Analytical Letters

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Determination of Naphthenic Acids in Oil Sand

Processed Water by Two-Dimensional Gas
Chromatography with Quadrupole Time-of-Flight
Mass Spectrometry (2D GC-QTOFMS)

Chenyu Qian, Changgang Li, Tong Zhan, Cai Wang & Zhangmin Xiang

To cite this article: Chenyu Qian, Changgang Li, Tong Zhan, Cai Wang & Zhangmin Xiang
(2022) Determination of Naphthenic Acids in Oil Sand Processed Water by Two-Dimensional Gas
Chromatography with Quadrupole Time-of-Flight Mass Spectrometry (2D GC-QTOFMS), Analytical
Letters, 55:1, 24-31, DOI: 10.1080/00032719.2021.1912068

To link to this article: https://doi.org/10.1080/00032719.2021.1912068

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ANALYTICAL LETTERS
2022, VOL. 55, NO. 1, 24–31
https://doi.org/10.1080/00032719.2021.1912068

GAS CHROMATOGRAPHY

Determination of Naphthenic Acids in Oil Sand Processed

Water by Two-Dimensional Gas Chromatography with
Quadrupole Time-of-Flight Mass Spectrometry (2D
GC-QTOFMS)
Chenyu Qiana,b, Changgang Lic, Tong Zhanc, Cai Wanga, and Zhangmin Xiangb
a
Guangdong Key Laboratory for Innovation Development and Utilization of Forest Plant Germplasm,
College of Forestry and Landscape Architecture, South China Agricultural University, Guangzhou, China;
b
Guangdong Provincial Key Laboratory of Emergency Test for Dangerous Chemicals, Guangdong
Institute of Analysis, China National Analytical Center Guangzhou Guangdong Academy of Sciences,
Guangzhou, China; cGuangdong University of Petrochemical Technology, Maoming, China

ABSTRACT ARTICLE HISTORY

Two-dimensional gas chromatography (2D GC)–quadrupole time-of- Received 7 December 2020
flight mass spectrometry (QTOFMS) combined with derivatization Accepted 29 March 2021
was applied to determine naphthenic acids (NAs) in oil sand proc-
KEYWORDS
essed water (OSPW). Using the excellent resolution of 2D GC and
Gas chromatography-mass
mass resolution of QTOFMS with derivatization, 8 cyclohexane car- spectrometry (GC-MS);
boxylic acid isomers, 18 methylcyclohexyl carboxylic acid isomers, naphthenic acids; oil sand
and 18 methylcyclohexyl acetic acid isomers were identified. Linear processed water;
relationships across wide concentration ranges were established with quadrupole time-of-flight
correlation coefficients (R2) of 0.9995, 0.9992, and 0.9990, for cyclo- mass spectrometry
hexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, and 4- (QTOFMS); Two-dimensional
methylcyclohexane acetic acid. The precision, expressed as the rela- gas chromatography
tive standard deviation (RSD, n ¼ 5), was from 7. 7–9.5% with recov- (2D GC)
eries between 72.0% and 84.9%. This method was applied to analyze
sewage and showed high concentrations of naphthenic acids in
untreated samples.

Introduction
The oil industrial processing in Guangdong, China generates large volumes of oil sand
processed water (OSPW) that contains numerous organic compounds, including the
acid-extractable organic matter, acknowledged as naphthenic acids (NAs), which are
complex mixtures of petroleum-derived carboxylic acids (Rowland et al. 2012). These
compounds have been identified as the primary toxic chemicals in refinery wastewater
and in oil sands extraction water (Clemente and Fedorak 2005). This group of organic
acids is classically defined as the family of alkyl-substituted saturated cyclic and acyclic
carboxylic acids with general formula CnH2nþZOx, where n indicates the number of car-
bons (7 ＜ n ＜ 26); Z is zero or an even negative integer (0 ＜ –Z ＜ 18), which

