Comparison of high- and low-resolution electrospray ionization mass spectrometry for the analysis of naphthenic acid mixtures in oil sands process water

The oil sands regions of Northern Alberta, Canada, contain an estimated 1.7 trillion barrels of oil in the form of bitumen, representing the second largest deposit of crude oil in the world. A rapidly expanding industry extracts surface-mined bitumen using alkaline hot water, resulting in large volumes of oil sands process water (OSPW) that must be contained on site due to toxicity. The toxicity has largely been attributed to naphthenic acids (NAs), a complex mixture of naturally occurring aliphatic and (poly-)alicyclic carboxylic acids. Research has increasingly focused on the environmental fate and remediation of OSPW NAs, but an understanding of these processes necessitates an analytical method that can accurately characterize and quantify NA mixtures. Here we report results of an interlaboratory comparison for the analysis of pure commercial NAs and environmental OSPW NAs using direct injection electrospray ionization mass spectrometry (ESI-MS) and high-pressure liquid chromatography/high-resolution mass spectrometry (HPLC/HRMS). Both methods provided very similar characterization of pure commercial NA mixture; however, the m/z selectivity of HPLC/HRMS was essential to prevent substantial false-positive detections and misclassifications in OSPW NA mixtures. For a range of concentrations encompassing those found in OSPW (10-100 mg/L), both methods produced linear response, although concentrations of commercial NAs above 50 mg/L resulted in slight non-linearity by HPLC/HRMS. A three-fold lower response factor for total OSPW NAs by HPLC/HRMS was largely attributable to other organic compounds in the OSPW, including hydroxylated NAs, which may explain the substantial misclassification by ESI-MS. For the quantitative analysis of unknown OSPW samples, both methods yielded total NA concentrations that correlated with results from Fourier transform infrared (FTIR), but the coefficients of determination were not high. Quantification by either MS method should therefore be considered semi-quantitative at best, albeit either method has substantial value in environmental fate experiments where relative concentration changes are the desired endpoints rather than absolute concentrations.     

Preliminary fingerprinting of Athabasca oil sands polar organics in environmental samples using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

There is a growing need to develop analytical methods that can distinguish compounds found within industrially derived oil sands process water (OSPW) from those derived from natural weathering of oil sands deposits. This is a difficult challenge as possible leakage beyond tailings pond containments will probably be in the form of mixtures of water-soluble organics that may be similar to those leaching naturally into aquatic environments. We have evaluated the potential of negative ion electrospray ionization high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) for comparing oil sands polar organics from tailing ponds, interceptor wells, groundwater, river and lake surface waters. Principal component analysis was performed for all species observed. which included the O(2) class (often assumed to be monocarbxoylic naphthenic acids) along with a wide range of other species including humic substances in the river and lake samples: O(n) where n=1-16; NO(n) and N(2)O(n) where n=1-13; and O(n)S and O(n)S(2) where n=1-10 and 1-8, respectively. A broad range of species was investigated because classical naphthenic acids can be a small fraction of the 'organics' detected in the polar fraction of OSPW, river water and groundwater. Aquatic toxicity and environmental chemistry are attributed to the total organics (not only the classical naphthenic acids). The distributions of the oil sands polar organics, particularly the sulfur-containing species, O(n)S and O(n)S(2), may have potential for distinguishing sources of OSPW. The ratios of species containing O(n) along with nitrogen-containing species: NO(n), and N(2)O(n), were useful for differentiating organic components derived from OSPW from those found in river and lake waters. Further application of the FTICRMS technique for a diverse range of OSPW of varying ages and composition, as well as the surrounding groundwater wells, may be critical in assessing whether leakage from industrial sources to natural waters is occurring.     

Determination of C(80) tetra-acid content in calcium naphthenate deposits

A method is described which allows to determine the content of the so-called C(80) tetra-acid molecules (TA) in calcium naphthenate deposits. The method consists of four steps. Molecules present in the deposit are dissolved in a mixture of toluene and 2-butanol after an acidic treatment. All acid molecules are then selectively extracted and concentrated by a solid-phase extraction (SPE) method. After derivatization of acids into their naphthacyl esters to increase the sensitivity of the detection, TA is separated and detected by reversed-phase HPLC with UV detection. We have checked that all the steps are quantitative and the method appears selective. The TA content can be determined in presence of other naphthenic acids. Using this methodology we have determined the TA content in three calcium naphthenate deposits from different oil fields. It appears that these deposits have a similar TA concentration between 28 and 41% (w/w).     

