便携式X射线荧光光谱法快速检测化妆品中汞

doi:10.3969/j.issn.1001-1803.2021.01.012

摘要/Abstract

摘要：

建立便携式X射线荧光光谱仪分析技术快速检测化妆品中汞含量的方法。通过配制不同含量汞的化妆品标准物质,优化便携式X射线荧光光谱仪仪器参数：土壤分析模式,主范围时间150 s,低范围时间5 s,轻范围时间5 s,标准偏差1 σ,厚度不修正。经过方法验证,以固体、膏状、乳液3种空白化妆品考察基质,结果显示,方法检出限为1.0 mg/kg,灵敏度≥95%、特异性≥85%、假阴性≤5%、假阳性≤15%。在104批次实际样品检测过程中,与国标方法结果比较相对误差在5.93%~14.58%之间。该方法快捷、简单,可以在化妆品汞超标应急事件、化妆品日常监督抽检中对汞含量进行快速检测。

关键词: 便携式X射线荧光光谱仪, 化妆品, 汞元素, 快速检测, 元素分析

Abstract:

This paper established a method using portable X-ray fluorescence spectrometer to rapidly detect of mercury content in cosmetics. The instrument parameters of portable X-ray fluorescence spectrometer were optimized by preparing cosmetics reference materials with different contents of mercury: soil analysis mode, main range time 150 s, low range time 5 s, light range time 5 s, standard deviation 1 σ, thickness was not corrected. After verification of the method, three kinds of blank cosmetics, solid matrix, paste and emulsion were used to examine the matrix. The results show that the detection limit is 1.0 mg/kg, sensitivity is more than 95%, specificity is more than 85%, false negative is less than 5%, and false positive is less than 15%. In the detection process of 104 batches of actual samples, the relative error is 5.93%-14.58% compared with the results of national standard method. The method is fast and simple, and can be used for quick detection of mercury content in cosmetics in the emergency incident of cosmetic mercury exceeding the standard and in the daily supervision and sampling of cosmetics.

Key words: portable X-ray fluorescence spectrometer, cosmetics, mercury, rapid detection, element analysis

中图分类号:

TQ658

梁剑锋,李亚,梁燕妮,卓梅芳,杨韶平. 便携式X射线荧光光谱法快速检测化妆品中汞[J]. 日用化学工业, 2021, 51(1): 68-72.

LIANG Jian-feng,LI Ya,LIANG Yan-ni,ZHUO Mei-fang,YANG Shao-ping. Rapid detection of mercury in cosmetics by portable X-rayfluorescence spectrometer[J]. China Surfactant Detergent & Cosmetics, 2021, 51(1): 68-72.

图/表 3

表1

表2

表3

实际样品检测结果"

样品编号	方法2汞含量/（mg·kg^-1）	方法1汞含量/（mg·kg^-1）	RSD/%	假阳性	样品编号	方法2汞含量/（mg·kg^-1）	方法1汞含量/（mg·kg^-1）	RSD/%	假阳性
T001	25	28	12.00		T003	0.12	<1	/
T002	0.05	<1	/		T004	0.75	<1	/
T005	120	133	10.83		T041	LOD	<1	/
T006	LOD	<1	/		T042	LOD	<1	/
T007	LOD	<1	/		T043	LOD	<1	/
T008	0.37	<1	/		T044	296	332	12.16
T009	LOD	<1	/		T045	LOD	<1	/
T010	LOD	<1	/		T046	LOD	<1	/
T011	LOD	<1	/		T047	LOD	<1	/
T012	0.92	<1	/		T048	LOD	<1	/
T013	12 489	13 229	5.93		T049	LOD	<1	/
T014	LOD	<1	/		T050	LOD	<1	/
T015	LOD	<1	/		T051	LOD	<1	/
T016	LOD	<1	/		T052	0.01	3	/	＊
T017	LOD	<1	/		T053	0.45	<1	/
T018	LOD	<1	/		T054	0.54	<1	/
T019	LOD	<1	/		T055	LOD	<1	/
T020	LOD	<1	/		T056	LOD	<1	/
T021	LOD	<1	/		T057	LOD	<1	/
T022	LOD	<1	/		T058	LOD	<1	/
T023	0.54	<1	/		T059	96	82	-14.58
T024	4 978	5 292	6.31		T060	LOD	<1	/
T025	LOD	<1	/		T061	LOD	<1	/
T026	LOD	<1	/		T062	LOD	<1	/
T027	LOD	<1	/		T063	LOD	<1	/
T028	LOD	<1	/		T064	0.02	2	/	＊
T029	LOD	<1	/		T065	0.11	<1	/
T030	LOD	<1	/		T066	0.32	<1	/
T031	0.86	<1	/		T067	0.56	<1	/
T032	0.71	2	/	＊	T068	0.24	<1	/
T033	LOD	<1	/		T069	LOD	2	/	＊
T034	LOD	<1	/		T070	LOD	<1	/
T035	LOD	<1	/		T071	LOD	<1	/
T036	LOD	<1	/		T072	LOD	<1	/
T037	0.32	<1	/		T073	LOD	<1	/
T038	1 957	2 095	7.05		T074	LOD	<1	/
T039	0.02	<1	/		T075	LOD	<1	/
T040	LOD	<1	/		T076	LOD	<1	/
T077	LOD	<1	/		T091	LOD	<1	/
T078	0.05	3	/	＊	T092	0.68	<1	/
T079	378	430	13.76		T093	LOD	<1	/
T080	0.44	<1	/		T094	LOD	<1	/
T081	0.62	<1	/		T095	658	742	12.77
T082	0.44	<1	/		T096	LOD	<1	/
T083	0.39	<1	/		T097	LOD	<1	/
T084	LOD	<1	/		T098	LOD	<1	/
T085	LOD	<1	/		T099	LOD	<1	/
T086	LOD	<1	/		T100	0.85	4	/	＊
T087	228	255	11.84		T101	LOD	<1	/
T088	LOD	<1	/		T102	LOD	<1	/
T089	LOD	<1	/		T103	LOD	<1	/
T090	LOD	<1	/		T104	0.09	<1	/

表3

参考文献 15

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标准物质含量/（mg·kg^-1）	便携式X射线荧光光谱法检测结果/（mg·kg^-1）	RSD/%
1	2	20.2
5	7	18.7
10	12	15.4
50	59	13.9
100	117	11.0
200	236	8.9
500	582	6.7
1 000	1 205	5.0
2 000	2 149	3.8

盲样情况	固体基质			膏状基质			乳液基质
盲样情况	阳性	阴性	总数	阳性	阴性	总数	阳性	阴性	总数
阳性	150	1	151	150	4	154	150	6	156
阴性	0	99	99	0	96	96	0	94	94
灵敏度（p+）	p+=150/151=99.34%			p+=150/154=97.04%			p+=150/156=96.16%
特异性（p-）	p-=99/99=100%			p-=96/96=100%			p-=94/94=100%
假阴性率（pf-）	pf-=1/151=0.66%			pf-=4/154=2.60%			pf-=6/156=3.85%
假阳性率（pf+）	pf+=0/99=0%			pf+=0/96=0%			pf+=0/94=0%
相对准确度	（150+99）/（151+99）=99.6%			（150+96）/（154+96）=98.4%			（150+94）/（156+94）=97.6%
显著性差异（χ²）	/			（\|4-0\|-1）2/（4+0）=2.25 自由度（df）=1			（\|6-0\|-1）2/（6+0）=4.17 自由度（df）=1