电感耦合等离子体质谱法（ICP-MS）测定牙膏中多种元素

doi:10.3969/j.issn.1001-1803.2021.11.014

摘要/Abstract

摘要：

建立了电感耦合等离子体质谱法（ICP-MS）测定牙膏中多种元素的含量。采用微波消解法消解样品,选用铑（Rh）、铼（Re）作为内标,ICP-MS法同时测定牙膏中镁（Mg）、铝（Al）、钾（K）、钙（Ca）、钛（Ti）、铬（Cr）、锰（Mn）、铁（Fe）、镍（Ni）、铜（Cu）、锌（Zn）、砷（As）、硒（Se）、锶（Sr）、钼（Mo）、银（Ag）、镉（Cd）、锡（Sn）、锑（Sb）、钡（Ba）、汞（Hg）、铊（Tl）、铅（Pb） 23种元素的含量,以内标法计算。结果表明,对于所测元素,标准曲线相关系数r≥0.998 8。重复性试验的相对标准偏差（RSD）在2.5%~9.5%（n=6）。低、中、高浓度加样回收率（n=9）范围为85.6%~105.9%。该方法灵敏度高、专属性强、简便、快速、准确,适用于牙膏中多种元素的含量测定。

关键词: 电感耦合等离子体质谱法（ICP-MS）, 微波消解法, 牙膏, 元素

Abstract:

A method for the determination of multiple elements in toothpaste by ICP-MS was established. Microwave digestion was used for sample pre-treatment. Rh and Re were used as the internal standard. The contents of 23 kinds of elements in toothpaste, including Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Sr, Mo, Ag, Cd, Sn, Sb, Ba, Hg, Tl and Pb were determined by ICP-MS. The internal standard method was used for quantitative analysis. The results show that the correlation coefficient of the calibration curve is over 0.998 8 for all the analyzed elements. RSD of repeatability test ranges from 2.5% to 9.5% （n=6）. The recovery of low, medium and high concentration （n=9） ranges from 85.6% to 105.9%. The method is sensitive, specific, simple, rapid and accurate. It is suitable for the determination of multiple elements in toothpaste.

Key words: inductively coupled plasma mass spectrometry （ICP-MS）, microwave digestion, toothpaste, elements

中图分类号:

TQ658

吴莉,周娟娟,方方,冯有龙,曹玲. 电感耦合等离子体质谱法（ICP-MS）测定牙膏中多种元素[J]. 日用化学工业, 2021, 51(11): 1134-1141.

Wu Li,Zhou Juanjuan,Fang Fang,Feng Youlong,Cao Ling. Determination of multiple elements in toothpaste by inductively coupled plasma mass spectrometry （ICP-MS）[J]. China Surfactant Detergent & Cosmetics, 2021, 51(11): 1134-1141.

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参考文献 20

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待测元素	m/z	内标	待测元素	m/z	内标
Mg	24	¹⁰³Rh	Se	78	¹⁰³Rh
Al	27	¹⁰³Rh	Sr	88	¹⁰³Rh
K	39	¹⁰³Rh	Mo	95	¹⁰³Rh
Ca	43	¹⁰³Rh	Ag	107	¹⁰³Rh
Ti	48	¹⁰³Rh	Cd	111	¹⁰³Rh
Cr	52	¹⁰³Rh	Sn	118	¹⁰³Rh
Mn	55	¹⁰³Rh	Sb	123	¹⁰³Rh
Fe	56	¹⁰³Rh	Ba	137	¹⁰³Rh
Ni	60	¹⁰³Rh	Hg	202	¹⁸⁵Re
Cu	63	¹⁰³Rh	Tl	205	¹⁸⁵Bi
Zn	66	¹⁰³Rh	Pb	208	¹⁸⁵Bi
As	75	¹⁰³Rh

