Determination of 18 phenolic compounds in water by gas chromatography-tandem mass spectrometry coupled with solid phase extraction

doi:10.3724/SP.J.1123.2020.01016

Abstract

Abstract:

At present, the kinds and the hazards of phenolic compounds in water were unclear. Research aimed at methods for the simultaneous detection of multiple phenolic compounds is still in its nascent stages. It is necessary to establish a method for the simultaneous determination of phenolic compounds in water. An analytical method was developed for the simultaneous determination of the 18 phenolic compounds in water by gas chromatography-tandem mass spectrometry (GC-MS/MS) coupled with solid phase extraction (SPE). The phenolic compounds in water were enriched and separated on an SPE column. The optimal pretreatment method was established by optimizing the chromatographic and mass spectrometric conditions. The effects of the initial pH of the water sample, type of eluting solvent, and dosage of the washing solution were investigated. Then, the 18 phenolic compounds in the water samples were determined. The optimal pretreatment extraction conditions were determined to be as follows:final pH of water sample, 3.0; eluting solvent, ethyl acetate (10 mL); and elution rate, 1 mL/min. The phenolic compounds enriched and purified by SPE were finally determined by GC-MS/MS with an electrospray ionization (EI) source. The phenolic compounds were then quantitatively analyzed by the external standard method. The average recoveries of the 18 phenolic compounds were in the range of 51.7%-117.3% at four spiked levels, and the relative standard deviations (RSDs) were in the range of 3.1%-7.4%. The limits of detections (LODs) were 0.04-0.6 μg/L. Good linear relationships were observed for the phenolic compounds in their corresponding concentration ranges. The developed method was applied to determine the phenolic compounds in six kinds of water samples from rivers and lakes, domestic water, and process water. Fifteen of the phenolic compounds were detected, but 4-nonylphenol, 3-methyl-4-nitrophenol, and 2-methyl-4, 6-dinitrophenol were not. Moreover, bisphenol A, 2, 4, 6-tribromophenol, and 2, 4-dibromophnol had the highest contents of 49.4 μg/L. The contents and kinds of phenolic compounds in the rivers and lakes were highest. However, the contents of phenolic compounds in the domestic water were adverse compared with the rivers and lakes, in accord with National Standard GB 8537-2008. As opposed to traditional analytical methods, the present method is characterized by simple operation without derivative or the need for anhydrous sodium sulfate for water removal, as well as high sensitivity, good stability, and reliability. The establishment of this method has important theoretical and practical significance for the development of standards and for the control of residue phenolic residue levels in water.

Key words: gas chromatography tandem mass spectrometry (GC-MS/MS), solid phase extraction (SPE), determination, phenolic compounds, water

LI Yang, ZHANG Shufen, XING Jiali, YING Lu, CHENG Hai, ZHENG Ruihang, MAO Lingyan, LI Hesheng. Determination of 18 phenolic compounds in water by gas chromatography-tandem mass spectrometry coupled with solid phase extraction[J]. Chinese Journal of Chromatography, 2020, 38(8): 953-960.

