Naphthenic Acid Fraction Components Research Articles

A Light Touch: Solar Photocatalysis Detoxifies Oil Sands Process-Affected Waters Prior to Significant Treatment of Naphthenic Acids.

Environmental reclamation of Canada's oil sands tailings ponds is among the single largest water treatment challenges globally. The toxicity of oil sands process-affected water (OSPW) has been associated with its dissolved organics, a complex mixture of naphthenic acid fraction components (NAFCs). Here, we evaluated solar treatment with buoyant photocatalysts (BPCs) as a passive advanced oxidation process (P-AOP) for OSPW remediation. Photocatalysis fully degraded naphthenic acids (NAs) and acid extractable organics (AEO) in 3 different OSPW samples. However, classical NAs and AEO, traditionally considered among the principal toxicants in OSPW, were not correlated with OSPW toxicity herein. Instead, nontarget petroleomic analysis revealed that low-polarity organosulfur compounds, composing <10% of the total AEO, apparently accounted for the majority of waters' toxicity to fish, as described by a model of tissue partitioning. These findings have implications for OSPW release, for which a less extensive but more selective treatment may be required than previously expected.

Naphthenic acid fraction components from oil sands process-affected water from the Athabasca Oil Sands Region impair murine osteoblast differentiation and function.

The extraction of bitumen from surface mining in the Athabasca Oil Sands Region (AOSR) produces large quantities of oil sands process-affected water (OSPW) that needs to be stored in settling basins near extraction sites. Chemical constituents of OSPW are known to impair bone health in some organisms, which can lead to increased fracture risk and lower reproductive fitness. Naphthenic acid fraction components (NAFCs) are thought to be among the most toxic class of compounds in OSPW; however, the effect of NAFCs on osteoblast development is largely unknown. In this study, we demonstrate that NAFCs from OSPW inhibit osteoblast differentiation and deposition of extracellular matrix, which is required for bone formation. Extracellular matrix deposition was inhibited in osteoblasts exposed to 12.5-125 mg/L of NAFC for 21 days. We also show that components within NAFCs inhibit the expression of gene markers of osteoblast differentiation and function, namely, alkaline phosphatase (Alp), osteocalcin, and collagen type 1 alpha 1 (Col1a1). These effects were partially mediated by the induction of glucocorticoid receptor (GR) activity; NAFC induces the expression of the GR activity marker genes Sgk1 (12.5mg/L) and p85a (125 mg/L) and inhibits GR protein (125 mg/L) and Opg RNA (12.5mg/L) expression. This study provides evidence that NAFC concentrations of 12.5mg/L and above can directly act on osteoblasts to inhibit bone formation and suggests that NAFCs contain components that can act as GR agonists, which may have further endocrine disrupting effects on exposed wildlife.

Effects of asphaltenes on the photolytic and toxic behavior of bitumen and conventional oil products on saltwater

The effects of asphaltenes on the photolytic and toxic behavior of petroleum oil on seawater was investigated by exposing five original oils and their maltenes to solar irradiation for seven days. Polycyclic aromatic hydrocarbons (PAHs) experienced the fastest photo-oxidation, but negligible photolytic loss was observed for most normal alkanes and all the petroleum biomarkers from tri-cyclic to pentyl-cyclic terpanes in the test total oil and maltenes. The removal of most PAHs from some maltenes was greater than the corresponding total oils. Deasphalting process did not affect the characteristics of naphthenic acid fraction components (NAFCs) in all control samples. In all test oils, solar irradiation formed abundant NAFCs, in particular those only containing oxygen as the heteroatoms (Oo species). The formed Oo species were abundant in congeners having highly saturated congeners, and shifted to a lighter carbon number after exposed. Deasphalting process significantly enhanced the formation of Oo species (o from 2 to 4) for all test oils, in particular for the Cold Lake Blend and Bunker C. The toxicity of exposed maltenes was generally higher than the exposed total oil for most oils, suggesting the aqueous toxicity level was positively related to the formed NAFC intermediates.