元素	线性方程	相关系数（r）	线性范围/（μg·L^-1）	检测限/（mg·kg^-1）	定量限/（mg·kg^-1）
Mg	y=5.597 2×10^-5x+4.119 7×10^-5	1.000 0	27~5 000	1	3.3
Al	y=1.249 2×10^-5x+2.059 6×10^-5	1.000 0	13~5 000	0.5	1.7
K	y=3.175 9×10^-5x+2.823 2×10^-5	1.000 0	27~5 000	1	3.3
Ca	y=1.999 4×10^-6x+2.957 3×10^-6	0.999 9	27~5 000	1	3.3
Ti	y=2.154 0×10^-4x+1.295 9×10^-5	0.999 8	2.7~50	0.1	0.33
Cr	y=0.001 3x+2.236 3×10^-5	1.000 0	2.7~50	0.1	0.33
Mn	y=3.947 6×10^-4x+1.118 8×10^-5	0.999 9	1.3~50	0.05	0.17
Fe	y=8.703 1×10^-4x+7.603 6×10^-4	1.000 0	11~5 000	0.4	1.3
Ni	y=7.140 0×10^-4x+4.587 5×10^-5	1.000 0	2.7~50	0.1	0.33
Cu	y =0.002 1x+7.534 3×10^-5	1.000 0	0.53~50	0.02	0.067
Zn	y=2.192 8×10^-4x+9.585 6×10^-5	1.000 0	13~5 000	0.5	1.7
As	y=1.266 9×10^-4x-1.233 4×10^-6	1.000 0	1.3~50	0.05	0.17
Se	y=4.213 9×10^-6x+5.938 0×10^-7	0.998 8	2.7~50	0.1	0.33
Sr	y=3.177 3×10^-4x+1.240 2×10^-5	1.000 0	5.3~5 000	0.2	0.67
Mo	y=7.683 4×10^-4x+1.782 6×10^-6	1.000 0	0.27~5	0.01	0.033
Ag	y=0.002 7x+7.096 4×10^-6	1.000 0	0.27~50	0.01	0.033
Cd	y=2.714 6×10^-4x	1.000 0	0.53~50	0.02	0.067
Sn	y=4.230 2×10^-4x-7.789 6×10^-9	0.999 7	0.27~5	0.01	0.033
Sb	y=5.018 4×10^-4x+1.249 4×10^-9	1.000 0	0.27~5	0.01	0.033
Ba	y=1.353 7×10^-4x+7.627 8×10^-6	1.000 0	0.53~50	0.02	0.067
Hg	y=0.003 9x-1.315 4×10^-5	0.999 9	0.48~5	0.02	0.06
Tl	y=0.019 9x-9.645 2×10^-8	1.000 0	0.27~50	0.01	0.033
Pb	y=0.025 1x+0.002 4	0.999 7	0.80~50	0.03	0.1

元素	本底值/（mg·kg^-1）	加标值/（mg·kg^-1）	测定值/（mg·kg^-1）	回收率/%	元素	本底值/（mg·kg^-1）	加标值/（mg·kg^-1）	测定值/（mg·kg^-1）	回收率/%
Mg	1.93	25	25.53	94.4	Zn	ND	25	22.17	88.7
		125	126.31	99.5			125	115.74	92.6
		250	255.18	101.3			250	239.12	95.6
Al	10.04	25	33.24	92.8	As	ND	0.25	0.24	96.0
		125	130.42	96.3			1.25	1.23	98.4
		250	260.04	100.0			2.5	2.48	99.2
K	9.07	25	31.90	91.3	Se	ND	0.25	0.22	88.0
		125	125.7	93.3			1.25	1.12	89.6
		250	244.82	94.3			2.5	2.28	91.2
Ca	1.35	25	24.48	92.5	Sr	0.22	25	24.25	96.1
		125	125.48	99.3			125	123.35	98.5
		250	247.60	98.5			250	255.72	102.2
Ti	3.58	0.25	3.79	85.6	Mo	ND	0.025	0.024	96.0
		1.25	4.90	105.6			0.125	0.128	102.4
		2.5	6.23	105.9			0.25	0.261	104.4
Cr	0.55	0.25	0.79	96.0	Ag	ND	0.25	0.24	96.0
		1.25	1.80	100.0			1.25	1.22	97.6
		2.5	2.96	96.4			2.5	2.57	102.8
Mn	0.35	0.25	0.60	100.0	Cd	ND	0.25	0.25	100.0
		1.25	1.53	94.4			1.25	1.21	96.8
		2.5	2.82	98.8			2.5	2.51	100.4
Fe	1.25	25	26.48	100.9	Sn	0.070	0.025	0.096	104.0
		125	121.50	96.2			0.125	0.193	98.4
		250	247.00	98.3			0.25	0.313	97.2
Ni	0.15	0.25	0.39	96.0	Sb	0.022	0.025	0.048	104.8
		1.25	1.37	97.6			0.125	0.140	94.5
		2.5	2.65	100.0			0.25	0.263	96.3
Cu	ND	0.25	0.24	96.0	Ba	0.45	0.25	0.70	100.0
		1.25	1.23	98.4			1.25	1.64	95.2
		2.5	2.48	99.2			2.5	2.97	100.8
Hg	ND	0.025	0.024	96.0	Pb	0.14	0.25	0.40	104.0
		0.125	0.127	101.2			1.25	1.38	99.2
		0.25	0.249	99.6			2.5	2.65	100.4
Tl	ND	0.25	0.25	100.0
		1.25	1.28	102.4
		2.5	2.59	103.6

