Acid-extractable Organics Research Articles

Anaerobic biodegradation of surrogate naphthenic acids

Surface bitumen extraction from the Alberta's oil sands region generates large settling basins known as tailings ponds. The oil sands process-affected water (OSPW) stored in these ponds contain solid and residual bitumen-associated compounds including naphthenic acids (NAs) that can potentially be biodedgraded by indigenous tailings microorganisms. While the biodegradation of some NAs is known to occur under aerobic conditions, little is understood about anaerobic NA biodegradation even though tailings ponds are mainly anoxic. Here, we investigated the potential for anaerobic NA biodegradation by indigenous tailings microorganisms. Enrichment cultures were established from anoxic tailings that were amended with 5 single-ringed surrogate NAs or acid-extractable organics (AEO) from OSPW and incubated under nitrate-, sulfate-, iron-reducing, and methanogenic conditions. Surrogate NA depletion was observed under all anaerobic conditions tested to varying extents, correlating to losses in the respective electron acceptor (sulfate or nitrate) or the production of predicted products (Fe(II) or methane). Tailings-containing cultures incubated under the different electron-accepting conditions resulted in the enrichment and putative identification of microbial community members that may function in metabolizing surrogate NAs under the various anoxic conditions. In addition, more complex NAs (in the form of AEO) was observed to drive sulfate and iron reduction relative to controls. Overall, this study has shown that simple surrogate NAs can be biodegraded under a variety of anoxic conditions, a key first step in understanding the potential anaerobic metabolism of NAs in oil sands tailings ponds and other industrial wastewaters.

Solar photocatalytic degradation of naphthenic acids in oil sands process-affected water.

Bitumen mining in the Canadian oil sands creates large volumes of oil sands process-affected water (OSPW), the toxicity of which is due in part to naphthenic acids (NAs) and other acid extractable organics (AEO). The objective of this work was to evaluate the potential of solar photocatalysis over TiO2 to remove AEO from OSPW. One day of photocatalytic treatment under natural sunlight (25 MJ/m(2) over ∼14 h daylight) eradicated AEO from raw OSPW, and acute toxicity of the OSPW toward Vibrio fischeri was eliminated. Nearly complete mineralization of organic carbon was achieved within 1-7 day equivalents of sunlight exposure, and degradation was shown to proceed through a superoxide-mediated oxidation pathway. High resolution mass spectrometry (HRMS) analysis of oxidized intermediate compounds indicated preferential degradation of the heavier and more cyclic NAs (higher number of double bond equivalents), which are the most environmentally persistent fractions. The photocatalyst was shown to be recyclable for multiple uses, and thus solar photocatalysis may be a promising "green" advanced oxidation process (AOP) for OSPW treatment.

Biostimulation of Oil Sands Process-Affected Water with Phosphate Yields Removal of Sulfur-Containing Organics and Detoxification.

The ability to mitigate toxicity of oil sands process-affected water (OSPW) for return into the environment is an important issue for effective tailings management in Alberta, Canada. OSPW toxicity has been linked to classical naphthenic acids (NAs), but the toxic contribution of other acid-extractable organics (AEOs) remains unknown. Here, we examine the potential for in situ bioremediation of OSPW AEOs by indigenous algae. Phosphate biostimulation was performed in OSPW to promote the growth of indigenous photosynthetic microorganisms and subsequent toxicity and chemical changes were determined. After 12 weeks, the AEO fraction of phosphate-biostimulated OSPW was significantly less toxic to the fission yeast Schizosaccharomyces pombe than unstimulated OSPW. Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) analysis of the AEO fraction in phosphate-biostimulated OSPW showed decreased levels of SO3 class compounds, including a subset that may represent linear arylsulfonates. A screen with S. pombe transcription factor mutant strains for growth sensitivity to the AEO fraction or sodium dodecylbenzenesulfonate revealed a mode of toxic action consistent with oxidative stress and detrimental effects on cellular membranes. These findings demonstrate a potential algal-based in situ bioremediation strategy for OSPW AEOs and uncover a link between toxicity and AEOs other than classical NAs.