Identification of individual acids in a commercial sample of naphthenic acids from petroleum by two-dimensional comprehensive gas chromatography/mass spectrometry

The identification of most individual members of the complex mixtures of carboxylic acids found in petroleum ('naphthenic acids') has eluded chemists for over a century; they remain unresolved by conventional gas chromatographic methods. Recently, however, we successfully used two-dimensional comprehensive gas chromatography/mass spectrometry to identify numerous individual diamondoid acids in the naphthenic acids of oil sands process water (OSPW). We have now applied the same methods to a study of a mixture of commercially available naphthenic acids originally refined from petroleum. The results confirm that OSPW and refined petroleum contain very different distributions of acids, as noted previously, although some of the diamondoid acids recently identified in OSPW were detectable in both. Rather, two-dimensional comprehensive gas chromatography/time-of-flight mass spectrometry (GCxGC/ToF-MS) of the methyl esters of the petroleum acids and of numerous acids synthesised for comparison showed that the former comprised mainly C(8-18) straight-chain, methyl-branched, acyclic isoprenoid, cyclohexyl and isomeric octahydropentalene, perhydroindane and perhydronaphthalene (decalin) acids. Some of the latter bicyclic acids occurred as both the non-alkyl-substituted isomers and the bicyclic ethanoic and propanoic acids. Also present in minor quantities was a range of phenyl carboxylic and substituted phenyl alkanoic acids, and traces of non-acids, including trimethylnaphthalenes, again identified by comparison with the synthesised compounds. These results represent some of the first identifications of multiple individual naphthenic acids in commercial mixtures originating from petroleum and provide a basis for future studies of the petroleum geochemistry, toxicities and environmental impacts of the acids. Furthermore, characterisation of the acids will be important for improving the understanding of the role of naphthenic acids in petroleum engineering, particularly for oil pipeline deposition problems.     

Naphthenic acids as indicators of crude oil biodegradation in soil,based on semi‐quantitative electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Crude oil contaminated soil cores were collected from a basin that contained oily solids left from three decades of oil production. Hydrocarbon biomarker analyses revealed that the soil extracts were moderately biodegraded compared with the non‐degraded source oil. The degree of biodegradation also decreased with core depth (7 cm to 1 m). These data were correlated to compositional changes observed in acidic NSO‐compounds that were selectively ionized and mass resolved by negative ion electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT‐ICR MS). Among the NSO‐compounds ionized, the increase in naphthenic acid concentration (e.g., acyclic and alicyclic carboxylic acids) best correlated with the increase in biodegradation (e.g., from non‐degraded to moderately degraded) as determined by the hydrocarbon biomarker analyses. The most biodegraded surface extracts (7 cm) exhibited an 80% increase in the abundance of acids relative to the source oil. Use of an internal standard allowed the semi‐quantitative determination of the total naphthenic acid concentration, which decreased significantly (P < 0.05) with soil depth. Furthermore, the shift to higher double bond equivalents (DBEs), from acyclic to alicyclic acids, indicated that the increase in acids in the soil extracts was predominately due to biotic processes. This work demonstrates the potential of ESI FT‐ICR MS as a semi‐quantitative tool to monitor the production of naphthenic acids during crude oil biotransformation in the environment. Copyright © 2008 John Wiley & Sons, Ltd.     

气相色谱/化学电离-质谱法检测石油中的环烷酸

采用柱色谱和阴离子交换树脂法分离出原油200~420 ℃馏分中的羧酸,通过红外光谱仪检验分离效果及分离出的羧酸的类型。采用气相色谱及以异丁烷为反应气的化学电离(CI)质谱法分析分离出的羧酸。在对其结构进行推断和归类中,以纯脂肪酸、环烷酸以及分离出的石油酸的CI质谱数据为基础,结合环烷酸z系列通式CnH2n+zO2,分别得到了不同碳数的脂肪酸及一环、二环……六环环烷酸的分析结果。结果表明,含酸原油中的羧酸主要是环烷酸,相对分子质量分布为170~510,碳数分布为C10~C35,其中双环、三环环烷酸含量较高。     

