Determination of 15 carbonyl compounds in soil using improved solid phase extraction-high performance liquid chromatography

doi:10.3724/SP.J.1123.2022.05021

Abstract

Abstract:

An improved solid phase extraction (SPE)-high performance liquid chromatography method was established to determine 15 carbonyl compounds, namely, formaldehyde (FOR), acetaldehyde (ACETA), acrolein (ACR), acetone (ACETO), propionaldehyde (PRO), crotonaldehyde (CRO), butyraldehyde (BUT), benzaldehyde (BEN), isovaleraldehyde (ISO), n-valeraldehyde (VAL), o-methylbenzaldehyde (o-TOL), m-methylbenzaldehyde (m-TOL), p-methylbenzaldehyde (p-TOL), n-hexanal (HEX), and 2,5-dimethylbenzaldehyde (DIM), in soil. The soil was ultrasonically extracted with acetonitrile, and the extracted samples were derivatized with 2,4-dinitrophenylhydrazine (2,4-DNPH) to generate stable hydrazone compounds. The derivatized solutions were cleaned using an SPE cartridge (Welchrom^® BRP) packed with N-vinylpyrrolidone/divinylbenzene copolymer. Separation was performed on an Ultimate^® XB-C18 column (250 mm×4.6 mm, 5 μm), isocratic elution was performed with acetonitrile-water (65∶35, v/v) as the mobile phase, and detection was performed at a wavelength of 360 nm. The 15 carbonyl compounds in the soil were then quantified using an external standard method. The proposed method improves the sample processing method described in the environmental standard HJ 997-2018: Soil and sediment-Determination of carbonyl compounds-High performance liquid chromatography. A series of experiments revealed the following optimal conditions for soil extraction: acetonitrile as the extraction solvent, extraction temperature of 30 ℃, and extraction time of 10 min. The results showed that the purification effect of the BRP cartridge was significantly better than that of the conventional silica-based C18 cartridge. The 15 carbonyl compounds showed good linearities, and all correlation coefficients were above 0.996. The recoveries ranged from 84.6% to 115.9%, the relative standard deviations (RSDs) ranged from 0.2% to 5.1%, and the detection limits were 0.02-0.06 mg/L. The method is simple, sensitive, and suitable for the accurate quantitative analysis of the 15 carbonyl compounds in soil specified in HJ 997-2018. Thus, the improved method provides reliable technical support for studying the residual status and environmental behavior of carbonyl compounds in soil.

Key words: solid phase extraction (SPE), high performance liquid chromatography (HPLC), carbonyl compounds, soil

CLC Number:

O658

XUE Kunpeng, YU Lingyu, REN Xingfa, TU Bingfang, CHEN Chao, XU Ting, HE Huan, HU Shuai. Determination of 15 carbonyl compounds in soil using improved solid phase extraction-high performance liquid chromatography[J]. Chinese Journal of Chromatography, 2023, 41(3): 265-273.

Figures/Tables 11

Fig. 1 Chromatograms of the 15 carbonyl compound- dinitrophenylhydrazine (DNPH) derivatives in the national standard HJ 997-2018[23] Peak identifications: 1. formaldehyde (FOR); 2. acetaldehyde (ACETA); 3. acrolein (ACR); 4. acetone (ACETO); 5. propionaldehyde (PRO); 6. crotonaldehyde (CRO); 7. butanal (BUT); 8. benzaldehyde (BEN); 9. isovaleraldehyde (ISO); 10. valeraldehyde (VAL); 11. o-tolualdehyde (o-TOL); 12. m-tolualdehyde (m-TOL); 13. p-tolualdehyde (p-TOL); 14. hexanal (HEX); 15. 2,5-dimethylbenzaldehyde (DIM).

Fig. 2 Chromatograms of 15 carbonyl compound-DNPH derivatives in the standard solution Experimental conditions: mixed standard solution of the 15 carbonyl compounds at 0.1 mg/L; separation column, Ultimate? XB-C18 (250 mm×4.6 mm, 5 μm); mobile phase: acetonitrile-water; flow rate: 1.0 mL/min; column temperature: 30 ℃; injection volume: 20 μL; detection wavelength: 360 nm.

Fig. 3 Derivative effects of different solvents on the 15 carbonyl compounds The sample solution was prepared from a 10.0 g sample spiked with a mixed standard solution of the 15 carbonyl compounds at 0.1 mg/L.Conditions: a. 100 mL of sample solution, extracted with 0.065 mol/L acetic acid sodium-acetate buffer solution, added with 4 mL pH 3.0 citric acid-sodium citrate buffer solution and 6 mL 2,4-DNPH acetonitrile solution, derivatized at 40 ℃ for 1 h; b. 100 mL of sample solution, extracted with 0.065 mol/L acetic acid-sodium acetate buffer, added with 4 mL acetonitrile and 6 mL 2,4-DNPH acetonitrile solution, derivatized at 40 ℃ for 1 h; c. 100 mL of sample solution, extracted with acetonitrile, added with 6 mL 2,4-DNPH acetonitrile solution and 1.0 mL 20% phosphoric acid solution, derivatized at 4 ℃ for 6 h.

