基于巯基化衍生的气相色谱-质谱法测定有机相及水相中氯化氰

doi:10.3724/SP.J.1123.2020.12004

摘要/Abstract

摘要：

氯化氰(ClCN)是常用的化工中间体,也是《禁止化学武器公约》附表颁布的化学毒剂之一。采用传统的比色法或气相色谱法对ClCN进行分析时,稳定性差且检出限高。研究建立了有机相及水相中ClCN的巯基化衍生过程及气相色谱-质谱(GC-MS)的检测方法。经比较后选择1-丁基硫醇作为衍生试剂,有机相中ClCN的衍生条件为衍生温度40 ℃,体系pH=9,反应时间10 min,反应结束后直接进行GC-MS分析。水相中ClCN的衍生条件与有机相相同,衍生完毕后进行顶空-固相微萃取(HS-SPME)。实验考察了萃取温度对萃取吸附效果的影响,确定最佳萃取温度为55 ℃。通过GC-EI/MS确认ClCN的巯基化衍生产物为硫氰酸丁酯,并对质谱图中主要的离子碎片进行结构确认。采用气相色谱-串联质谱法(GC-MS/MS)对硫氰酸丁酯裂解规律进行了分析。采用GC-MS/SIM对有机相及水相中的ClCN进行分析。方法学考察结果表明,ClCN在有机相(20~2000 μg/L)及水相(20~1200 μg/L)中相应的范围内线性关系良好(相关系数(R ²)>0.99);在3个添加水平下有机相中CICN的回收率为87.3%~98.8%,不同的水相基质中CICN的回收率为97.6%~102.2%, RSD分别为2.1%~4.7%和2.8%~4.2%,衍生过程具有良好的专属性。采用禁止化学武器公约组织(OPCW)的水平考试空白有机样品(样品基质为正己烷)对研究方法进行验证,该方法能够成功检出目标物。该研究建立的巯基化衍生-气相色谱-质谱法灵敏度高,精密度好,能够为环境中ClCN的定性定量分析提供技术支持。

关键词: 气相色谱-质谱, 顶空-固相微萃取, 巯基化衍生, 氯化氰

Abstract:

Cyanogen chloride (ClCN) has been widely used in industrial production. ClCN is also listed in the Schedule of the Chemical Weapons Convention (CWC). The use of traditional colorimetric analysis or gas chromatography for the detection of ClCN has been characterized by low efficiency and poor sensitivity. In this study, a method was established for the qualitative analysis and quantitative detection of ClCN in organic and water matrices by gas chromatography-mass spectrometry (GC-MS) based on thiol derivatization. 1-Butylthiol was selected as the optimal derivatization reagent. The optimal temperature for thiol derivatization in the organic matrices was 40 ℃ and the reaction time was 10 min. The pH for derivatization was approximately 9. The ClCN in the organic matrices was directly analyzed by GC-MS after derivatization. The conditions of ClCN derivatization in the water matrices were the same as those in the organic matrices. After the derivatization of ClCN, headspace-solid phase microextraction (HS-SPME) was employed during sample preparation for water matrices. Different temperatures for HS-SPME were explored, and the optimal temperature was found to be 55 ℃. The product of thiol derivatization was confirmed as butyl thiocyanate. The main fragmentation patterns and mass spectrometric cleavage pathway were investigated by GC-MS/MS. The quantitative determination of ClCN in organic and water matrices was conducted via the internal standard and external standard methods, respectively. ClCN showed good linearity in the corresponding ranges in the organic and water matrices. The correlation coefficients for both matrices were greater than 0.99. The linearities of ClCN in the organic and water matrices were in the range of 20-2000 μg/L and 20-1200 μg/L, respectively. An organic sample and water samples from different substrates were selected to verify the accuracy and precision of the method at three spiked levels. The average spiked recoveries of ClCN in the organic sample and water samples were 87.3%-98.8% and 97.6%-102.2%, respectively. The corresponding relative standard deviations (RSDs, n=6) were 2.1%-4.7% and 2.8%-4.2%. The derivatization method established in this study showed good reaction specificity. The method was successfully applied in the analysis of samples obtained from the Organisation for the Prohibition of Chemical Weapons (OPCW). The method established in this study for the detection of ClCN showed high sensitivity and precision, and could aid in the analysis and detection of ClCN in the environment.