元素	芹菜（GSB-26）			霜类化妆品基体中重金属铅、砷元素成分分析标准物质（GBW09305）
元素	标准值	HF测定值	H₂O₂测定值	标准值	HF测定值	H₂O₂测定值
Mg	（0.53±0.03）×10^-2	0.26×10^-2	0.53×10^-2
Al	0.14×10^-2	0.06×10^-2	0.05×10^-2
K	（2.7±0.2）×10^-2	2.7×10^-2	2.7×10^-2
Ca	（1.66±0.06）×10^-2	0.2×10^-2	0.15×10^-2
Ti	45×10^-6	47×10^-6	46×10^-6
Cr	（1.35±0.22）×10^-6	1.35×10^-6	1.16×10^-6
Mn	（45±2）×10^-6	45×10^-6	45×10^-6
Fe	（597±34）×10^-6	463×10^-6	597×10^-6
Ni	（1.8±0.4）×10^-6	1.7×10^-6	1.5×10^-6
Cu	（8.2±0.4）×10^-6	7.7×10^-6	7.7×10^-6
Zn	（26±2）×10^-6	24×10^-6	25×10^-6
As	（0.39±0.08）×10^-6	0.48×10^-6	0.34×10^-6	（9.0±0.4）×10^-6	8.9×10^-6	8.9×10^-6
Se	（0.118±0.017）×10^-6	0.134×10^-6	0.189×10^-6
Sr	（213±19）×10^-6	209×10^-6	215×10^-6
Mo	（1.02±0.09）×10^-6	1.0×10^-6	0.96×10^-6
Ag	0.012×10^-6	0.007×10^-6	0.003×10^-6
Cd	（0.092±0.006）×10^-6	0.089×10^-6	0.089×10^-6
Sn	0.10×10^-6	0.10×10^-6	0.11×10^-6
Sb	56×10^-9	57×10^-9	46×10^-9
Ba	（17.3±2.3）×10^-6	17.0×10^-6	16.0×10^-6
Hg	（14.6±2.4）×10^-9	13.5×10^-9	16.4×10^-9
Tl	（21±4）×10^-9	17×10^-9	16×10^-9
Pb	（2.7±0.7）×10^-6	2.7×10^-6	2.3×10^-6	（37.2±0.8）×10^-6	36.9×10^-6	37.0×10^-6

元素	儿童牙膏含量/（mg·kg^-1）	成人牙膏含量/（mg·kg^-1）	未检出件数	元素	儿童牙膏含量/（mg·kg^-1）	成人牙膏含量/（mg·kg^-1）	未检出件数
Mg	1.93~287.15	12.86~1991.86	0+0	Se	未检出	未检出	15+15
Al	10.04~487.46	未检出~1628.60	0+4	Sr	未检出~1.15	0.54~1492.13	1+0
K	2.47~135.08	6.87~500.73	0+0	Mo	未检出~0.051	0.015~0.066	7+0
Ca	未检出~18.69	6.72~3375.79	4+0	Ag	未检出	未检出	15+15
Ti	3.58~84.56	19.08~2683.26	0+0	Cd	未检出	未检出~0.31	15+6
Cr	0.45~2.04	0.22~1.33	0+0	Sn	0.02~0.93	0.018~0.14	0+0
Mn	0.28~0.68	0.60~19.33	0+0	Sb	0.02~0.05	0.013~0.45	0+0
Fe	1.25~58.04	13.21~68.11	0+0	Ba	0.20~10.21	0.95~5.25	0+0
Ni	0.15~0.84	0.20~1.13	0+0	Hg	未检出	未检出	15+15
Cu	未检出~0.66	0.14~16.23	1+0	Tl	未检出	未检出	15+15
Zn	未检出~497.11	未检出~843.76	9+4	Pb	0.14~0.59	0.15~0.32	0
As	未检出~1.81	1.42~1.81	1+0