Figures/Tables 6

References

1	Ji X H . Environmental Protection and Circular Economy, 2018, 38(3): 58
1	纪晓红. 环境保护与循环经济, 2018, 38(3): 58
2	Yang C X , Yang X Q , Yan X P . Chinese Journal of Chromatography, 2019, 37(8): 824
2	杨成雄, 杨雪清, 严秀平. 色谱, 2019, 37(8): 824
3	Luo E L , Wang J , Li Y L . Modern Food, 2017 (6): 70
3	罗尔伦, 王杰, 黎永乐. 现代食品, 2017 (6): 70
4	Lv Y Z , Zhao J L , Yao L , et al. Environmental Chemistry, 2019, 38(3): 443
4	吕银知, 赵建亮, 姚理, et al. 环境化学, 2019, 38(3): 443
5	Jin D , Mai J H , Peng X H , et al. Journal of Instrumental Analysis, 2015, 34(1): 80
5	金铎, 麦锦欢, 彭旭辉, et al. 分析测试学报, 2015, 34(1): 80
6	Li H H , Han X , Si Y C . Guangdong Chemical Industry, 2018, 45(1): 108
6	李惠惠, 韩香, 司玉昌. 广东化工, 2018, 45(1): 108
7	Jing Y , He D . Chemical Enterprise Management, 2017 (11): 217
7	景阳, 贺调. 化工管理, 2017 (11): 217
8	Li X Q. [MS Dissertation]. Nanjing: Southeast University, 2016
8	李晓晴. [硕士学位论文].南京: 东南大学, 2016
9	Joaquin H F , Erika R . J Chromatogr A, 2019, 1607: 460442
10	Luo X L , Zheng H , Zhang Z H , et al. Microchem J, 2018, 137: 148
11	Mu S . Public Communication of Science & Technology, 2012, 4(21): 100
11	穆肃. 科技传播, 2012, 4(21): 100
12	Liu M , Zhu H Y , Gan P S , et al. Chinese Journal of Health Laboratory Technology, 2017, 27(2): 163
12	刘苗, 朱惠扬, 甘平胜, et al. 中国卫生检验杂志, 2017, 27(2): 163
13	Zhou H , Zhang Y Q , Liu Z , et al. The Administration and Technique of Environmental Monitoring, 2017, 29(4): 53
13	周浩, 张瑶琴, 刘中, et al. 环境监测管理与技术, 2017, 29(4): 53
14	Zhao H , Ai S Y , Ding K Y , et al. Journal of Inspection and Quarantine, 2015, 25(6): 66
14	赵晗, 艾仕云, 丁葵英, et al. 检验检疫学刊, 2015, 25(6): 66
15	Wu Y J. [MS Dissertation]. Xinxiang: Henan Normal University, 2016
15	吴玉军. [硕士学位论文].新乡: 河南师范大学, 2016
16	Jing J , Jiang H , Li F , et al. Applied Chemical Industry, 2016, 45(2): 320
16	荆静, 姜恒, 李飞, et al. 应用化工, 2016, 45(2): 320
17	Zhao C C , Wang C , Guo W J , et al. Chinese Journal of Analytical Chemistry, 2018, 46(8): 1306
17	赵陈晨, 王超, 郭文建, et al. 分析化学, 2018, 46(8): 1306
18	Zhang L , Zhang Y T , Zhang C L , et al. Journal of Chinese Mass Spectrometry Society, 2018, 39(5): 623
18	张莉, 张永涛, 张辰凌, et al. 质谱学报, 2018, 39(5): 623
19	Hou B , Zhang W Z , Han Y H , et al. Chemical Reagents, 2019, 41(8): 802
19	侯博, 张万智, 韩永辉, et al. 化学试剂, 2019, 41(8): 802
20	Yu S X , Chai J R , Ruan Z , et al. Journal of Hygiene Research, 2010, 39(6): 770
20	俞苏霞, 柴剑荣, 阮征, et al. 卫生研究, 2010, 39(6): 770
21	Liang C Z , Dong S Y , Li L , et al. Physical Testing and Chemical Analysis Part B: Chemical Analysis, 2013, 49(3): 349
21	梁存珍, 董思远, 李丽, et al. 理化检验(化学分册), 2013, 49(3): 349
22	Zhang S Q , He G , Zhang L , et al. Journal of Southwest China Normal University, 2011, 36(4): 50
22	张淑琼, 何刚, 张丽, et al. 西南师范大学学报, 2011, 36(4): 50
23	Yuan H F , Zhu Z H , Xu X , et al. Science & Technology Information, 2012 (33): 248
23	袁荷芳, 朱振华, 徐霞, et al. 科技资讯, 2012 (33): 248
24	Xu J L , Yan X J , Xu N J , et al. Journal of Fisheries of China, 2004 (1): 100
24	徐继林, 严小军, 徐年军, et al. 水产学报, 2004 (1): 100
25	Ye C P , Feng J , Li W Y , et al. Journal of Taiyuan University of Technology, 2010, 41(5): 661
25	叶翠平, 冯杰, 李文英, et al. 太原理工大学学报, 2010, 41(5): 661
26	Qiu X Z , Guo H S , Chen B Q , et al. Chinese Journal of Chromatography, 2013, 31(8): 809
26	丘秀珍, 郭会时, 陈步青, et al. 色谱, 2013, 31(8): 809
27	Yu Y . Periodical of Ocean University of China, 2016, 46(8): 64
27	余颖. 中国海洋大学学报, 2016, 46(8): 64