CONTACT Zhangmin Xiang xiangzm@live.com Guangdong Provincial Key Laboratory of Emergency Test for
Dangerous Chemicals, Guangdong Institute of Analysis, Guangzhou 510070, China.
Supplemental data for this article is available online at https://doi.org/10.1080/00032719.2021.1912068.
ß 2021 Taylor & Francis Group, LLC
 ANALYTICAL LETTERS 25

specifies the hydrogen deficiency resulting from ring formation; and x represents the
number of oxygen atoms (Brown and Ulrich 2015; Huang et al. 2016). Concerns have
increased about effects from OSPW entering the environment (Scarlett et al. 2013). The
characterization of naphthenic acids is necessary to characterize their toxicities and
treatment methodologies (Yassine and Dabek-Zlotorzynska 2018). The composition and
individual isomers of NAs in OSPW at different locations vary considerably (Grewer
et al. 2010), making their identification and quantification a challenge.
There are many methods for naphthenic acids in oil sand processed water. NAs are
weak acidic compounds and typically separated from the OSPW matrix by liquid-liquid
extraction (Wang et al. 2013; Huang et al. 2016; Ripmeester and Duford 2019) at pH
2.0 using CH2Cl2 as the solvent (Tiwari et al. 2019). However, naphthenic acids are
presents in crude oils as salts and may not be removed (Shepherd et al. 2010). Many
studies have reported the failure of naphthenic acid extraction, which have resulted low
recovery values (Borgund et al. 2007).
OSPW samples have been characterized by high-performance liquid
chromatography – mass spectrometry (HPLC-MS) (Scott et al. 2008; Hughes et al. 2017;
Leshuk et al. 2018). HPLC is sometimes replaced by gas chromatography (GC).
However, conventional GC produces insufficient resolution of the complex mixtures
(Rowland et al. 2011). Comprehensive two-dimensional gas chromatography (2D GC)
with enhanced resolution is promising for separating and identifying individual NAs in
OSPW samples (Rowland et al. 2011). Quadrupole time-of-flight mass spectrometry
(QTOFMS) provides advantages compared to normal mass spectrometry, including
higher mass resolution and is advantageous for isomers in complex samples. In this
study, the combination of 2D GC and QTOFMS is employed for the identification of
naphthenic acids. Oil sand processed water was treated by liquid-liquid extraction and
the analytes determined by 2D GC-QTOFMS. The derivatization and the pH conditions
were also optimized.

Experimental
Chemicals and standards
The extraction solvent dichloromethane was supplied by Merck (Germany). All chemi-
cals and solvents were chromatographic grade. Standards of 4-methylcyclohexanoic acid
(98%), 4-methylcyclohexane acetic acid (97%), and cyclohexanecarboxylic acid
(99.5%) were obtained from Sigma-Aldrich (Oakville, Canada).

Sample preparation and optimization of extraction conditions

Oil sand processed water (OSPW) (total volume of 3 L) was obtained from an oil plat-
form in Maoming (Guangdong, China) in June 2019 and stored at 4  C. The raw
OSPW had a natural pH of 8.5. The 1 N hydrochloric acid was added to adjust the pH
of the samples and blanks. Each sample was acidified to between 1.0 and 7.0. All
samples including blanks were treated by liquid-liquid extraction. Naphthenic acids
(NAs) were thrice extracted by 10 mL CH2Cl2 from 20 mL of aqueous solution.
The extracted solutions were evaporated by nitrogen to a final volume of 1 mL.
26 C. QIAN ET AL.

Table 1. Determination of naphthenic acids in oil sand processed water samples by 2D GC

method (n ¼ 5).
Linear Correlation Limit of Relative
range Calibration coefficient detection Recovery standard
Standard name (ng/mL) relationship (R2) (LOD, ng/L) (%) deviation (%)
4-Methylcyclohexanecarboxylic 0.21–41.96 y ¼ 644806x þ 13430 0.9992 2.5 84.9 9.5
acid
4-Methylcyclohexane acetic 0.23–42.31 y ¼ 454243x – 219738 0.9990 3.1 72.0 8.4
acid
Cyclohexanecarboxylic acid 0.35–43.68 Y ¼ 829101x – 108557 0.9995 2.3 79.6 7.7

N,O-bis-(trimethylsilyl) trifluoroacetamide (BSTFA, Sigma-Aldrich, purity > 99.5%) and

trimethylchlorosilane (TMCS, Sigma-Aldrich, purity > 99.5%) were used for derivatiza-
tion. The preliminary experimental design variables are presented in Supporting mater-
ial Table S1. The extraction reagent and pH were first characterized. Subsequently,
derivatization reagent quantities, derivatization temperature, and contact time
were optimized.