Trace analysis of total naphthenic acids in aqueous environmental matrices by liquid chromatography/mass spectrometry-quadrupole time of flight mass spectrometry direct injection

A rapid and sensitive liquid chromatography quadrupole time of flight method has been established for the determination of total naphthenic acid concentrations in aqueous samples. This is the first methodology that has been adopted for routine, high resolution, high throughput analysis of total naphthenic acids at trace levels in unprocessed samples. A calibration range from 0.02 to 1.0μgmL−1 total Merichem naphthenic acids was validated and demonstrated excellent accuracy (97–111% recovery) and precision (1.9% RSD at 0.02μgmL−1). Quantitative validation was also demonstrated in a non-commercial oil sands process water (OSPW) acid extractable organics (AEOs) fraction containing a higher percentage of polycarboxylic acid isomers than the Merichem technical mix. The chromatographic method showed good calibration linearity of ≥0.999 RSQ to 0.005μgmL−1 total naphthenic acids with a precision <3.1% RSD and a calculated detection limit of 0.0004μgmL−1 employing Merichem technical mix reference material. The method is well suited to monitoring naturally occurring and industrially derived naphthenic acids (and other AEOs) present in surface and ground waters in the vicinity of mining developments. The advantage of the current method is its direct application to unprocessed environmental samples and to examine natural naphthenic acid isomer profiles. It is noted that where the isomer profile of samples differs from that of the reference material, results should be considered semi-quantitative due to the lack of matching isomer content. The fingerprint profile of naphthenic acids is known to be transitory during aging and the present method has the ability to adapt to monitoring of these changes in naphthenic acid content. The method's total ion scan approach allows for data previously collected to be examined retrospectively for specific analyte mass ions of interest. A list of potential naphthenic acid isomers that decrease in response with aging is proposed and a quantitative assay of an adamantane carboxylic acid is reported.

Enhanced characterization of oil sands acid-extractable organics fractions using electrospray ionization-high-resolution mass spectrometry and synchronous fluorescence spectroscopy.

The open pit oil sands mining operations north of Fort McMurray, Alberta, Canada, are accumulating tailings waste at a rate approximately equal to 4.9 million m(3) /d. Naphthenic acids are among the most toxic components within tailings to aquatic life, but structural components have largely remained unidentified. In the present study, electrospray ionization high-resolution mass spectrometry (ESI-HRMS) and synchronous fluorescence spectroscopy (SFS) were used to characterize fractions derived from the distillation of an acid-extractable organics (AEO) mixture isolated from oil sands process-affected water (OSPW). Mean molecular weights of each fraction, and their relative proportions to the whole AEO extract, were as follows: fraction 1: 237 Da, 8.3%; fraction 2: 240 Da, 23.8%; fraction 3: 257 Da, 26.7%; fraction 4: 308 Da, 18.9%; fraction 5: 355 Da, 10.0%. With increasing mean molecular weight of the AEO fractions, a concurrent increase occurred in the relative abundance of nitrogen-, sulfur-, and oxygen-containing ions, double-bond equivalents, and degree of aromaticity. Structures present in the higher-molecular-weight fractions (fraction 4 and fraction 5) suggested the presence of heteroatoms, dicarboxyl and dihydroxy groups, and organic acid compounds with the potential to function as estrogens. Because organic acid compositions become dominated by more recalcitrant, higher-molecular-weight acids during natural degradation, these findings are important in the context of oil sands tailings pond water remediation.

In situ biodegradation of naphthenic acids in oil sands tailings pond water using indigenous algae–bacteria consortium

In this study, the biodegradation of total acid-extractable organics (TAOs), commonly called naphthenic acids (NAs), was investigated. An indigenous microbial culture containing algae and bacteria was taken from the surface of a tailings pond and incubated over the course of 120days. The influence of light, oxygen and the presence of indigenous algae and bacteria, and a diatom (Navicula pelliculosa) on the TAO removal rate were elucidated. The highest biodegradation rate was observed with bacteria growth only (without light exposure) with a half-life (t1/2) of 203days. The algae–bacteria consortium enhanced the detoxification process, however, bacterial biomass played the main role in toxicity reduction. Principal component analysis (PCA) conducted on FT-IR spectra, identified functional groups and bonds (representing potential markers for biotransformation of TAOs) as follows: hydroxyl, carboxyl and amide groups along with CH, arylH, arylOH and NH bonds.

Power generation and oil sands process-affected water treatment in microbial fuel cells

Oil sands process-affected water (OSPW), a product of bitumen isolation in the oil sands industry, is a source of pollution if not properly treated. In present study, OSPW treatment and voltage generation were examined in a single chamber air–cathode microbial fuel cell (MFC) under the effect of inoculated carbon source and temperature. OSPW treatment with an anaerobic sludge-inoculated MFC (AS-MFC) generated 0.55±0.025V, whereas an MFC inoculated with mature-fine tailings (MFT-MFC) generated 0.41±0.01V. An additional carbon source (acetate) significantly improved generated voltage. The voltage detected increased to 20–23% in MFCs when the condition was switched from ambient to mesophilic. The mesophilic condition increased OSPW treatment efficiency in terms of lowering the chemical oxygen demand and acid-extractable organics. Pyrosequencing analysis of microbial consortia revealed that Proteobacteria were the most abundant in MFCs and microbial communities in the AS-MFC were more diverse than those in the MFT-MFC.

