvents (EGMBE and isopropyl alcohol) can effectively remove naphthenate deposits. The test results show that formic acid dissolved all of the naphthenates, while citric acid had 97% efficacy, isopropyl alcohol had 95% efficacy, and EGMBE showed 94% efficacy. The impacts of commercial naphthenate inhibitors on the bottle test results and interfacial tension measurements were also investigated. It was shown that commercial naphthenate inhibitors can decrease the interfacial tension between oil and water by more than 30% when used at dosages of 400 ppm. Full article

The ethylenediamine-N,N′-disuccinic acid (EDDS) was utilized to form Fe-EDDS complex to activate peroxymonosulfate (PMS) in the electrochemical (EC) co-catalytic system for effective oxidation of naphthenic acids (NAs) under neutral pH conditions. 1-adamantanecarboxylic acid (ACA) was used as a model compound to represent NAs, which are persistent pollutants that are abundantly present in oil and gas field wastewater. The ACA degradation rate was significantly enhanced in the EC/PMS/Fe(III)-EDDS system (96.6%) compared to that of the EC/PMS/Fe(III) system (65.4%). The addition of EDDS led to the formation of a stable complex of Fe-EDDS under neutral pH conditions, which effectively promoted the redox cycle of Fe(III)-EDDS/Fe(II)-EDDS to activate PMS to generate oxidative species for ACA degradation. The results of quenching and chemical probe experiments, as well as electron paramagnetic resonance (EPR) analysis, identified significant contributions of ^•OH, ¹O₂, and SO₄^•− in the removal of ACA. The ACA degradation pathways were revealed based on the results of high resolution mass spectrometry analysis and calculation of the Fukui index. The presence of anions, such as NO₃⁻, Cl⁻, and HCO₃⁻, as well as humic acids, induced nonsignificant influence on the ACA degradation, indicating the robustness of the current system for applications in authentic scenarios. Overall results indicated the EC/PMS/Fe(III)-EDDS system is a promising strategy for the practical treatment of NAs in oil and gas field wastewater. Full article

Large volumes of oil sands process-affected waters (OSPW) result from heavy oil extraction in Alberta, Canada. Currently, a toxic legacy of ca. 500 Mm³ is stored in tailings ponds under a zero-discharge policy. OSPW is a complex mixture of suspended and dissolved materials including a wide range of inorganic and organic contaminants. Classically defined naphthenic acids (NAs; C_nH_2n+ZO₂) are one of the primary toxic fractions in OSPW and have therefore been the subject of considerable research interest. Most studies employ considerable sample cleanup followed by liquid chromatography and/or high-resolution mass spectrometry (HRMS) for the characterization of these complex mixtures. However, these strategies can be time- and cost-intensive, limiting the scope of research and adoption for regulatory purposes. Condensed phase membrane introduction mass spectrometry (CP-MIMS) is emerging as a “fit-for-purpose” approach for the analysis of NAs. This technique directly interfaces the mass spectrometer with an aqueous sample using a hydrophobic semi-permeable membrane, requiring only pH adjustment to convert NAs to a membrane-permeable form. Here, we examine the perm-selectivity of classical NAs (O₂) relative to their more oxidized counterparts (O₃–O₇) and heteroatomic (N, S) species collectively termed naphthenic acid fraction compounds (NAFCs). The investigation of 14 model compounds revealed that classically defined NAs are greater than 50-fold more membrane permeable than their oxidized/heteroatomic analogs. HRMS analysis of real OSPW extracts with and without membrane clean-up further supported selectivity towards the toxic O₂ class of NAs, with >85% of the overall signal intensity attributable to O₂ NAs in the membrane permeate despite as little as 34.7 ± 0.6% O₂ NAs observed in the directly infused mixture. The information collected with HRMS is leveraged to refine our method for analysis of NAs at unit mass resolution. This new method is applied to 28 archived real-world samples containing NAs/NAFCs from constructed wetlands, OSPW, and environmental monitoring campaigns. Concentrations ranged from 0–25 mg/L O₂ NAs and the results measured by CP-MIMS (unit mass) and SPE-HRMS (Orbitrap) showed good agreement (slope = 0.80; R² = 0.76). Full article

Resins have enormous potential in the removal of naphthenic acids (NAs) from transformer oil due to their rich porosity and high mechanical and diversified functionality, whereas their poor adsorption capacity limits application. In this work, the polystyrene–diethylamine resin (PS−DEA−x) was prepared by grafting diethylamine (DEA) onto chloromethylated polystyrene (PS−Cl) resin to efficiently adsorb cyclopentane carboxylic acid from transformer oil for the first time. The characterization analysis results indicated that amine contents were significantly enhanced with the increase in DEA. Particularly, resin with a molar ratio of 1:5 depending on chloromethyl to DEA (PS−DEA−5) exhibited the highest amine contents and efficient adsorption of cyclopentane carboxylic acid (static adsorption capacity up to 110.0 mg/g), which was about 5 times higher than that of the pristine PS−Cl. The thermodynamic and kinetic studies showed that the adsorption behaviors could be well fitted to the Langmuir isotherm equation and pseudo−second−order rate equation. Moreover, it was found that 1 g of the PS−DEA−5 can decontaminate about 760 mL transformer oil to meet reuse standards by a continuous stream, indicating its potential application in industry. Full article