Fig. 4 Effect of extraction solvent on the recoveries of the 15 carbonyl compounds

Fig. 5 Effect of extraction temperature on the recoveries of the 15 carbonyl compounds

Fig. 6 Effect of extraction time on the recoveries of the 15 carbonyl compounds The extracted solution was prepared from a 10.0 g sample spiked with a mixed standard solution of the 15 carbonyl compounds at 0.1 mg/L.

Table 1 Physicochemical properties of the packing materials of the three reversed-phase SPE cartridges

SPE column type	Stationary phase group	Morphology	Specific surface area/(m²/g)	Particle size/μm	Pore size/nm
C18	octadecyl	amorphous	500	40-63	4
PS-DVB	polystyrene-divinyl polymer	spherical	700	50-70	20
BRP	N-vinylpyrrolidone-divinyl polymer	spherical	700	50-70	20

Fig. 7 SEM images of three SPE cartridge packing materials a. C18; b. PS-DVB; c. BRP.

Table 2 Matrix effects of the SPE packing materials on the 15 carbonyl compounds (n=6)

Compound	C18		PS-DVB		BRP
Compound	ME/%	RSD/%	ME/%	RSD/%	ME/%	RSD/%
FOR	110.4	1.8	108.7	1.2	90.5	1.3
ACETA	125.6	3.4	129.0	3.6	115.9	3.1
ACR	113.9	2.8	110.2	2.1	102.7	4.6
ACETO	129.0	2.7	118.0	3.5	98.4	1.3
PRO	112.8	2.4	116.1	2.4	105.2	2.3
CRO	127.2	4.6	125.4	3.6	107.8	1.0
BUT	145.4	5.6	132.1	5.3	109.7	2.2
BEN	128.0	3.7	127.1	2.0	104.4	1.3
ISO	120.9	4.1	123.7	4.7	108.3.	2.8
VAL	130.5	4.3	124.3	4.4	109.1	3.0
o-TOL	115.7	3.2	118.6	3.5	92.0	1.7
m-TOL	113.3	4.0	113.7	3.0	101.7	2.5
p-TOL	117.3	4.2	118.5	3.7	103.6	1.3
HEX	111.2	1.6	116.4	1.9	103.8	1.3
DIM	115.6	1.8	118.9	2.3	107.6	1.6

Table 3 Linear relationships, limits of detection (LODs) and limits of quantification (LOQs) of the 15 carbonyl compounds

Compound	Linear range/ (μg/mL)	Linear equation	r²	LODs/(mg/L)		LOQs/(mg/L)
Compound	Linear range/ (μg/mL)	Linear equation	r²	This method	HJ 997-2018	This method	HJ 997-2018
FOR	0.1-20.0	y=13.613x+0.052	0.997	0.02	0.02	0.05	0.08
ACETA	0.2-20.0	y=10.242x+0.045	0.996	0.03	0.04	0.10	0.16
ACR	0.2-20.0	y=9.355x+0.038	0.996	0.03	0.04	0.10	0.16
ACETO	0.2-20.0	y=7.977x+0.040	0.997	0.03	0.04	0.10	0.16
PRO	0.2-20.0	y=7.419x+0.017	0.996	0.03	0.04	0.10	0.16
CRO	0.2-20.0	y=6.648x+0.017	0.997	0.04	0.04	0.14	0.16
BUT	0.5-20.0	y=4.789x+0.005	0.998	0.04	0.04	0.13	0.16
BEN	0.2-20.0	y=4.633x+0.024	0.996	0.04	0.06	0.13	0.24
ISO	0.5-20.0	y=4.037x+0.015	0.996	0.05	0.06	0.18	0.24
VAL	0.5-20.0	y=3.558x+0.067	0.997	0.05	0.06	0.18	0.24
o-TOL	0.5-20.0	y=3.865x+0.012	0.996	0.05	0.05	0.10	0.20
m-TOL	0.5-20.0	y=4.113x+0.014	0.999	0.05	0.06	0.18	0.24
p-TOL	0.5-20.0	y=3.588x+0.025	0.999	0.05	0.06	0.18	0.24
HEX	0.5-20.0	y=3.931x-0.047	0.998	0.06	0.06	0.20	0.24
DIM	0.5-20.0	y=3.294x-0.003	0.999	0.06	0.06	0.20	0.24

Table 4 Spiked recoveries and RSDs of the 15 carbonyl compounds (n=6)

Compound	0.2 mg/kg		0.5 mg/kg		2.0 mg/kg
Compound	Recovery/ %	RSD/ %	Recovery/ %	RSD/ %	Recovery/ %	RSD/ %
FOR	84.6	1.7	88.3	2.6	90.5	1.3
ACETA	112.7	4.1	110.2	4.1	115.9	4.1
ACR	99.3	5.0	106.9	2.8	102.7	4.6
ACETO	104.4	1.2	101.1	1.7	98.4	1.3
PRO	105.1	3.5	106.1	2.7	105.2	2.3
CRO	107.2	1.6	108.4	2.5	107.8	1.0
BUT	100.2	3.5	99.8	3.6	109.7	0.2
BEN	106.3	3.9	105.4	2.7	104.4	1.3
ISO	107.0	4.3	110.6	3.0	108.3	2.8
VAL	105.2	1.9	98.6	1.6	109.1	3.0
o-TOL	87.5	0.6	89.7	3.6	92.0	1.7
m-TOL	85.4	2.8	90.2	2.7	101.7	2.5
p-TOL	91.2	5.1	96.6	2.9	103.6	1.3
HEX	104.0	2.9	106.5	2.5	103.8	0.3
DIM	97.6	2.0	96.1	1.8	107.6	0.6

