Determination of Trace Ga in Water and Plant Samples by O2-doped Air-Acetylene FAAS with Solid Phase Extraction Preconcentration
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摘要: 目前研究萃取分离富集镓大多偏向在强酸性体系中，一定程度上给操作带来安全风险，另需耐酸器皿设备，易污染，空白背景值高。本文开发了一种在弱酸性条件下萃取分离富集痕量镓的方法。以大孔吸附树脂为载体，十六烷基三甲基溴化铵调节其表面极性，热固化负载2-乙基己基磷酸（2-乙基己基）酯，制备了镓的萃取树脂。动态考察了固相萃取镓的吸附容量，优化选择固相萃取分离富集条件，实验表明萃取条件温和，分离富集痕量镓效果理想。当溶液酸度为pH 2.5时，Ga（Ⅲ）达到最大的回收率99%，并确定了掺氧空气乙炔火焰原子吸收光谱法（FAAS）测定镓的最佳参数，提升了常规空气乙炔FAAS测定镓的灵敏度。方法检出限（3σ）为2.6ng/mL，相对标准偏差（RSD，n=7）为2.87%，加标回收率在95.7%~102.0%之间，理论富集倍数为40。本方法已应用于自来水、中药材和水培蔬菜样品中痕量镓的测定，简便、快速、可靠。要点
(1) 制备价廉的固相萃取介质。
(2) 在弱酸性体系中对痕量Ga进行固相萃取分离预富集前处理。
(3) 优化了固相萃取O2-空气-乙炔FAAS测定镓的方法，拓宽了FAAS使用范围。
HIGHLIGHTS(1) A cheap solid-phase extraction media was prepared.
(2) Preconcentration of trace Ga in weak acidic system by solid phase extraction was established.
(3) A method for determination of trace gallium by O2-air-C2H2 FAAS with solid phase extraction was established, and the application of FAAS was extended.
Abstract:BACKGROUNDAt present, research on the extraction separation and enrichment of gallium is mostly biased to the strong acidic system, which brings a safety risk to the operation and needs acid-proof apparatus. Furthermore, the procedure is easily contaminated, resulting in high background values.OBJECTIVESTo develop a method for extraction separation and preconcentration of trace Ga under weakly acidic condition.METHODSSolid phase extraction medium for Ga was prepared by using modified large porous adsorption resin with cetyl-trimethyl-ammonium bromide and loading it with 2-ethylhexyl phosphonic acid-2-ethylhexyleste. The separation and enrichment conditions of solid phase extraction were studied in detail.RESULTSExperiments showed that the separation and enrichment of trace gallium was ideal when the extraction conditions were mild. The maximum recovery (99%) of Ga was achieved in sample solution with pH of 2.5. The determination parameters of gallium were optimized for oxygen doped air-acetylene flame atomic absorption spectrometry (FAAS), and the sensitivity was improved on that of the current method. The detection limit of the overall method (3σ) was 2.6ng/mL by IUPAC definition and the relative standard deviation (RSD, n=7) was 2.87%. The recoveries for spiked solution ranged from 95.7% to 102.0%, and a theory enrichment factor of 40 was obtained.CONCLUSIONSThis method has been successfully applied to the determination of trace gallium in tap water, Chinese medicine and hydroponic vegetable samples. It is simple, quick and reliable.
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Keywords:
- water /
- plant /
- Ga /
- solid phase extraction /
- oxygen doped air acetylene flame /
- atomic absorption spectrometry
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表 1 本文与文献报道固相萃取分析镓的方法性能比较
Table 1 Comparison of the method with those reported in the literature for Ga(Ⅲ)
吸附剂 方法 富集倍数 检出限 样品 文献 聚氨酯塑料 SPE-ICP-MS - 22ng/g 稀土矿石 [24] 改性胺基硅胶 SPE-FAAS 200 4.1ng/mL 水，沉积物 [25] Amberlite XAD-4树脂 SPE-UV-Vis 500 3.1ng/mL 水，生物 [26] 聚氨酯泡沫体强酸阳离子交换纤维 SPE-FAAS
SPE-ICP-AES40
-6.0ng/mL
3.9ng/mL铝合金，尿液
铝土岩[27]
[28]离子印迹多壁碳纳米管 SPE-FAAS 43 3.03ng/mL 飞灰 [29] 磷酸三丁酯纤维棉 SPE-ICP-AES 5 65ng/mL 地质样品 [30] 改性大孔树脂 SPE-掺氧空气乙炔FAAS 40 2.6ng/mL 水，植物 本研究 
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表 2 样品测定分析结果(n=3)
Table 2 Analytical results for Ga(Ⅲ) in water solution and solid samples (n=3)
样品 样品含量水样(μg/L)
植物(μg/g)平均值水样(μg/L)
植物(μg/g)加标量水样(μg/L) 测定值水样(μg/L) 回收率
(%)ICP-MS法水样(μg/L)
植物(μg/g)自来水 20.9，20.3, 19.1 20.1 15
2533.6
46.095.7
102.019.3 何首乌 1.27，1.29, 1.36 1.31 - - - 1.27 花生芽 61.3, 61.9, 60.5 61.2 - - - 62.3 注：标注“-”为植物固体样未做加标回收实验。
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