This paper represents a detailed techno-economic analysis of a typical commercial-scale catalytic decarboxylation process of naphthenic acids over HZSM-5 zeolite. Simulation of the process has been performed in ASPEN Plus^®. The performance of the modeled unit was compared to experimental results data from a similar plant. Two models were developed for the proposed industrial plant based on continuous flow reactors; the first is based on a fluidized bed reactor, and it was modeled as a continuous stirred tank reactor (CSTR) unit, and the second is a semi-regenerative process that consists of three fixed-bed reactors with intermediate preheaters and are modeled as three plug flow reactors (PFR). The outcome of the economic analysis of the two proposed commercial scale reactors of a decarboxylation process of a capacity of 11,000 bbl/day showed that the CAPEX, including the total equipment cost for the fluidized bed reactor plant and semi-regenerative process plant, was $44,319,362 and $4,447,919, respectively. The annual operating cost for the fluidized bed plant and semi-regenerative process plant is 45,269,180 $/year and 1,771,839 $/year, respectively. Our results demonstrated that catalytic decarboxylation over HZSM-5 zeolite is economically feasible using a semi-regenerative process, and is a promising method for removing naphthenic acid. The insight obtained from this work can be used as a basis for more comprehensive future financial and risk modeling of the process. The cost estimated in this work was compared to the Khartoum refinery cost for the naphthenic acid corrosion mitigation system, with a saving of $29,459,528. Full article

The greenhouse gas (GHG) emission mandate on jet fuel requires a gradual reduction in the fuel’s GHG emissions, up to 50%, by 2050. For this reason, the demand for bio-jet fuel blended with conventional petroleum-derived jet fuel will increase. In order to meet the quality requirement of blended fuels (ASTM D7566), modeling that can predict the correlation between properties is required. Our aim was to predict the low-temperature properties using the distillation profile results obtained from Simulated Distillation (SIMDIS) according to the carbon number and chemical compositions of bio-jet fuel through correlation and regression analysis. We used hydroprocessed ester and fatty acid (HEFA) bio-jet fuel and hydrocarbon reagents that included C₈, C₁₀, and C₁₂ carbons and five main families of hydrocarbons for blended jet fuel. This study shows an overall trend for each component, indicating that the distilled volume fraction is more affected than the carbon number. In the case of the freezing point, by composition, n-paraffin and naphthene have regression coefficients of more than 0.85 for the 50% and 60% recovery temperatures, respectively. In terms of carbon number, the C₈ sample has a significant regression coefficient for the 40% recovery temperature, and C₁₀ has a significant regression coefficient for the initial boiling point (IBP) and 10% recovery temperature. In the case of kinematic viscosity, by composition, the regression coefficient is significant for the 20% to 40% recovery temperatures. For naphthene, the kinematic viscosity exhibited no relationship with carbon number. This information can be utilized to determine the blended ratio of bio-jet fuel and conventional jet fuel in newly certified or commercial applications. Full article

Naphthenic Acids (NA) are important oil extraction subproducts. These chemical species are one of the leading causes of marine pollution and duct corrosion. For this reason, understanding the behavior of NAs in different saline conditions is one of the challenges in the oil industry. In this work, we simulated several naphthenic acid species and their mixtures, employing density functional theory calculations with the MST-IEFPCM continuum solvation model, to obtain the octanol–water partition coefficients, together with microsecond classical molecular dynamics. The latter consisted of pure water, low-salinity, and high-salinity environment simulations, to assess the stability of NAs aggregates and their sizes. The quantum calculations have shown that the longer chain acids are more hydrophobic, and the classical simulations corroborated: that the longer the chain, the higher the order of the aggregate. In addition, we observed that larger aggregates are stable at higher salinities for all the studied NAs. This can be one factor in the observed low-salinity-enhanced oil recovery, which is a complex phenomenon. The simulations also show that stabilizing the aggregates induced by the salinity involves a direct interplay of Na⁺ cations with the carboxylic groups of the NAs inside the aggregates. In some cases, the ion/NA organization forms a membrane-like circular structural arrangement, especially for longer chain NAs. Full article

Naphthenic acids are naturally occurring carboxylic acids in crude oil with cyclic or aromatic rings in their structure. These carboxylic acids are responsible for the acidity of crude oil, leading to corrosion problems in refinery equipment and the deactivation of catalysts while creating a continuous need for maintenance. Therefore, removing naphthenic acids has become an important requirement in refining acidic crude oil. In this paper, experiments are conducted to investigate the use of HZSM-5 zeolite catalyst to reduce the total acid number (TAN) of a typical acidic crude oil obtained from Al-Fula blocks in Western Sudan. TAN is an important metric signifying the acidity of crude oil. A full factorial design of the experiment (DOE) framework enabled a better understanding of the efficacy of the catalyst at three parametric levels (reaction temperature: 250-270-300 °C, reaction time: 2-3-4 h, and oil:catalyst weight ratio: 20-22-25 g/g). The results demonstrate that the HZSM-5 zeolite catalyst provides up to 99% removal of naphthenic acids via the decarboxylation route. Additionally, the removal efficiency increases with increasing temperature and residence time. The acidity of the crude oil was shown to decrease after treatment with the catalyst for four hrs.; from 6.5 mg KOH/g crude to 1.24; 0.39 and 0.17 mg KOH/g at 250; 270 and 300 °C, respectively. A sharp decrease of TAN was observed at the oil catalyst mass ratio of 20 g/g at 250 °C, and almost complete conversion of acids was achieved after 4 hrs. Another experiment at 270 °C showed a converse relationship between the oil:catalyst ratio and acid removal; suggesting the activation of side reactions at higher temperature conditions catalyzed by excess acid. Finally; a Langmuir–Hinshelwood (LH) kinetic model has been developed to enable rapid prediction of the performance of the HZSM-5 zeolite catalyst for decarboxylation reaction. The model has also been validated and tested in ASPEN^® software for future simulation and scalability studies. Full article