Biodegradation of oil sands process affected water in sequencing batch reactors and microbial community analysis by high-throughput pyrosequencing

Two sequencing batch reactors (SBR) were constructed and filled with different inocula of activated sludge (AS) and mature fine tailings (MFT) to treat oil sands process-affected water (OSPW). The COD was reduced by 82% in the AS-SBR and 43% in the MFT-SBR during phase I using 10% OSPW and 90% synthetic wastewater as reactor feed. However, COD removal reached 12% and 20% in the AS-SBR and the MFT-SBR, respectively, when 100% raw OSPW was fed into the reactors. Maximum removal of acid-extractable organics (AEO) was 8.7% and 16.6% in the AS-SBR and the MFT-SBR, respectively with a hydraulic retention time of one day. Pyrosequencing analysis revealed that Proteobacteria was the dominant phylum and beta- and gamma-Proteobacteria were dominant classes in both reactors. Evidence of a microbial community change was observed when influent raw OSPW was switched from 50 to 100%. More significant changes in the AS-SBR community were detected.

Profiling Oil Sands Mixtures from Industrial Developments and Natural Groundwaters for Source Identification

The objective of this study was to identify chemical components that could distinguish chemical mixtures in oil sands process-affected water (OSPW) that had potentially migrated to groundwater in the oil sands development area of northern Alberta, Canada. In the first part of the study, OSPW samples from two different tailings ponds and a broad range of natural groundwater samples were assessed with historically employed techniques as Level-1 analyses, including geochemistry, total concentrations of naphthenic acids (NAs) and synchronous fluorescence spectroscopy (SFS). While these analyses did not allow for reliable source differentiation, they did identify samples containing significant concentrations of oil sands acid-extractable organics (AEOs). In applying Level-2 profiling analyses using electrospray ionization high resolution mass spectrometry (ESI-HRMS) and comprehensive multidimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF/MS) to samples containing appreciable AEO concentrations, differentiation of natural from OSPW sources was apparent through measurements of O2:O4 ion class ratios (ESI-HRMS) and diagnostic ions for two families of suspected monoaromatic acids (GC × GC-TOF/MS). The resemblance between the AEO profiles from OSPW and from 6 groundwater samples adjacent to two tailings ponds implies a common source, supporting the use of these complimentary analyses for source identification. These samples included two of upward flowing groundwater collected <1 m beneath the Athabasca River, suggesting OSPW-affected groundwater is reaching the river system.

Potential for in situ chemical oxidation of acid extractable organics in oil sands process affected groundwater

The process of bitumen extraction from oil sands in Alberta, Canada leads to an accumulation of toxic acid-extractable organics (AEOs) in oil sands process water (OSPW). Infiltration of OSPW from tailings ponds and from their retaining sand dykes and subsequent transport towards surface water has occurred. Given the apparent lack of significant natural attenuation of AEOs in groundwater, remediation may be required. This laboratory study evaluates the potential use of unactivated persulfate and permanganate as in situ oxidation agents for remediation of AEOs in groundwater. Naphthenic acids (NAs; CnH2n+zO2), which are a component of the acutely toxic AEOs, were degraded by both oxidants in OSPW samples. Permanganate oxidation yielded some residual dissolved organic carbon (DOC) whereas persulfate mineralized the AEO compounds with less residual DOC. Acid-extractable organics from oxidized OSPW had essentially no Microtox toxicity.