Fathead Minnows Exposed to Organic Compounds from Oil Sands Tailings as Embryos Have Reduced Survival, Impaired Development, and Altered Behaviors That Persist into Larval Stages.

Our study evaluated whether exposure to naphthenic acid fraction compounds (NAFCs) extracted from oil sands process–affected waters (OSPW) has adverse effects on fish embryos that persist into later life. We exposed fathead minnow (Pimephales promelas) embryos to concentrations of NAFCs found in OSPW (2.5–54 mg/L) for 7 days (1 day postfertilization to hatch), then raised surviving larvae in outdoor mesocosms of uncontaminated lake water for 1 month. Embryos exposed to NAFCs were more likely to exhibit malformations (by up to 8‐fold) and had slower heart rates (by up to 24%) compared to controls. Fish raised in uncontaminated lake water following exposure to NAFCs as embryos, were 2.5‐fold less likely to survive during the larval stage than control fish. These fish also showed up to a 45% decrease in swim activity and a 36% increase in swim burst events during behavioral tests relative to controls. We conclude that exposure to NAFCs during the embryonic stage can have lasting effects on fish survival, physiology, and behavior that persist at least through the larval stage. These findings of delayed mortalities and persistent sublethal effects of embryonic NAFC exposure are relevant to informing the development of regulations on treated OSPW releases from mining operations. Environ Toxicol Chem 2022;41:1319–1332. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

The effects of oil sands process-affected water naphthenic acid fraction components on GDF15 secretion in extravillous trophoblast cells

Exposure to compounds present in petroleum and wastewaters from oil and gas extraction sites in the Alberta Oil Sands Region can impair reproductive health. It has been established that acid extractable organics found in oil sands process-affected water (OSPW) such as naphthenic acids (NA-fraction components; NAFC) can adversely affect reproductive outcomes. We have shown that NAFC exposure results in a significant upregulation of GDF15 in placental trophoblasts, a cellular stress marker known to be involved in human embryonic development and necessary for the maintenance of pregnancy. However, little is known regarding the mechanism(s) underlying NAFC-induced increases in GDF15 production during early placentation. The goal of this study was to examine the effects of NAFC exposure on the regulation of critical transcription factors of GDF15 in extravillous trophoblast cells. Of these transcription factors, inflammatory mediators including prostaglandins have been reported to inhibit proliferation and migration of trophoblast cells in vitro. Hence, the secondary goal of this study was to determine whether inflammation mediated through prostaglandin production is critical to GDF15 secretion. HTR-8/SVneo cells were exposed to an NAFC for 6 and 24 h to assess the expression of key transcriptional regulators, GDF15 secretion, and prostaglandin (PGE2) output. Treatment with NAFC (125 mg/L only) significantly increased GDF15 expression and secretion in association with upregulation of the transcription factors KLF4, EGR1, ATF3 and TP53. Similarly, PTGS2 (i.e. COX2) expression and PGE2 output were significantly increased at the same concentration. However, co-treatment with a COX2 selective antagonist (SC236) only partially blocked the NAFC-induced increase in PGE2 output and did not block GDF15 expression or secretion. These findings suggest that while NAFC may affect GDF15 production, it is not exclusively a result of prostaglandin-mediated inflammation. This study provides new insights into the mechanisms by which NAFC may adversely affect placental trophoblast cell function in mammals.

Occurrence and characterisation of naphthenic acid fraction components in oil residues and sediments stranded on the shoreline of Chedabucto Bay, Nova Scotia, Canada

