Determination of Toxic and Low-Temperature Elements As, Sb, Cd and Tl in Rapeseeds by Inductively Coupled Plasma-Mass Spectrometry with Slurry-emulsion System Sampling
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摘要:
油菜籽品质及重金属污染程度直接关系到人类健康，对油菜籽中As、Sb、Cd和Tl等有毒元素含量进行监测有助于对食用油生产原材料的提前监控。避开强酸消解前处理的繁琐，为了实现快速测定菜籽中As、Sb、Cd和Tl等易挥发有毒元素的准确含量，以及解决粮油食品脂肪含量高对前处理的挑战，本文采用一种悬浮-乳化协同制样技术，详细考察了影响悬浮-乳化的诸多条件，制得均匀稳定的悬浮-乳化试液(Slurry-Emulsion Solution，SES)体系。在进样效率高的电热蒸发器(ETV)中，优化程序升温参数和改进剂硝酸钯的用量，SES直接进样，采用电感耦合等离子体质谱(ICP-MS)测定了油菜籽中As、Sb、Cd和Tl。该方法对As、Sb、Cd和Tl的相对标准偏差(RSD)分别为10.1%、8.8%、8.9%、6.4% [c=0.5%(m/V)，n=5]。在最佳实验条件下，As、Sb、Cd和Tl检出限(3σ)分别为40.0ng/L、20.0ng/L、50.0ng/L和10.0ng/L，对应原始固体样品的检出限(3σ)分别为8.0ng/g、4.0ng/g、10.0ng/g和2.0ng/g。菜籽样品中As、Sb、Cd和Tl含量的测定范围分别在50.4~90.5ng/g、28.0~59.9ng/g、51.3~69.1ng/g、91.3~216.6ng/g。本文建立的悬浮-乳化协同处理高油脂含量菜籽的分析方法简便快速、成本低，充分发挥ETV进样优势，助推了ETV-ICP-MS固体进样分析应用。
Abstract:BACKGROUND The quality of rapeseed and the degree of heavy metal pollution are directly related to human health. Monitoring the content of toxic elements such as As, Sb, Cd, and Tl in rapeseed is helpful for early monitoring of raw materials for edible oil production.
OBJECTIVES To avoid the cumbersome pretreatment of strong acid digestion, quickly determine the accurate content of volatile toxic elements such as As, Sb, Cd, and Tl in rapeseed, and to solve the challenge of pretreatment due to the heavy fat content of grains, oils, and foods.
METHODS A suspension-emulsion synergistic sample preparation technique was used to investigate conditions affecting suspension-emulsion, and a homogeneous and stable slurry-emulsion solution (SES) system was prepared. In the electrothermal vaporizer (ETV) with high sampling efficiency, the temperature-programmed parameters and the dosage of improver palladium nitrate were all optimized. SES was directly injected, and inductively coupled plasma-mass spectrometry (ICP-MS) was used to determine As, Sb, Cd and Tl.
RESULTS The overall reproducibility (relative standard deviation, RSD) of the suspension-emulsion sampling-ETV-ICP-MS detection method were 10.1%, 8.8%, 8.9% and 6.4% [c=0.5% (m/V), n=5] for As, Sb, Cd and Tl, respectively. Under the optimum conditions, the limits of detection (3σ) were 40.0ng/L, 20.0ng/L, 50.0ng/L and 10.0ng/L for As, Sb, Cd and Tl, respectively. Accordingly, the limits of detection for the original solid samples were 8.0ng/g, 4.0ng/g, 10.0ng/g and 2.0ng/g for As, Sb, Cd and Tl, respectively. The contents of As, Sb, Cd and Tl in tested rapeseed samples were 50.4-90.5ng/g, 28.0-59.9ng/g, 51.3-69.1ng/g and 91.3-216.6ng/g, respectively.
CONCLUSIONS The suspension-emulsion synergistic treatment of rapeseed with high oil content is simple, fast, and cost efficient. It utilizes the advantages of ETV sampling and promotes the application of ETV-ICP-MS solid sampling analysis.
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Key words:
- rapeseed /
- slurry-emulsion solution /
- electrothermal vaporization /
- inductively coupled plasma-mass spectrometry /
- As /
- Sb /
- Cd /
- Tl
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表 1 悬乳液进样-电热蒸发-电感耦合等离子体质谱工作条件
Table 1. Operation parameters of SES-ETV-ICP-MS
ICP-MS等离子体工作参数 条件 ETV加热过程工作参数 条件 射频功率 1250W 干燥 110℃，爬升10s，保持20s 外部气体流量 15L/min 灰化 600℃，爬升15s，保持20s 中间气体流量 0.9L/min 蒸发 2400℃，爬升0s，保持6s 辅助载气流量 0.6L/min 冷却 50℃, 爬升0s，保持5s 取样深度 7.0mm 清洁 2600℃，爬升0s，保持3s 采样锥(镍锥)直径 1.0mm 载气流速 0.4L/min 截取锥(镍锥)直径 0.4mm 数据采集参数 条件 悬乳液准备参数 条件 扫描模式 时间分辨分析 样品溶液体积 5.0mL 积分模式 峰面积 酸度 3.0% (V/V) 硝酸 停留时间 20ms 分散乳化剂曲拉通X-100浓度 1.0% (V/V) 每个谱峰点数 1 改进剂硝酸钯浓度 300μg/mL 每次读取的扫描次数 1 分析元素 75As、111Cd、121Sb、205Tl 采样量 10μL 
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表 2 样品测定分析结果(n=3)
Table 2. Analytical results of elements in rapeseeds (n=3)
油菜籽样品编号 悬乳液ETV-ICP-MS外标法测定值(ng/g) 加酸消解DC-ICP-MS外标法测定值(ng/g) As Sb Cd Tl As Sb Cd Tl JS-1 61.2±5.6 31.3±2.7 51.3±4.5 91.3±6.1 68.7±4.0 33.9±2.0 50.8±3.0 89.7±6.0 BD-2 70.9±6.4 52.9±4.6 69.1±5.8 161.7±11.2 74.6±5.2 54.9±3.2 67.0±3.9 159.8±7.9 YLS-3 90.5±9.1 28.0±2.3 58.4±5.6 119.7±8.2 95.1±6.1 25.4±1.5 55.9±3.1 126.4±7.5 YLS-4 50.4±5.1 59.9±5.3 60.2±5.3 216.6±13.6 55.7±3.3 56.9±3.6 54.7±2.9 188.9±10.1 注：悬乳液为水溶液标准(含有3%硝酸、1%曲拉通X-100、300μg/mL硝酸钯溶液)校准。
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