Characterization and Quantification of Mining-Related “Naphthenic Acids” in Groundwater near a Major Oil Sands Tailings Pond

The high levels of acid extractable organics (AEOs) containing naphthenic acids (NAs) found in oil sands process-affected waters (OSPW) are a growing concern in monitoring studies of aquatic ecosystems in the Athabasca oil sands region. The complexity of these compounds has substantially hindered their accurate analysis and quantification. Using a recently developed technique which determines the intramolecular carbon isotope signature of AEOs generated by online pyrolysis (δ(13)Cpyr), natural abundance radiocarbon, and high resolution Orbitrap mass spectrometry analyses, we evaluated the sources of AEOs along a groundwater flow path from a major oil sands tailings pond to the Athabasca River. OSPW was characterized by a δ(13)Cpyr value of approximately -21‰ and relatively high proportions of O₂ and O₂S species classes. In contrast, AEO samples located furthest down-gradient from the tailings pond and from the Athabasca River were characterized by a δ(13)Cpyr value of around -29‰, a greater proportion of highly oxygenated and N-containing compound classes, and a significant component of nonfossil and, hence, non-bitumen-derived carbon. The groundwater concentrations of mining-related AEOs determined using a two end-member isotopic mass balance were between 1.6 and 9.3 mg/L lower than total AEO concentrations, implying that a less discriminating approach to quantification would have overestimated subsurface levels of OSPW. This research highlights the need for accurate characterization of "naphthenic acids" in order to quantify potential seepage from tailings ponds.

Coupling bioelectricity generation and oil sands tailings treatment using microbial fuel cells

In this study, four dual-chambered microbial fuel cells (MFC1-4) were constructed and filled with different ratios of mature fine tailings and oil sands process-affected water to test the feasibility of MFCs to simultaneously generate electricity and treat oil sands tailings. After 800 h of operation, the maximum voltage was observed in MFC4 at 0.726 V with 1.2kΩ external resistance loaded. The maximum power density reached 392 ± 15 mW/m(2) during the 1,700 h of MFC4 operation. With continuous electricity generation, MFC4 removed 27.8% of the total COD, 81.8% of the soluble COD and 32.9% of the total acid extractable organics. Moreover, effective removal of eight heavy metals, includes 97.8% of (78)Se, 96.8% of Ba, 94.7% of (88)Sr, 81.3% for (66)Zn, 77.1% of (95)Mo, 66.9% of (63)Cu, 44.9% of (53)Cr and 32.5% of Pb, was achieved.

Rapid assessment of the toxicity of oil sands process-affected waters using fish cell lines

Rapid and reliable toxicity assessment of oil sands process-affected waters (OSPW) is needed to support oil sands reclamation projects. Conventional toxicity tests using whole animals are relatively slow, costly, and often subjective, while at the same time requiring the sacrifice of test organisms as is the case with lethal dosage/concentration assays. A nonlethal alternative, using fish cell lines, has been developed for its potential use in supporting oil sands reclamation planning and to help predict the viability of aquatic reclamation models such as end-pit lakes. This study employed six fish cell lines (WF-2, GFSk-S1, RTL-W1, RTgill-W1, FHML, FHMT) in 24 h viability assays for rapid fluorometric assessment of cellular integrity and functionality. Forty-nine test water samples collected from the surface of oil sands developments in the Athabasca Oil Sands deposit, north of Fort McMurray, Alberta, Canada, were evaluated in blind. Small subsample volumes (8 ml) were mixed with 2 ml of 5× concentrated exposure media and used for direct cell exposures. All cell line responses in terms of viability as measured by Alamar blue assay, correlated well with the naphthenic acids (NA) content in the samples (R (2) between 0.4519 and 0.6171; p<0.0001) when data comparisons were performed after the bioassays. NA or total acid-extractable organics group has been shown to be responsible for most of the acute toxicity of OSPW and our results further corroborate this. The multifish cell line bioassay provides a strong degree of reproducibility among tested cell lines and good relative sensitivity of the cell line bioassay as compared to available in vivo data that could lead to cost effective, high-throughput screening assays.

The impacts of ozonation on oil sands process-affected water biodegradability and biofilm formation characteristics in bioreactors

To examine the effects of the ozonation process (as an oxidation treatment for water and wastewater treatment applications) on microbial biofilm formation and biodegradability of organic compounds present in oil sands process-affected water (OSPW), biofilm reactors were operated continuously for 6weeks. Two types of biofilm substrate materials: polyethylene (PE) and polyvinylchloride (PVC), and two types of OSPW—fresh and ozonated OSPWs—were tested. Endogenous microorganisms, in OSPW, quickly formed biofilms in the reactors. Without ozonation, the bioreactor (using endogenous microorganisms) removed 13.8% of the total acid-extractable organics (TAO) and 18.5% of the parent naphthenic acids (NAs) from fresh OSPW. The combined ozonation and biodegradation process removed 87.2% of the OSPW TAO and over 99% of the OSPW parent NAs. Further UPLC/HRMS analysis showed that NA biodegradability decreased as the NA cyclization number increased. Microbial biofilm formation was found to depend on the biofilm substrate type.