In June 2016, oil residues and sediment samples were collected from the shoreline of Chedabucto Bay, Nova Scotia, Canada, at sites affected by the 1970 Arrow oil spill. This study aimed to investigate the occurrence, fate, and behaviour of oil components 45 years post-spill by analysing polar naphthenic acid fraction components (NAFCs) through high-performance liquid chromatography–high-resolution mass spectrometry (HPLC–HRMS). In all samples, the most abundant NAFC species were those having only oxygen as the heteroatom (Oo species, o indicating the number of oxygen atoms, from 1 to 8) and a high degree of saturation. NAFC species only containing two oxygen atoms (O2) accounted for 50–70% of all Oo species. The abundance of all remaining species was negligible compared with Oo species. NAFCs in most Arrow oil residues had higher levels of oxygen species than the oil remaining stored in the sunken tanker. Environmental sediment samples collected from near a marina away from the spill site contained a dominant biological, whereas all Arrow oil residues were mainly composed of NAFCs that are characteristic of petroleum. The abundance of NAFCs in the Arrow oil residues varied between sites, confirming that site-specific environmental conditions play a major role in controlling the fate and behaviour of oil components, including NAFCs.

Development of a Reduced-Volume Acute Lethality Toxicity Test for Hyalella azteca.

Effects‐directed analysis (EDA) is used to identify the principal toxic components within a complex mixture using iterative steps of chemical fractionation guided by bioassay results. Bioassay selection can be limited in EDA because of the volume requirements for many standardized test methods, and therefore, a reduced‐volume acute toxicity test that also provides whole‐organism responses is beneficial. To address this need, a static, 7‐d, water‐only, reduced‐volume method (50 mL, 10 organisms) was developed for Hyalella azteca that substantially decreases the volume requirements of standard‐volume acute test exposures (200–500 mL of test solution, 15–20 organisms) while maintaining water quality and meeting control survival criteria. Standard‐ and reduced‐volume methods were compared by conducting concurrent toxicity tests with 2 inorganic toxicants (KCl and CdCl2) and 2 organic mixtures of naphthenic acid fraction components (NAFCs) to evaluate test performance. There was no difference between methods when comparing the median lethal concentrations (LC50s) for KCl and both NAFC mixtures (p > 0.05). The LC50s for CdCl2 were statistically different (p = 0.0002); however, this was not considered biologically meaningful because the difference between LC50s was <2‐fold. In conclusion, the reduced‐volume H. azteca test method generated results comparable to standard‐volume test methods and is suitable for use in situations where limited testing material is available, such as when conducting EDA. Environ Toxicol Chem 2020;39:2221–2227. © 2020 Her Majesty the Queen in Right of Canada. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. Reproduced with the permission of the Minister of Environment and Climate Change Canada.

Investigating the toxicity of naphthenic acid fraction components from oil sands process-affected water to developing fathead minnow (Pimephales promelas)

The extraction of bitumen from Alberta’s oil sands region generates large volumes of oil sands process-affected water (OSPW) that is stored in tailings ponds. Toxic constituents present in OSPW such as naphthenic acid fraction components (NAFCs) can cause adverse effects to aquatic life. Recent research has focused on the toxicity of NAFCs to highly vulnerable early life stages of fish. Here we examined the embryotoxicity of NAFCs (0-54 mg/L) extracted from OSPW to native fathead minnow (Pimephales promelas) from 1-day post-fertilization to hatch in a semi-natural setting at Queen’s University’s Biological Station. Embryo heart rate, mortality, prevalence and severity of malformations at hatch, post-hatch mass, and basal activity at hatch was examined. Embryo heart rates declined with increasing NAFC concentration, preceding pronounced exposure-response patterns of mortality and non-viable hatches. Visible malformations included cardiovascular (pericardial edema; present in 81.51% of non-viable hatches), craniofacial (reduced jaw and head size; 68.96%), myoskeletal (spinal curvatures; 60.90%), and peritoneal (yolk sac edema; 26.44%) malformations, that significantly increased in severity with increasing NAFC concentration. Fish that survived lethal concentrations displayed evidence of nervous system impairment including elevated patterns of erratic twitching. Post-hatch mass generally increased with increasing NAFC exposure, potentially as a compensatory-like response. Results of this work are the first to be reported in a semi-natural exposure setting and provide important toxicological information that will aid future policy directives for the management of OSPW in Alberta, Canada.

Can the toxicity of naphthenic acids in oil sands process-affected water be mitigated by a green photocatalytic method?