气相色谱-质谱法测定变压器油正构烃含量

环烷基油是生产高性能变压器油的优质原料,以此为基础油生产的变压器油其凝点一般都小于-40℃,而变压器油在使用过程中对凝点(即低温流动性)有着非常高的要求,凝点的高低直接影响着油品的物理化学性能及电器性能。而油品的低温流动性与其组成中的正构烃(蜡)含量密切相关,据有关     

Ultrahigh‐resolution mass spectrometry of simulated runoff from treated oil sands mature fine tailings

There is interest in using mature fine tailings (MFT) in reclamation strategies of oil sands mining operations. However, simulated runoff from different dried MFT treatments is known to have elevated levels of salts, toxic ions, and naphthenic acids, and alkaline pH and it is phytotoxic to the emergent macrophyte, common reed (Phragmites australis). Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS) of the acidic species in the runoff confirmed that the distribution of oil sands naphthenic acids and associated oil sand acids was dependent on the MFT treatment. Furthermore, FT‐ICR MS studies of the acidic species in hydroponic systems revealed that there was no plant‐mediated change in the electrospray ionization mass spectra of the runoff. O_o‐containing species were prevalent (>90%), O_oS_s were predominant (<10% relative abundance), and O_oN_n were least abundant in all runoff water samples. O_oS_s species were predominant in all the samples investigated. The heteroatomic classes present in runoff water at greater than 1% relative abundance include: O₂N₁, O₃N₁, O₂, O₂S₁ O₃, O₃S₁, O₄, O₄S₁, O₅, O₅S₁, O₆, O₆S₁, O₇, O₇S₁, O₈ and O₈S₁. Assuming the same response factor for all O_o species, the O₄ class, presumably dicarboxylic acids, was generally more prevalent than the O₂ class in all samples. The O₂ class is indicative of classical naphthenic acids. However, dicarboxylic acids will form negative ions more readily than the monocarboxylic acids as there are two acidic hydrogens available for formation of these species. Copyright © 2010 John Wiley & Sons, Ltd.     

Langmuir films of naphthenic acids at different pH and electrolyte concentrations

Langmuir films of naphthenic acids at different pH and electrolyte concentrations are reported. The polydisperse naphthenic acids were commercially available, while two single-component naphthenic acids [5#(H)-cholanoic acid and 1-naphthalenepentanoic acid, decahydro- (9CI)] were synthesized. 1-naphthalenepentanoic acid, decahydro- is too water-soluble to form stable monolayers. 5#(H)-Cholanoic acid and Fluka naphthenic acid form stable films when cations are present in the aqueous subphase. At lower pH the cations are less influential since the naphthenic acids are not protolysed and metal naphthenates cannot be formed. pK_a^s for 5#(H)-cholanoic acid is determined to 5.65. The micellisation of the naphthenates at high pH is described.     

Novel Determination of Organic Acids in Diesel and Motor Oil by Ion Chromatography

A robust analytical method is required for the determination of low-molecular weight organic acids, which are potential causes of refinery and internal combustion engine corrosion. The ion chromatographic method developed in this study allows the determination of acetic acid and formic acid in diesel oil mixtures with a motor oil volume fraction of up to 10%. The hydrophobic matrix is automatically removed in-line through a matrix elution step with organic solvent and nonaqueous anion-exchange analyte extraction. Acetic acid and formic acid, as the smallest and most acidic aliphatic naphthenic acids, were determined. Gradient anion-exchange chromatography on high-capacity columns in combination with suppressed conductivity detection allowed their selective and sensitive determination. Typical recovery values were from 82 to 107% for each acid in the matrices evaluated with reproducibility less than 5% for acid fortified samples.     