Determination of naphthenic acids

The NA concentrations were calculated by the method of standard addition (Zhu et al.
2017). Calibration curves were prepared with standards from 0.21 to 43.68 ng/mL. The
calibration curves of the NAs were constructed according to the peak areas of the
selected quantitative ions: 4-methylcyclohexanecarboxylic acid, 199.1152; 4-methylcyclo-
hexane acetic acid, 213.1307; and cyclohexanecarboxylic acid, 185.1033. The linearities
were characterized by their correlation coefficients. The concentrations of NAs were
evaluated using the calibration relationships.

Instrumentation
Two-dimensional gas chromatography (GC  GC) system was a 7890B instrument
(Agilent, USA) with an autosampler (PAL RSI 120, CTC Technologies) and a 7250 high
resolution quadrupole time-of-flight mass spectrometer (QTOFMS) (Agilent, USA). The
instrument may generate up to 20,000 spectra/s. The 0.5 lL of sample were injected at
250  C in splitless mode. Helium (99.999%) was used as the carrier gas at a constant
flow rate of 1.2 mL/min. This gas chromatography was equipped with a solid-state
modulator (SSM, J&X Technologies SSM1800). The column used for the first-dimension
separation was a HP-5 MS (5% phenyl-95% dimethylpolysiloxane, 30 m  250 lm,
0.25 lm film, Agilent). The column in the second dimension was a DB-17 MS (50%
phenyl-50% dimethylpolysiloxane, 1.2 m  180 lm, 0.18 lm film, Agilent). The oven
temperature program included a 50  C hold for 5 min, a ramp of 4  C/min to 230  C,
and a hold for 2 min. The cold zone temperature of the solid-state modulator was
50  C, while the temperatures of the entry hot zone and exit hot zone were offset at
þ30 and þ120  C relative to oven temperature, respectively, with a maximum of 320  C
for both. The modulation period was 4 s. All samples including blanks were analyzed
using the same conditions.
 ANALYTICAL LETTERS 27

Figure 1. Two-dimensional mass chromatograms of naphthenic acids in oil sand processed water.

For the identification of naphthenic acids, SIM mode was used to integrate the chro-
matograms to obtain the signal for each with a mass accuracy of ±5 ppm.

Results and discussion

Separation of naphthenic acids by GC 3 GC
Naphthenic acid composition includes numerous isomers. Detailed distributions of the
individual components were difficult to determine by conventional one-dimensional gas
chromatography, emphasizing the necessity of the 2D GC profiles for distinguishing
isomers (Shepherd et al. 2010). The derivatized naphthenic acids were examined by
high-resolution QTOFMS and the results are shown in Figure 1. The naphthenic acid
distribution is shown in the spectra. 8 cyclohexane carboxylic acid isomers with a char-
acteristic ion of 185.0994, 18 methylcyclohexyl carboxylic acid isomers with a character-
istic ion of 199.1152, and 18 methylcyclohexyl acetic acid isomers with a characteristic
ion of 213.1306 were identified. Figure 1 shows that numerous NA isomers are present
in OSPW, showing that 2D GC-QTOFMS was superior in characterizing the individual
naphthenic acids in the samples.

Qualitative analysis
NAs generally require derivatization of the carboxy group before the gas chromato-
graphic analysis. After derivatization, the mass spectra of NAs contained clear molecular
ions that were matched with those in the NIST17 library. Figure 2 shows the NAs were
identified following derivatization by their characteristic ions. The spectra of these NAs
were similar to the library results, with relatively high match factors of 912, 934, and
28 C. QIAN ET AL.

Figure 2. Mass spectra of oil sand processed water showing naphthenic acids that were characterized
by molecular ions at (a) m/z 185.0994, (b) m/z 199.1152, and (c) m/z 213.1206.