Our study evaluates the efficacy of a “green” (i.e., sustainable, recyclable, and reusable) technology to treat waste waters produced by Canada’s oil sands industry. We examined the ability of a novel advanced oxidative method—ultra-violet photocatalysis over titanium dioxide (TiO2)-coated microparticles—to reduce the toxicity of naphthenic acid fraction components (NAFC) to early life stages of the fathead minnow ( Pimephales promelas). Lengthening the duration of photocatalysis resulted in greater removal of NAFC from bioassay exposure waters; low- and high-intensity treatments reduced NAFC concentrations to about 20 and 3 mg/L (by Fourier-transformed infrared spectroscopy, FTIR), respectively. Treatments reduced the acute lethality of NAFC to fathead minnows by over half after low-intensity treatment and three-fold after high-intensity treatment. However, incomplete degradation in low-intensity treatments increased the incidence of chronic toxicity relative to untreated NAFC solutions and cardiovascular abnormalities were common even with &gt;80% of NAFC degraded. Our findings demonstrate that photocatalysis over TiO2 microparticles is a promising method for mitigating the toxicity of oil sands process-affected water-derived NAFC to fish native to the oil sands region, but the intensity of the photocatalytic treatment needs to be considered carefully to ensure adequate mineralization of toxic constituents.

Transcriptome Profiling in Larval Fathead Minnow Exposed to Commercial Naphthenic Acids and Extracts from Fresh and Aged Oil Sands Process-Affected Water.

Surface mining and extraction of oil sands results in the generation of and need for storage of large volumes of oil sands process-affected water (OSPW). More structurally complex than classical naphthenic acids (NAs), naphthenic acid fraction components (NAFCs) are key toxic constituents of OSPW, and changes in the NAFC profile in OSPW over time have been linked to mitigation of OSPW toxicity. Molecular studies targeting individual genes have indicated that NAFC toxicity is likely mediated via oxidative stress, altered cell cycles, ontogenetic differentiation, endocrine disruption, and immunotoxicity. However, the individual-gene approach results in a limited picture of molecular responses. This study shows that NAFCs, from aged or fresh OSPW, have a unique effect on the larval fathead minnow transcriptome and provides initial data to construct adverse outcome pathways for skeletal deformities. All three types of processed NAs (fresh, aged, and commercial) affected the immunome of developing fish. These gene networks included immunity, inflammatory response, B-cell response, platelet adhesion, and T-helper lymphocyte activity. Larvae exposed to both NAFCs and commercial NA developed cardiovascular and bone deformities, and transcriptomic networks reflected these developmental abnormalities. Gene networks found only in NAFC-exposed fish suggest NAFCs may alter fish cardiovascular health through altered calcium ion regulation. This study improves understanding regarding the molecular perturbations underlying developmental deformities following exposure to NAFCs.

Characterization of Athabasca lean oil sands and mixed surficial materials: Comparison of capillary electrophoresis/low-resolution mass spectrometry and high-resolution mass spectrometry.

Oil sands mining in Alberta, Canada, requires removal and stockpiling of considerable volumes of near-surface overburden material. This overburden includes lean oil sands (LOS) which cannot be processed economically but contain sparingly soluble petroleum hydrocarbons and naphthenic acids, which can leach into environmental waters. In order to measure and track the leaching of dissolved constituents and distinguish industrially derived organics from naturally occurring organics in local waters, practical methods were developed for characterizing multiple sources of contaminated water leakage. Capillary electrophoresis/positive-ion electrospray ionization low-resolution time-of-flight mass spectrometry (CE/LRMS), high-resolution negative-ion electrospray ionization Orbitrap mass spectrometry (HRMS) and conventional gas chromatography/flame ionization detection (GC/FID) were used to characterize porewater samples collected from within Athabasca LOS and mixed surficial materials. GC/FID was used to measure total petroleum hydrocarbon and HRMS was used to measure total naphthenic acid fraction components (NAFCs). HRMS and CE/LRMS were used to characterize samples according to source. The amounts of total petroleum hydrocarbon in each sample as measured by GC/FID ranged from 0.1 to 15.1mg/L while the amounts of NAFCs as measured by HRMS ranged from 5.3 to 82.3mg/L. Factors analysis (FA) on HRMS data visually demonstrated clustering according to sample source and was correlated to molecular formula. LRMS coupled to capillary electrophoresis separation (CE/LRMS) provides important information on NAFC isomers by adding analyte migration time data to m/z and peak intensity. Differences in measured amounts of total petroleum hydrocarbons by GC/FID and NAFCs by HRMS indicate that the two methods provide complementary information about the nature of dissolved organic species in a soil or water leachate samples. NAFC molecule class Ox Sy is a possible tracer for LOS seepage. CE/LRMS provides complementary information and is a feasible and practical option for source evaluation of NAFCs in water.