Key words: gas chromatography-mass spectrometry (GC-MS), headspace solid phase microextraction (HS-SPME), thiol derivatization, cyanogen chloride (CICN)

中图分类号:

O658

李晓森, 吴姬娜, 夏俊美, 袁铃, 杨旸. 基于巯基化衍生的气相色谱-质谱法测定有机相及水相中氯化氰[J]. 色谱, 2021, 39(8): 913-920.

LI Xiaosen, WU Jina, XIA Junmei, YUAN Ling, YANG Yang. Determination of cyanogen chloride in organic and water matrices by gas chromatography-mass spectrometry based on thiol derivatization[J]. Chinese Journal of Chromatography, 2021, 39(8): 913-920.

图/表 9

图1 ClCN(10 mg/L)/甲苯标准工作溶液的色谱图

Fig. 1 Chromatograms of ClCN (10 mg/L)/toluene standard working solution CICN: cyanogen chloride.

图2 采用不同衍生试剂时ClCN衍生产物的色谱图

Fig. 2 Chromatograms of ClCN derivative products with different derivatization reagents

表1 正交试验结果

Table 1 Orthogonal array testing results

Level	Temperature/ ℃	Time/min	Solvent	pH value
1	30	5	toluene	9 (adjusted by triethylamine)
2	40	10	dichloromethane	no addition
3	50	20	chloroform	5 (adjusted by acetic acid)
Mean square	5.12×10⁸	2.13×10⁸	4.32×10⁷	1.24×10¹¹
F	2.48	1.08	0.21	874.2
Significance	no influence	no influence	no influence	highly significant

图3 不同顶空-固相微萃取温度对ClCN衍生产物峰面积的影响(n=3)

Fig. 3 Effect of different temperatures for HS-SPME on the peak area of derivative of ClCN (n=3)

图4 水样基质中10 mg/L ClCN衍生产物的色谱图

Fig. 4 Chromatogram of derivative of ClCN at 10 mg/L in the water matrix

图5 不同碰撞能量下m/z 57的碎片离子作为母离子时的质谱图

Fig. 5 Mass spectra with fragment ions of m/z 57 as the precursor ions under different collision energies

图6 硫氰酸丁酯的质谱裂解规律

Fig. 6 MS fragmentation route of butyl thiocyanate

表2 不同基质中ClCN的线性范围、线性方程、相关系数(R2)、检出限及定量限

Table 2 Linear ranges, linear equations, correlation coefficients (R2), LODs and LOQs of ClCN in the different matrices

Matrix	Linear range/ (μg/L)	Linear equation	R²	LOD/ (μg/L)	LOQ/ (μg/L)
Organic	20-2000	y₁=2.4781x-1.0415	0.9972	15	20
Water	20-1200	y₂=2.5893x+0.8397	0.9902	17	20

表3 不同基质中ClCN的加标回收率和相对标准偏差(n=6)

Table 3 Spiked recoveries and RSDs of ClCN in the different matrices (n=6)

Matrix	Spiked level/(μg/L)	Recovery/%	RSD/%
Toluene	40	98.8	4.7
	900	93.4	3.3
	1800	87.3	2.1
Deionized water	100	98.2	3.2
	500	97.6	3.1
	1000	98.9	2.8
River water	100	102.2	3.3
	500	100.4	4.2
	1000	100.2	3.2
Tap water	100	98.5	2.8
	500	98.3	3.4
	1000	99.8	3.5
Drinking water	100	101.3	3.1
	500	100.3	3.2
	1000	101.4	2.9

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