Compound	Retention time/min	Quantitative ion (m/z)	Qualitative ions (m/z)	pK_a
pK_a values were calculated at 25 ℃.
2-Bromophenol (2-BP)	6.26	174.00	65.00, 93.00, 172.00	8.45
2-Nitrophenol	7.29	139.00	65.00, 109.00	7.23
3-Methyl-2-nitrophenol	8.98	136.00	77.00, 153.00	7.00
4-Methyl-2-nitrophenol	9.28	153.00	77.00, 154.00	7.45
5-Methyl-2-nitrophenol	9.50	153.00	77.00, 123.00	7.41
4-Bromophenol (4-BP)	9.94	172.00	65.00, 93.00, 174.00	9.37
2, 4-Dibromophenol (2, 4-DBP)	10.99	252.00	143.00, 250.00, 254.00	7.86
2, 6-Dibromophenol (2, 6-DBP)	11.49	252.00	143.00, 250.00, 254.00	6.67
3-Nitrophenol	13.09	139.00	65.00, 93.00	8.36
2, 4-Dinitrophenol (DNP)	13.50	184.00	107.00, 154.00	4.09
4-Nitrophenol (AR)	14.10	139.00	65.00, 109.00	7.15
Octylphenol (OP)	15.03	135.00	107.00, 136.00, 206.00	10.15
3-Methyl-4-nitrophenol	15.38	136.00	77.00, 153.00	7.39
2-Methyl-4, 6-dinitrophenol	15.48	121.00	105.00, 198.00	4.31
2, 6-Dimethyl-4-nitrophenol	15.95	167.00	91.00, 137.00	7.19
2, 4, 6-Tribromophenol (2, 4, 6-TBP)	16.15	332.00	62.00, 143.00, 330.00	6.34
Nonylphenol (NP)	21.61	107.00	108.00, 220.00	10.20
Bisphenol A (BPA)	27.40	213.00	119.00, 218.00	10.30

Compound	Retention time/min	Quantitative ion (m/z)	Qualitative ions (m/z)	pK_a
pK_a values were calculated at 25 ℃.
2-Bromophenol (2-BP)	6.26	174.00	65.00, 93.00, 172.00	8.45
2-Nitrophenol	7.29	139.00	65.00, 109.00	7.23
3-Methyl-2-nitrophenol	8.98	136.00	77.00, 153.00	7.00
4-Methyl-2-nitrophenol	9.28	153.00	77.00, 154.00	7.45
5-Methyl-2-nitrophenol	9.50	153.00	77.00, 123.00	7.41
4-Bromophenol (4-BP)	9.94	172.00	65.00, 93.00, 174.00	9.37
2, 4-Dibromophenol (2, 4-DBP)	10.99	252.00	143.00, 250.00, 254.00	7.86
2, 6-Dibromophenol (2, 6-DBP)	11.49	252.00	143.00, 250.00, 254.00	6.67
3-Nitrophenol	13.09	139.00	65.00, 93.00	8.36
2, 4-Dinitrophenol (DNP)	13.50	184.00	107.00, 154.00	4.09
4-Nitrophenol (AR)	14.10	139.00	65.00, 109.00	7.15
Octylphenol (OP)	15.03	135.00	107.00, 136.00, 206.00	10.15
3-Methyl-4-nitrophenol	15.38	136.00	77.00, 153.00	7.39
2-Methyl-4, 6-dinitrophenol	15.48	121.00	105.00, 198.00	4.31
2, 6-Dimethyl-4-nitrophenol	15.95	167.00	91.00, 137.00	7.19
2, 4, 6-Tribromophenol (2, 4, 6-TBP)	16.15	332.00	62.00, 143.00, 330.00	6.34
Nonylphenol (NP)	21.61	107.00	108.00, 220.00	10.20
Bisphenol A (BPA)	27.40	213.00	119.00, 218.00	10.30

Compound	Linear range/(μg/L)	Linear equation	R²	MDL/(μg/L)
y: peak area; x: mass concentration, μg/L.
2-BP	0.5-20	y=7.030×10⁶x	0.9948	0.40
2-Nitrophenol	0.5-20	y=3.841×10⁶x	0.9933	0.30
3-Methyl-2-nitrophenol	0.5-20	y=1.417×10⁶x	0.9986	0.20
4-Methyl-2-nitrophenol	0.5-20	y=3.968×10⁶x	0.9992	0.20
5-Methyl-2-nitrophenol	0.5-20	y=4.331×10⁶x	0.9971	0.10
4-BP	0.5-20	y=3.878×10⁶x	0.9989	0.40
2, 4-DBP	0.5-20	y=4.368×10⁶x	0.9984	0.20
2, 6-DBP	0.5-20	y=4.749×10⁶x	0.9980	0.10
3-Nitrophenol	0.5-20	y=8.893×10⁵x	0.9994	0.10
DNP	5.0-200	y=1.868×10⁵x	0.9917	0.60
AR	5.0-200	y=3.107×10⁶x	0.9992	0.20
OP	5.0-200	y=4.532×10⁴x	0.9979	0.50
3-Methyl-4-nitrophenol	5.0-200	y=2.678×10⁶x	0.9997	0.20
2-Methyl-4, 6-dinitrophenol	5.0-200	y=1.373×10⁶x	0.9926	0.50
2, 6-Dimethyl-4-nitrophenol	0.5-20	y=4.016×10⁶x	0.9989	0.20
2, 4, 6-TBP	0.5-20	y=2.447×10⁶x	0.9983	0.40
NP	0.5-20	y=2.938×10⁶x	0.9998	0.06
BPA	0.5-20	y=2.275×10⁷x	0.9939	0.04