915, respectively. The corresponding M-CH3 peaks are observed in Figure 2. Using
high-resolution molecular weights, cyclohexyl carboxylic acid at 185.0994 (C9H17O2Siþ),
methylcyclohexyl carboxylic acid at 199.1152 (C10H19O2Siþ), and methylcyclohexyl
acetic acid at 213.1307 (C10H19O2Siþ), were selected to be the characteristic ions for the
naphthenic acids.

Quantitative analysis
In order to perform accurate quantitative analysis, the naphthenic acid concentrations
were determined using the method of standard addition. Calibration curves were
obtained from the ratios of the peak areas of the targets to the peak areas of the internal
standards (Cheng et al. 2019). 4-Methylcyclohexanecarboxylic acid, 4-methylcyclohexane
acetic acid, and cyclohexanecarboxylic acid were employed as standards (Table 1). The
results showed linear relationships across wide concentration ranges. Accordingly, cor-
relation coefficients (R2) of 0.9995, 0.9992 and 0.9990 were obtained for cyclohexanecar-
boxylic acid from 0.35 to 43.68 ng/mL, 4-methylcyclohexanecarboxylic acid from 0.21 to
41.96 ng/mL, and 4-methylcyclohexane acetic acid from 0.23 to 42.31 ng/mL
(Supporting material Figure S2). The precision, expressed as the relative standard devi-
ation (RSD, n ¼ 5), was lower than 7.7% for all analytes. In addition, using the optimum
conditions, the limits of detection were 2.5, 3.1, and 2.3 ng/L for 4-methylcyclohexane-
carboxylic acid, 4-methylcyclohexane acetic acid, and cyclohexanecarboxylic acid,
respectively. The quantitative determination for naphthenic acid isomers in this study
provided good results compared to the literature (Yassine and Dabek-
Zlotorzynska 2018).

Optimization of the extraction conditions

Figure S3 (Supporting material) shows the extraction results for naphthenic acids based
on peak area using various conditions. Compared with trimethylchlorosilane, the use of
BSTFA leaded to an increase in peak area, and hence was deemed to be the optimal
derivatization reagent (Supporting material Figure S1). The extraction efficiency fol-
lowed the order pH5–7 < pH3–5 < pH1–3 < pH1 (Supporting material Figure S3), which
was consistent with a literature report (Huang et al. 2016). The optimum conditions for
derivatization were 80  C for 60 min using 200 lL of reagent.
 ANALYTICAL LETTERS 29

Table 2. Analysis of sewage (mg/kg) as mean ± standard deviation.