Toxicity of naphthenic acids to invertebrates: Extracts from oil sands process-affected water versus commercial mixtures

The toxicity of oil sands process-affected water (OSPW) has been primarily attributed to polar organic constituents, including naphthenic acid fraction components (NAFCs). Our objective was to assess the toxicity of NAFCs derived from fresh and aged OSPW, as well as commercial naphthenic acid (NA) mixtures. Exposures were conducted with three aquatic species: Hyalella azteca (freshwater amphipod), Vibrio fischeri (marine bacterium, Microtox® assay), and Lampsilis cardium (freshwater mussel larvae (glochidia)). Commercial NAs were more toxic than NAFCs, with differences of up to 30-, 4-, and 120-fold for H. azteca, V. fischeri, and L. cardium, respectively, demonstrating that commercial NAs are not reliable surrogates for assessing the toxicity of NAFCs. Differences in toxicity between species were striking for both commercial NAs and NAFCs. Overall, V. fischeri was the least sensitive and H. azteca was the most sensitive organism. Responses of V. fischeri and H. azteca to NAFC exposures were consistent (< 2-fold difference) regardless of source and age of OSPW; however, effects on L. cardium ranged 17-fold between NAFCs. NAFCs derived from fresh OSPW sources were similarly or less toxic to those from aged OSPW. Our results support the need to better characterize the complex mixtures associated with bitumen-influenced waters, both chemically and toxicologically.

Molecular responses of Walleye (Sander vitreus) embryos to naphthenic acid fraction components extracted from fresh oil sands process-affected water

Naphthenic acid fraction components (NAFCs) are constituents of oil sands process-affected water (OSPW), which is generated as a result of unconventional oil production via surface mining in the Athabasca oil sands region. NAFCs are often considered to be major drivers of OSPW toxicity to various taxa, including fishes. However, the molecular targets of these complex mixtures are not fully elucidated. Here we examined the effects in walleye (Sander vitreus) embryos after exposure to NAFCs extracted from fresh OSPW. Eleutheroembryos (exposed to 0, 4.2 or 8.3mg/L NAFCs from 1day post-fertilization to hatch) were subsampled, measured for growth and deformities, and molecular responses were assessed via real-time polymerase chain reaction (PCR). Fourteen genes were evaluated, with a focus on the aryl-hydrocarbon receptor (AhR) − cytochrome P450 pathway (arnt, cyp1a1), the oxidative stress axis (cat, gst, sod, gpx1b), apoptosis (e.g. casp3, bax and p53), growth factor signaling (e.g. insulin-like growth factors igf1, igf1b, and igf1bp), and tissue differentiation (vim). NAFC exposure was associated with an increase in the expression of cyp1a1, and a decrease in gpx1b and ribosomal protein rps40. These results indicate that NAFC effects on walleye early-life stages may be mediated through oxidative stress via pathways that include AhR.