Petroleum coke adsorption as a water management option for oil sands process-affected water

Water is integral to both operational and environmental aspects of the oil sands industry. A water treatment option based on the use of petroleum coke (PC), a by-product of bitumen upgrading, was examined as an opportunity to reduce site oil sands process-affected water (OSPW) inventories and net raw water demand. Changes in OSPW quality when treated with PC included increments in pH levels and concentrations of vanadium, molybdenum, and sulphate. Constituents that decreased in concentration after PC adsorption included total acid-extractable organics (TAO), bicarbonate, calcium, barium, magnesium, and strontium. Changes in naphthenic acids (NAs) speciation were observed after PC adsorption. A battery of bioassays was used to measure the OSPW toxicity. The results indicated that untreated OSPW was toxic towards Vibrio fischeri and rainbow trout. However, OSPW treated with PC at appropriate dosages was not acutely toxic towards these test organisms. Removal of TAO was found to be an adsorption process, fitting the Langmuir and Langmuir–Freundlich isotherm models. For TAO concentrations of 60mg/L, adsorption capacities ranged between 0.1 and 0.46mg/g. This study demonstrates that freshly produced PC from fluid cokers provides an effective treatment of OSPW in terms of key constituents' removal and toxicity reduction.

Adsorption of Acid Extractable Oil Sands Tailings Organics onto Raw and Activated Oil Sands Coke

The accumulation of organic contaminants in process-affected (PA) water represents an environmental liability for oil sands operators. Oil sands coke is a promising adsorbent for removing dissolved organic carbon (DOC), which includes toxic acid-extractable oil sands tailings organics (AEOSTO) found in PA water. The ability of raw and activated delayed and fluid coke to remove DOC and AEOSTO from PA water was assessed. Treatment with 5 g/L of activated delayed and fluid coke removed 91% of DOC and 92% of AEOSTO at levels of 36 mg/L and 60 mg/L, respectively. Heavy metal leaching of vanadium at 5.9 mg/L was observed for a 5 g/L application of activated delayed coke, representing a challenge to the approach. Microtox testing indicated that higher carbon doses of activated cokes were effective in reducing toxic the biological response caused by organic compounds; however, exposure to heavy metals increased the toxic effect with time. The proposed methodology should be coupled with an inorganic treatment technique for complete oil sands tailings water treatment.

Steroidal Aromatic ‘Naphthenic Acids’ in Oil Sands Process-Affected Water: Structural Comparisons with Environmental Estrogens

The large volumes, acute toxicity, estrogenicity, and antiandrogenicity of process-affected waters accruing in tailings ponds from the operations of the Alberta oil sands industries pose a significant task for environmental reclamation. Synchronous fluorescence spectra (SFS) suggest that oil sands process-affected water (OSPW) may contain aromatic carboxylic acids, which are among the potentially environmentally important toxicants, but no such acids have yet been identified, limiting interpretations of the results of estrogenicity and other assays. Here we show that multidimensional comprehensive gas chromatography-mass spectrometry (GCxGC-MS) of methyl esters of acids in an OSPW sample produces mass spectra consistent with their assignment as C(19) and C(20) C-ring monoaromatic hydroxy steroid acids, D-ring opened hydroxy and nonhydroxy polyhydrophenanthroic acids with one aromatic and two alicyclic rings and A-ring opened steroidal keto acids. High resolution MS data support the assignment of several of the so-called 'O3' species. When fractions of distilled, esterified, OSPW acid-extractable organics were examined, the putative aromatics were mainly present in a high boiling fraction; when examined by argentation thin layer chromatography, some were present in a fraction with a retardation factor between that of the methyl esters of synthetic monoalicyclic and monoaromatic acids. Ultraviolet absorption spectra of these fractions indicated the presence of benzenoid moieties. SFS of model octahydro- and tetrahydrophenanthroic acids produced emissions at the characteristic excitation wavelengths observed in some OSPW extracts, consistent with the postulations from ultraviolet spectroscopy and mass spectrometry data. We suggest the acids originate from extensive biodegradation of C-ring monoaromatic steroid hydrocarbons and offer a means of differentiating residues at different biodegradation stages in tailings ponds. Structural similarities with estrone and estradiol imply that such compounds may account for some of the environmental estrogenic activity reported in OSPW acid-extractable organics and naphthenic acids.