Analysis of 'ARN' naphthenic acids by high temperature gas chromatography and high performance liquid chromatography

Examination by high temperature GC (HTGC) of the methyl esters of the so-called 'ARN' naphthenic acids from crude oils of North Sea UK, Norwegian Sea and West African oilfields revealed the distributions of resolved 4-8 ring C80 tetra acids and trace amounts of other acids. Whilst all three oils contained apparently the same major acids, the proportions of each differed, possibly reflecting the growth temperatures of the archaebacteria from which the acids are assumed to have originated. The structures of the 4, 5, 7 and 8 ring acids are tentatively assigned by comparison with the known 6 ring acid and related natural products and an HPLC method for the isolation of the individual acids is described. ESI-MS of individual acids isolated by preparative HPLC established the elution order of the 4-8 ring acids on the HPLC and HTGC systems and revealed the presence of previously unreported acids tentatively identified as C81 and C82 7 and 8 ring analogues.     

Molecular dynamics studies of the stability of water/n-heptane interfaces with adsorbed naphthenic acids

The mechanism by which naphthenic acids stabilize water/oil interfaces has received extensive attention because of its industrial relevancy. In this work, we employed a molecular dynamics simulation to study its molecular origin. Two models were adopted, wherein naphthenic acid coverage of water/n-heptane interfaces, both spherical and flat, was hypothesized, respectively. It was found that the coalescence of two water clusters is entirely attributed to the diffusional motion of the components involved which requires the initial departure of the naphthenic acid molecules from the interface so that a water bridge can form. The naphthenic acids not only act as a steric barrier but also reduce the mobility of the water and n-heptane molecules making the formation of the water bridge rather difficult. In fact, our results show that the coalescence of two water clusters fully covered by naphthenic acid molecules is a low-probability event even at evaluated temperatures. In addition, the results from the flat interface models suggest that the emulsion stability is weakly dependent on the molecular weight of the naphthenic acids utilized. Order parameter calculations reveal liquid-crystal-like ordering of naphthenic acids at the water/n-heptane interfaces. All these observations are consistent with the corresponding experimental observations. The present work also suggests that the mobility of naphthenic acids is considerably enhanced with more n-heptane molecules present outside a water droplet. However, in such a case, coalescence could not occur as the water clusters are far apart from each other.     

A derivatisation and liquid chromatography/electrospray ionisation multistage mass spectrometry method for the characterisation of naphthenic acids

Naphthenic acids (NAs) are partially uncharacterised complex mixtures of carboxylic acids, resulting from the microbial oxidation of petroleum hydrocarbons. They are associated with the fouling of pipelines and process equipment in oil production and with corrosion in oil refineries. As by-products of the rapidly expanding oil (tar) sands industries, NAs are also pollutants and have proved to be toxic to a range of organisms. They also have important beneficial uses as fungicides, tyre additives and, paradoxically, also in the manufacture of corrosion inhibitors. These features make the characterisation of NAs an important goal for analytical chemists. Here we describe the synthesis of amide derivatives of NAs for characterisation by liquid chromatography/electrospray ionisation multistage mass spectrometry (LC/ESI-MS(n)). The method was applied to commercially available carboxylic acids, novel synthetic NAs, commercial NAs refined from crude oils, crude oil NAs and Athabasca oil sands NAs. In addition to confirming the number of alicyclic rings and length of alkyl side chain substituents (confirming information from existing methods), the MS(n) results provided further structural information. Most important of these was the finding that bi- to polycyclic acids containing ethanoate side chains, in addition to alkyl substituents, were widespread amongst the oil and oil sands NAs. The latter NAs are known end members of the beta-oxidation of NAs with even carbon number alkanoate chains. Since such NA mixtures are toxic, they should be targets for bioremediation. Bioremediation of NAs can also be monitored better by application of the methods described herein.     

Isolation and Characterization of Naphthenic Acids from a Metal Naphthenate Deposit: Molecular Properties at Oil‐Water and Air‐Water Interfaces

Naphthenic acids from a West African metal naphthenate deposit have been isolated and characterized by infrared (IR), nuclear magnetic resonance (NMR), and Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS). The sample has been shown to comprise a narrow group of 4‐protic naphthenic acids of molecular weight ～1230 Da. The determined mass of 1230.0627 Da suggests a compound with the elemental composition C₈₀H₁₄₂O₈. The NMR data show no sign of carbon‐carbon multiple bonds. Hence, the elemental composition indicates the presence of six saturated hydrocarbon rings. The naphthenic acids have proved to be highly oil‐water (o/w) interfacially active. On elevation of the pH from 5.6 to 9.0, interfacial activity increases gradually due to a higher degree of dissociation of the carboxylic groups. At pH 9.0, the interfacial tension (IFT) between water and toluene‐hexadecane (1–9 vol.) is lowered by ～40 mN/m at concentrations of only 0.0050–0.010 mM naphthenic acid. The time rate of decrease of the IFT (dγ/dt) is also concentration‐dependent, and a well‐defined IFT is attained at long observation periods.