References

[1]	Kong F T, Wang K, Zhao F H, et al. Henan Science and Technology, 2019, 28(10): 133
[1]	孔凡亭, 王坤, 赵芳辉, 等. 河南科技, 2019, 28(10): 133
[2]	Li S F, Jiang L L, Sun Y K. Chemical Analysis and Meterage, 2021, 30(5): 65
[2]	李少飞, 姜丽丽, 孙延康. 化学分析计量, 2021, 30(5): 65
[3]	Zhang Y, Zhai Y P. Guangdong Chemical Industry, 2021, 48(9): 251
[3]	张颖, 翟有朋. 广东化工, 2021, 48(9): 251
[4]	Wang Q, Xun Z Q, Huang J F, et al. Journal of Instrumental Analysis, 2018, 37(5): 582
[4]	王强, 寻知庆, 黄金凤, 等. 分析测试学报, 2018, 37(5): 582
[5]	Yin G L, Zhou L L, Liu C S, et al. Chemical Analysis and Meterage, 2020, 29(5): 138
[5]	尹桂林, 周龙龙, 刘成帅, 等. 化学分析计量, 2020, 29(5): 138
[6]	Fang S Y, Chen S L, He J H, et al. Chinese Journal of Chromatography, 2019, 37(6): 634
[6]	方思炀, 陈诗丽, 何嘉铧, 等. 色谱, 2019, 37(6): 634
[7]	Li L R, Wu Y F, Zhang Y H, et al. Industrial Water Treatment, 2019, 39(5): 88
[7]	李利荣, 吴宇峰, 张玉惠, 等. 工业水处理, 2019, 39(5): 88
[8]	Cui L X, Li L R, Wu Y F, et al. Physical Testing and Chemical Analysis (art B: Chemical Analysis), 2018, 54(4): 484
[8]	崔连喜, 李利荣, 吴宇峰, 等. 理化检验(化学分册), 2018, 54(4): 484
[9]	Si L G, Xing G H, Wang C, et al. Environmental Chemistry, 2019, 38(10): 2222
[9]	司利国, 邢冠华, 王超, 等. 环境化学, 2019, 38(10): 2222
[10]	Guan X G, Rubin E, Anni H. Alcohol: Clin Exp Res, 2012, 36(3): 398
[11]	Lü H X, Tian J J, Cai Q Y, et al. Aerosol Air Qual Res, 2016, 16(5): 1234
[12]	Heath1 A A, Vaitilingom M, Ehrenhauser F S. J Atmos Chem, 2015, 72(7): 165
[13]	Jo S H, Kim K H. J Chromatogr A, 2016, 429(15): 369
[14]	Uchiyama S, Senoo Y, Hayashida H, et al. Anal Sci, 2016, 32(5): 549
[15]	Li L R, Wu Y F, Zhang J, et al. Environmental Chemistry, 2021, 40(10): 3055
[15]	李利荣, 吴宇峰, 张静, 等. 环境化学, 2021, 40(10): 3055
[16]	Reinnig M C, Müller L, Warnke J, et al. Anal Bioanal Chem, 2008, 391(3): 171
[17]	Brandao P F, Ramos R M, DeAlmeida P J F, et al. J Agric Food Chem, 2017, 65(5): 1037
[18]	Gai Q Q, Wu P, Shi Y L, et al. Chinese Journal of Chromatography, 2015, 33(1): 90
[18]	盖青青, 武鹏, 石玉林, 等. 色谱, 2015, 33(1): 90
[19]	Malaei R, Ramezani A M. J Chromatogr B, 2018, 1089(1): 60
[20]	Blas M D, Navazo M, Alonso L, et al. Sci Total Environ, 2011, 409(24): 5459
[21]	Cui T H, Li H, Tang S Y, et al. Journal of Instrumental Analysis, 2018, 37(7): 766
[21]	崔婷惠, 李恒, 唐石云, 等. 分析测试学报, 2018, 37(7): 766
[22]	Gherghel S, Morgan R M, Liébanas J A. Forensic Sci Int, 2018, 290(9): 207
[23]	997- 2018
[24]	Li L R, Guan Y C, Wu Y F. Physical Testing and Chemical Analysis (Part B: Chemical Analysis), 2018, 54(7): 841
[24]	李利荣, 关玉春, 吴宇峰. 理化检测-化学分册, 2018, 54(7): 841
[25]	Zhao J Y, Li X M, Lu X H, et al. Chinese Journal of Chromatography, 2017, 35(7): 748
[25]	赵佳莹, 李晓敏, 卢晓华, 等. 色谱, 2017, 35(7): 748