Sensitivity of walleye (Sander vitreus) and fathead minnow (Pimephales promelas) early-life stages to naphthenic acid fraction components extracted from fresh oil sands process-affected waters

Unconventional oil production in Alberta's oil sands generates oil sands process-affected water (OSPW), which contains toxic constituents such as naphthenic acid fraction components (NAFCs). There have been few studies examining effects of NAFC exposure over long periods of early-life stage development in fish. Here we examined the effects of NAFCs extracted from OSPW to embryo-larval fathead minnow, exposed for 21 days. We compared the sensitivity of fathead minnow to walleye reared to 7 days post-hatch (18–20 days total). EC50s for hatch success, including deformities, and total survival were lower for walleye (10–11 mg/L) than fathead minnow (22–25 mg/L), with little post-hatch mortality observed in either species. NAFC exposure affected larval growth at concentrations below the EC50 in fathead minnow (total mass IC10 14–17 mg/L). These data contribute to an understanding of the developmental stages targeted by oil sands NAFCs, as well as their toxicity in a greater range of relevant taxa.

A novel solid-state fractionation of naphthenic acid fraction components from oil sands process-affected water

Various sorbent materials were evaluated for the fractionation of naphthenic acid fraction components (NAFCs) from oil sand process-affected water (OSPW). The solid phase materials include activated carbon (AC), cellulose, iron oxides (magnetite and goethite), polyaniline (PANI) and three types of biochar derived from biomass (BC-1; rice husks, BC-2; acacia low temperature and BC-3; acacia high temperature). NAFCs were semi-quantified using electrospray ionization high resolution Orbitrap mass spectrometry (ESI-MS) and the metals were assessed by inductively coupled plasma optical emission spectrometry (ICP-OES). The average removal efficacy of NAFCs by AC was 95%. The removal efficacy decreased in the following order: AC, BC-1>BC-2, BC-3, goethite>PANI>cellulose, magnetite. The removal of metals did not follow a clear trend; however, there was notable leaching of potassium by AC and biochar samples. The bound NAFCs by AC were desorbed efficiently with methanol. Methanol regeneration and recycling of AC revealed 88% removal on the fourth cycle; a 4.4% decrease from the first cycle. This fractionation method represents a rapid, cost-effective, efficient, and green strategy for NAFCs from OSPW, as compared with conventional solvent extraction.

Thermodynamic Properties of Inclusion Complexes between β-Cyclodextrin and Naphthenic Acid Fraction Components

The spectral displacement technique was used to determine the 1:1 equilibrium binding constants (K2) of the complexes formed between β-cyclodextrin and carboxylate anion guests, including either single components or mixtures in aqueous solution at variable temperatures (25–55 °C). A van’t Hoff analysis of the results afforded thermodyamic parameters (ΔH°, ΔS°, and ΔG°) of the single-component carboxylate anions and complex mixtures of carboxylic acid species, referred to as naphthenic acids (NAs). Three types of single-component examples of NAs with variable hydrogen deficiency (z) values were studied: n-octanoic (z = 0; S1), trans-4-pentylcyclohexanecarboxylic acid (z = −2; S2), and dicyclohexylacetic acid (z = −4; S3). The carboxylate anion mixtures were obtained from commercial suppliers and an industrial source obtained from oil sands process water. The estimated K2 values decrease with increasing temperature, and the standard Gibbs energy change (ΔG°) for complex formation is generally favorable (fro...

Toxicity of naphthenic acid fraction components extracted from fresh and aged oil sands process-affected waters, and commercial naphthenic acid mixtures, to fathead minnow (Pimephales promelas) embryos

Naphthenic acids (NAs) are constituents of oil sands process-affected water (OSPW). These compounds can be both toxic and persistent and thus are a primary concern for the ultimate remediation of tailings ponds in northern Alberta’s oil sands regions. Recent research has focused on the toxicity of NAs to the highly vulnerable early life-stages of fish. Here we examined fathead minnow embryonic survival, growth and deformities after exposure to extracted NA fraction components (NAFCs), from fresh and aged oil sands process-affected water (OSPW), as well as commercially available NA mixtures. Commercial NA mixtures were dominated by acyclic O2 species, while NAFCs from OSPW were dominated by bi- and tricyclic O2 species. Fathead minnow embryos less than 24h old were reared in tissue culture plates terminating at hatch. Both NAFC and commercial NA mixtures reduced hatch success, although NAFCs from OSPW were less toxic (EC50=5–12mg/L, nominal concentrations) than commercial NAs (2mg/L, nominal concentrations). The toxicities of NAFCs from aged and fresh OSPW were similar. Embryonic heart rates at 2 days post-fertilization (dpf) declined with increasing NAFC exposure, paralleling patterns of hatch success and rates of cardiovascular abnormalities (e.g., pericardial edemas) at hatch. Finfold deformities increased in exposures to commercial NA mixtures, not NAFCs. Thus, commercial NA mixtures are not appropriate surrogates for NAFC toxicity. Further work clarifying the mechanisms of action of NAFCs in OSPW, as well as comparisons with additional aged sources of OSPW, is merited.

Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Characterization of Treated Athabasca Oil Sands Processed Waters

Ultrahigh-resolution negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize Athabasca oil sands processed water (OSPW) treated by (A) coagulation flocculent with lime and bentonite, (B) coagulation flocculent with lime and bentonite followed by activated carbon, and (C) combined ozonation and ultrasonication. Treatment A was ineffective in reducing the level of total naphthenic acid fraction components [NAFCs, defined as the acid-extractable fraction of OSPWs or crude oils (CnH2n + zOwSxNy), where the values n, w, x, and y indicate the number of carbon, oxygen, sulfur, and nitrogen atoms, respectively, and z represents the hydrogen atom deficiency because of the presence of double bonds and ring formation]. Likewise, for treatment A, little or no change was observed for the double bond equivalent (DBE) distributions of the compound classes. Treatments B and C resulted in the reduction of total NAFCs by 26 ± 1.4 and 89 ± 1.1%, r...

Evaluation of biologically mediated changes in oil sands naphthenic acid composition by Chlamydomonas reinhardtii using negative-ion electrospray orbitrap mass spectrometry.

Industrial activity associated with oil-sands extraction in Canada's Athabasca region produces a variety of contaminants of concern, including naphthenic acid fraction components (NAFCs). NAFCs are a complex mixture of organic compounds that are poorly understood both in terms of their chemical composition and effects on the environment. NAFC toxicity in the unicellular green algae Chlamydomonas reinhardtii P.A.Dangeard was correlated with the presence of the algal cell wall. It was suggested that the toxicity of NAFCs in C.reinhardtii was due to surfactant effects. Surfactant-cell wall interactions are specific and governed by the compound class and structure, and by the nature of the biological material. Here, we investigate the effects of wildtype (WT) C.reinhardtii and two cell-wall mutants on specific classes of NAFCs when growing cultures were treated with a 100mg·L(-1) solution of NAFCs. Changes in the NAFC composition in the media were examined using high resolution mass spectrometry over a period of 4d. Algal mediated changes in the NAFCs were limited to specific classes of NAFCs. In particular, the removal of large, classical naphthenic acids, with a double bond equivalent of 8, was observed in WT C.reinhardtii cultures. The observed algal mediated changes in NAFC composition would have been masked by low resolution mass spectrometry and highlight the importance of this tool in examining bioremediation of complex mixtures of NAFCs.

Atmospheric Pressure Photoionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Characterization of Tunable Carbohydrate-Based Materials for Sorption of Oil Sands Naphthenic Acids

Synthetically engineered copolymers are receiving growing attention for sorption and possible degradation of components in oil sands processed water (OSPW). β-Cyclodextrin (β-CD) copolymers, for example, have been shown in recent studies of electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to adsorb oil sands naphthenic acid fraction components (NAFCs). Herein, we report complementary results for atmospheric pressure photoionization (APPI) for characterization of NAFCs in OSPW samples following sorption with cyclodextrin-based copolymers. The materials investigated were β-CD-cross-linked with three different types of diisocyanates, namely, (i) 4,4′-dicyclohexylmethane diisocyanate, (ii) 4,4′-diphenylmethane diisocyanate, and (iii) 1,4-phenylene diisocyanate. The APPI studies revealed variable sorption for a complementary range of NAFCs with compound classes not detected by ESI. For example, sorption was observed for new classes of NAFCs: HC, N1O1, N1O2, ...