Compound	Linear range/(μg/L)	Linear equation	R²	MDL/(μg/L)
y: peak area; x: mass concentration, μg/L.
2-BP	0.5-20	y=7.030×10⁶x	0.9948	0.40
2-Nitrophenol	0.5-20	y=3.841×10⁶x	0.9933	0.30
3-Methyl-2-nitrophenol	0.5-20	y=1.417×10⁶x	0.9986	0.20
4-Methyl-2-nitrophenol	0.5-20	y=3.968×10⁶x	0.9992	0.20
5-Methyl-2-nitrophenol	0.5-20	y=4.331×10⁶x	0.9971	0.10
4-BP	0.5-20	y=3.878×10⁶x	0.9989	0.40
2, 4-DBP	0.5-20	y=4.368×10⁶x	0.9984	0.20
2, 6-DBP	0.5-20	y=4.749×10⁶x	0.9980	0.10
3-Nitrophenol	0.5-20	y=8.893×10⁵x	0.9994	0.10
DNP	5.0-200	y=1.868×10⁵x	0.9917	0.60
AR	5.0-200	y=3.107×10⁶x	0.9992	0.20
OP	5.0-200	y=4.532×10⁴x	0.9979	0.50
3-Methyl-4-nitrophenol	5.0-200	y=2.678×10⁶x	0.9997	0.20
2-Methyl-4, 6-dinitrophenol	5.0-200	y=1.373×10⁶x	0.9926	0.50
2, 6-Dimethyl-4-nitrophenol	0.5-20	y=4.016×10⁶x	0.9989	0.20
2, 4, 6-TBP	0.5-20	y=2.447×10⁶x	0.9983	0.40
NP	0.5-20	y=2.938×10⁶x	0.9998	0.06
BPA	0.5-20	y=2.275×10⁷x	0.9939	0.04

Compound	Spiked levels/(μg/L)	Recoveries/%	RSDs/%
2-BP	1, 5, 10, 20	71.6, 85.9, 96.3, 101.7	5.4, 4.7, 2.7, 3.1
2-Nitrophenol	1, 5, 10, 20	61.7, 75.9, 85.6, 95.7	9.6, 8.1, 6.2, 5.8
3-Methyl-2-nitrophenol	1, 5, 10, 20	72.7, 81.4, 84.6, 92.7	7.3, 5.3, 4.2, 3.0
4-Methyl-2-nitrophenol	1, 5, 10, 20	69.7, 76.5, 89.1, 94.3	6.9, 4.4, 4.7, 3.6
5-Methyl-2-nitrophenol	1, 5, 10, 20	72.6, 82.0, 87.1, 91.7	6.2, 5.7, 3.5, 2.8
4-BP	1, 5, 10, 20	56.7, 85.7, 89.1, 98.7	4.4, 2.6, 3.7, 1.7
2, 4-DBP	1, 5, 10, 20	68.7, 73.6, 82.7, 84.3	4.2, 3.6, 2.7, 1.9
2, 6-DBP	1, 5, 10, 20	64.5, 83.2, 94.6, 101.4	5.6, 6.9, 5.5, 4.3
3-Nitrophenol	1, 5, 10, 20	65.0, 73.4, 82.6, 95.8	4.9, 3.6, 2.7, 2.3
DNP	10, 50, 100, 200	67.3, 78.4, 86.2, 110.1	6.5, 5.8, 4.8, 5.3
AR	10, 50, 100, 200	61.4, 77.8, 91.2, 114.0	6.7, 5.8, 5.6, 4.2
OP	10, 50, 100, 200	85.3, 96.7, 103.1, 117.3	5.8, 6.2, 3.8, 4.1
3-Methyl-4-nitrophenol	10, 50, 100, 200	51.7, 66.6, 89.4, 102.6	7.8, 6.7, 8.2, 5.1
2-Methyl-4, 6-dinitrophenol	10, 50, 100, 200	67.4, 86.6, 96.5, 113.5	4.4, 3.5, 3.8, 3.5
2, 6-Dimethyl-4-nitrophenol	1, 5, 10, 20	68.7, 79.6, 88.5, 94.6	8.4, 8.8, 5.2, 3.9
2, 4, 6-TBP	1, 5, 10, 20	79.0, 87.8, 93.5, 105.7	4.3, 4.6, 3.8, 2.3
NP	1, 5, 10, 20	69.5, 73.2, 81.7, 84.6	8.2, 7.6, 5.2, 4.3
BPA	1, 5, 10, 20	80.5, 92.6, 104.0, 113.5	8.9, 7.6, 3.8, 6.5