Analytes ID Sewage treatment A Sewage treatment B Sewage treatment C
Cyclohexyl carboxylic acid and isomers 1 0.666 ± 0.025 0.38 ± 0.088 0.164 ± 0.002
2 1.188 ± 0.016 1.49 ± 0.478 Not detected.
3 0.347 ± 0.01 0.41 ± 0.109 0.157 ± 0.002
4 9.919 ± 0.036 0.916 ± 0.284 0.5 ± 0.028
5 13.615 ± 0.651 2.161 ± 0.703 0.802 ± 0.049
6 1.347 ± 0.017 0.528 ± 0.149 0.187 ± 0.002
7 0.397 ± 0.024 0.587 ± 0.226 Not detected.
8 10.679 ± 0.686 0.948 ± 0.288 0.565 ± 0.034
Methylcyclohexyl acetic acid and isomers 1 0.95 ± 0.056 0.168 ± 0.062 0.026 ± 0.005
2 3.301 ± 0.166 0.207 ± 0.097 0.085 ± 0.005
3 3.924 ± 0.119 0.183 ± 0.092 0.099 ± 0.005
4 11.946 ± 0.356 0.504 ± 0.234 0.377 ± 0.01
5 1.425 ± 0.024 0.209 ± 0.112 0.041 ± 0.001
6 5.181 ± 0.196 0.145 ± 0.06 0.16 ± 0.01
7 0.909 ± 0.024 0.082 ± 0.037 0.02 ± 0.002
8 4.186 ± 0.109 0.319 ± 0.128 0.136 ± 0.008
9 11.293 ± 0.307 3.198 ± 0.284 0.659 ± 0.047
10 3.226 ± 0.083 0.202 ± 0.065 0.104 ± 0
11 28.833 ± 0.792 0.509 ± 0.222 1.315 ± 0.08
12 32.952 ± 0.928 0.526 ± 0.229 1.511 ± 0.092
13 23.529 ± 0.219 3.298 ± 0.128 1.345 ± 0.078
14 6.224 ± 0.298 0.721 ± 0.293 0.279 ± 0.016
15 6.227 ± 0.111 0.052 ± 0.02 0.181 ± 0.011
16 32.686 ± 0.899 1.268 ± 0.308 1.752 ± 0.138
17 5.478 ± 0.034 0.266 ± 0.111 0.175 ± 0.017
18 1.056 ± 0.027 0.013 ± 0.003 0.023 ± 0.002
Methylcyclohexyl carboxylic acid and isomers 1 4.19 ± 0.065 0.581 ± 0.041 0.607 ± 0.009
2 2.569 ± 0.057 0.579 ± 0.039 0.563 ± 0.01
3 4.653 ± 0.169 0.763 ± 0.059 0.636 ± 0.003
4 6.664 ± 0.025 0.75 ± 0.114 0.786 ± 0.122
5 6.51 ± 0.04 0.552 ± 0.014 0.673 ± 0.018
6 19.067 ± 0.133 0.68 ± 0.066 1.25 ± 0.059
7 4.795 ± 0.014 1.319 ± 0.352 0.718 ± 0.018
8 6.555 ± 0.039 0.77 ± 0.104 0.725 ± 0.001
9 7.11 ± 0.094 0.615 ± 0.054 0.693 ± 0.01
10 12.396 ± 0.199 0.778 ± 0.127 0.935 ± 0.053
11 10.968 ± 0.9 0.849 ± 0.178 1.109 ± 0.056
12 4.524 ± 0.552 0.586 ± 0.021 0.649 ± 0.02
13 4.887 ± 0.346 0.484 ± 0 0.612 ± 0.001
14 9.076 ± 0.292 0.858 ± 0.142 0.834 ± 0.029
15 4.443 ± 0.11 0.554 ± 0.027 0.619 ± 0.009
16 1.328 ± 0.09 0.554 ± 0.025 0.484 ± 0
17 3.337 ± 0.013 0.551 ± 0.002 0.583 ± 0.009
18 3.718 ± 0.063 0.779 ± 0.117 0.644 ± 0.039

Application of 2D GC -QTOFMS for the analysis of water samples

To estimate the reliability and practicability of the method, water samples from an oil
platform in Maoming were analyzed. Untreated sewage and sewage treated by disposal
processes A and B were analyzed (Table 2). Figure S4 (Supporting material) shows
untreated sewage contained variety of NAs: 183.32 mg/kg methylcyclohexyl acetic acid,
116.79 mg/kg methylcyclohexyl carboxylic acid, and 27.48 mg/kg cyclohexyl carboxylic
acid. The concentrations of naphthenic acids were significantly decreased by treatment,
with B more efficient than process A.
30 C. QIAN ET AL.

Conclusion
The 2D GC-QTOFMS was employed to determine naphthenic acids in oil sand proc-
essed water. The excellent separation by 2D GC and high mass resolution of QTOFMS
with derivatization allowed the separation of 8 cyclohexane carboxylic acid isomers, 18
methylcyclohexyl carboxylic acid isomers, and 18 methylcyclohexyl acetic acid isomers.
Linear relationships across wide concentration ranges were established with correlation
coefficients (R2) between 0.9990 and 0.9995. This method was employed to analyze sew-
age. The results indicated that the concentrations of NAs in untreated sewage was
higher than in processed samples. The developed method may provide accurate and
rapid determination of naphthenic acids in oil sand processed water.

Funding
This work was supported by the GDAS’ Project of Science and Technology Development (No.
2018GDASCX-0808 and 2019GDASYL-0105018).

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