The C₈₀ naphthenic acids form relatively unstable Langmuir monolayers. The stability decreases further with increasing pH as more monomers become dissociated and dissolve into the aqueous phase. The stability is altered upon addition of calcium ions into the subphase due to formation of calcium naphthenate at the surface. In the undissociated state, the acids have a molecular area of ～160 Å²/molecule in the noninteracting region. The high area reflects an extended molecular structure comprising four carboxylic head groups, which are likely to be separated by hydrocarbon chains.     

A semi‐quantitative approach for the rapid screening and mass profiling of naphthenic acids directly in contaminated aqueous samples

We report the use of a direct sampling, online analytical approach for the determination of acid extractable naphthenic acids in complex aqueous samples, known as condensed phase membrane introduction mass spectrometry (CP‐MIMS). The technique employs a capillary hollow fibre semi‐permeable membrane probe configured for immersion into a pH adjusted sample. A continuously flowing methanol acceptor phase transfers naphthenic acids to an electrospray ionization source, operated in negative ion mode, whereupon they are analysed by mass spectrometry as [M–H]^? ions. High‐resolution mass spectrometry is used to characterize the influence of sample pH on membrane transport of multiple components of complex naphthenic acid mixtures. We demonstrate the use of CP‐MIMS for semi‐quantitative analysis of real‐world samples using selected ion monitoring and full scan mass spectra at unit mass resolution. The technique has also been employed to continuously monitor the temporal evolution in the mass profile and concentrations of individual naphthenic acid isomer classes in heterogeneous solutions during adsorption processes. Copyright © 2015 John Wiley & Sons, Ltd.     

Degradation of a model naphthenic acid, cyclohexanoic acid, by vacuum UV (172 nm) and UV (254 nm)/H2O2

The mechanism of hydroxyl radical initiated degradation of a typical oil sands process water (OSPW) alicyclic carboxylic acid was studied using cyclohexanoic acid (CHA) as a model compound. By use of vacuum ultraviolet irradiation (VUV, 172 nm) and ultraviolet irradiation in the presence of hydrogen peroxide UV(254 nm)/H(2)O(2), it was established that CHA undergoes degradation through a peroxyl radical. In both processes the decay of the peroxyl radical leads predominantly to the formation of 4-oxo-CHA, and minor amounts of hydroxy-CHA (detected only in UV/H(2)O(2)). In UV/H(2)O(2), additional 4-oxo-CHA may also have been formed by direct reaction of the oxyl radical with H(2)O(2). The oxyl radical can be formed during decay of the peroxyl-CHA radical or reaction of hydroxy-CHA with hydroxyl radical. Oxo- and hydroxy-CHA further degraded to various dihydroxy-CHAs. Scission of the cyclohexane ring was also observed, on the basis of the observation of acyclic byproducts including heptadioic acid and various short-chain carboxylic acids. Overall, the hydroxyl radical induced degradation of CHA proceeded through several steps, involving more than one hydroxyl radical reaction, thus efficiency of the UV/H(2)O(2) reaction will depend on the rate of generation of hydroxyl radical throughout the process. In real applications to OSPW, concentrations of H(2)O(2) will need to be carefully optimized and the environmental fate and effects of the various degradation products of naphthenic acids considered.     

Evaluation of the analyses of tert-butyldimethylsilyl derivatives of naphthenic acids by gas chromatography-electron impact mass spectrometry

Naphthenic acids are a complex mixture of carboxylic acids with the general formula CnH(2n+Z)O2 and they are natural, toxic components of crude oils. GC-MS analyses of tert-butyldimethylsilyl esters of naphthenic acids are used to estimate component distribution within naphthenic acids mixtures. Our evaluations of the GC-MS method showed that ions from column bleed erroneously appear as C14 Z = -4 acids and that correcting for heavy isotopes of C and Si do not significantly affect ion distribution plots. Overall, the GC-MS method appears to overestimate the relative proportion of low-molecular-mass acids.     