Naphthenic acids speciation and removal during petroleum-coke adsorption and ozonation of oil sands process-affected water

The Athabasca Oil Sands industry produces large volumes of oil sands process-affected water (OSPW) as a result of bitumen extraction and upgrading processes. Constituents of OSPW include chloride, naphthenic acids (NAs), aromatic hydrocarbons, and trace heavy metals, among other inorganic and organic compounds. To address the environmental issues associated with the recycling and/or safe return of OSPW into the environment, water treatment technologies are required. This study examined, for the first time, the impacts of pretreatment steps, including filtration and petroleum-coke adsorption, on ozonation requirements and performance. The effect of the initial OSPW pH on treatment performance, and the evolution of ozonation and its impact on OSPW toxicity and biodegradability were also examined. The degradation of more than 76% of total acid-extractable organics was achieved using a semi-batch ozonation system at a utilized ozone dose of 150 mg/L. With a utilized ozone dose of 100 mg/L, the treated OSPW became more biodegradable and showed no toxicity towards Vibrio fischeri. Changes in the NA profiles in terms of carbon number and number of rings were observed after ozonation. The filtration of the OSPW did not improve the ozonation performance. Petroleum-coke adsorption was found to be effective in reducing total acid-extractable organics by a 91%, NA content by an 84%, and OSPW toxicity from 4.3 to 1.1 toxicity units. The results of this study indicate that the combination of petroleum-coke adsorption and ozonation is a promising treatment approach to treat OSPW.

Salting-out effects on the characterization of naphthenic acids from Athabasca oil sands using electrospray ionization

There is growing interest in the mass spectrometric characterization of oil sands acids present in natural waters and contaminated soils. This interest stems from efforts to isolate the principal toxic components of oil sands acid extractable organics in aquatic environment. Salting-out effects are demonstrated for nanospray ionization mass spectra of Athabasca oil sands acid extractable organics (naphthenic acids), using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The differences in spectra obtained for the sodium naphthenates in dichloromethane/acetonitrile cosolvents compared to spectra obtained in the absence of saturated sodium chloride salts, are used here as a surrogate to indicate the more bioavailable or toxic components in natural waters. Whereas, monocarboxylic compounds (CnH2n+ZO2) were prevalent in the Z =−4, −6, and −12 (2, 3 and 6-ring naphthenic acids respectively) family in the carbon number range of 13 to 19 in the dichloromethane/acetonitrile cosolvent systems, salting-out effects resulted in a general enhancement of Z =−4 species, relative to others. Likewise, the shift in relative intensities of species containing O1, O3, O4, O2S and O3S was dramatic for systems with and without saturated salts present. The O4 and O3S species for example, were prevalent in the dichloromethane/acetonitrile cosolvent but were non-detected in the presence of saturated salts. Interactions of oil sands acids with salts are expected to occur in oil sands processed waters and natural saline waters. As evident by the distribution of species observed, salting-out effects will play a major role in limiting the bioavailability of oil sands acids in aquatic systems.

Naphthenic acids and other acid-extractables in water samples from Alberta: What is being measured?

There is increasing international interest in naphthenic acids (NAs, classical formula C nH 2n + Z O 2) found in the oil sands from Alberta, Canada and in petroleum from around the world. The complexity of NAs poses major analytical challenges for their quantification and characterization. We used ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS) to probe the make up of NAs from various sources by searching for peaks corresponding to the formula C nH 2n + Z O x, for combinations of n = 8 to 30, Z = 0 to −12, and x = 2 to 5. The sources included three commercial NAs preparations, and the acid-extractable organics from eight oil sand process-affected waters (OSPW) and from six surface fresh waters. Extracts from OSPW contained between 1 and 7% sulfur. The mass spectra showed between 300 and 1880 peaks, with > 99% of the peaks having m/z between 145 and 600. In most cases, < 20% of the peaks were assigned as classical NAs (x = 2) and oxy-NAs (x = 3 to 5). The classical NAs from the OSPW were predominantly Z = −4 and −6, whereas those from the fresh waters were mainly Z = 0, with palmitic and stearic acids being the major components in the fresh waters. Remarkably, when the peak abundances were considered, < 50% of the total abundance could be assigned to the classical and oxy-NAs. Thus, > 50% of the compounds in the extracts of OSPW were not “naphthenic acids”. Based on these findings, it appears that the term “naphthenic acids”, which has been used to describe the toxic extractable compounds in OSPW, should be replaced by a term such as "oil sands tailings water acid-extractable organics (OSTWAEO)". Classical and oxy-NAs are components of OSTWAEO, but this term would not be as misleading as “naphthenic acids”.