全氢菲在分子筛催化剂上环烷环开环反应的研究

在小型固定流化床(FFB)装置上考察了Y与ZSM-5分子筛催化剂以及Y分子筛催化剂上温度、剂油比对全氢菲裂化环烷环开环反应的影响。结果表明,全氢菲在分子筛催化剂上通过环烷环开环反应生成环己烷、十氢萘等单环或双环环烷烃;单环或双环环烷烃进一步侧链断裂生成2-甲基戊烷、甲基己烷等异构烷烃等,异构化生成二甲基环戊烷、甲乙基环戊烷等烷基环戊烷,氢转移生成苯、甲苯、二甲苯等烷基苯,进行深度氢转移反应生成萘、烷基萘等双环芳烃;另外,全氢菲也会通过脱氢缩合生成菲、芘等三环以上芳烃甚至焦炭等。由于扩散和吸附性能的影响,其裂化开环反应的选择性在Y分子筛催化剂上比在ZSM-5分子筛催化剂上高。因此,全氢菲环烷环开环与脱氢缩合反应的相对比例(s(NRO)/s(DHC))在Y分子筛催化剂上较高;在Y分子筛催化剂上,温度为475~550 ℃、剂油比为3.0~9.0,反应温度升高或者剂油比增加,双分子氢转移以及脱氢缩合反应增强,导致环烷环开环反应产物选择性降低。     

Aquatic plant‐derived changes in oil sands naphthenic acid signatures determined by low‐, high‐ and ultrahigh‐resolution mass spectrometry

Mass spectrometry is a common tool for studying the fate of complex organic compound mixtures in oil sands processed water (OSPW), but a comparison of low‐, high‐ (～10 000), and ultrahigh‐resolution (～400 000) instrumentation for this purpose has not previously been made. High‐resolution quadrupole time‐of‐flight mass spectrometry (QTOF MS) and ultrahigh‐resolution Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS), with negative‐ion electrospray ionization, provided evidence for the selective dissipation of components in OSPW. Dissipation of oil sands naphthenic acids (NAs with general formula C_nH_2n+zO₂ where n is the number of carbon atoms, and Z is zero or a negative even number describing the number of rings) was masked (by components such as fatty acids, O₃, O₅, O₆, O₇, SO₂, SO₃, SO₄, SO₅, SO₆, and NO₄ species) at low resolution (1000) when using a triple quadrupole mass spectrometer. Changes observed in the relative composition of components in OSPW appear to be due primarily to the presence of plants, specifically cattails (Typha latifolia) and their associated microorganisms. The observed dissipation included a range of heteratomic species containing O₂, O₃, O₄, and O₅, present in Athabasca oil sands acid extracts. For the heteratomic O₂ species, namely naphthenic acids, an interesting structural relationship suggests that low and high carbon number NAs are dissipated by the plants preferentially, with a minimum around C₁₄/C₁₅. Other heteratomic species containing O₆, O₇, SO₂, SO₃, SO₄, SO₅, SO₆, and NO₄ appear to be relatively recalcitrant to the cattails and were not dissipated to the same extent in planted systems. Copyright © 2009 John Wiley & Sons, Ltd.     

Improved MEUF removal of naphthenic acids from produced water

Naphthenic acids are naturally occurring organics in produced waters from oil recovery operations. In principle, these contaminants can be removed using micellar-enhanced ultrafiltration (MEUF), which is an effective technique for the removal of organic contaminants from water streams. In this work, we show that the amphiphilic nature of the naphthenic acids contributed to decreasing the critical micelle concentration (CMC) of cetylpyridinium chloride (CPC), a widely used surfactant in MEUF. This reduction in CMC allowed a decrease in the CPC dosage required to attain certain removal of the organics, and hence, improved the performance of traditional MEUF as a result of reducing back contamination and potential fouling of the membrane. The effect of CPC feed concentration, and the concentration and carbon number of the naphthenic acids on permeate flux, recovery ratio and percent rejection of CPC and naphthenic acids were explored over a range of trans-membrane pressure. The MEUF setup employed hydrophilic polyacrylonitrile (PAN) hollow fiber membrane with 13 kDa MWCO, since it allowed for high permeate flux and contaminant rejection.