微波消解-电感耦合等离子体质谱法测定粉煤灰中铀
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摘要
粉煤灰是一种宝贵的铀资源,为了满足我国日益增长的核电对铀的需求,必须加大对粉煤灰中铀的综合回收利用,因此准确测定粉煤灰中铀含量意义重大。采用HNO_3-HF-HClO_4体系微波消解样品,选择~(187)Re为内标元素,~(238)U为铀测定同位素,建立了微波消解-电感耦合等离子体质谱法(ICP-MS)准确快速测定粉煤灰中铀的分析方法。对溶样条件进行了优化,确定溶样酸用量为5.0mL HNO_3、3.0mL HF、0.50mL HClO_4,消解程序如下所示:消解功率为800W,15min从室温升到150℃,保温10min,15min从150℃升到200℃,保温30min。实验表明,当铀的质量浓度范围为0.5～20ng/mL时,铀的质量浓度与其对应的信号强度呈线性关系,线性相关系数为0.9999,方法检出限为0.05μg/g。将实验方法应用于粉煤灰实际样品分析,测定结果的相对标准偏差(RSD,n=6)为3.2%,加标回收率为95%～104%。选取来自不同地方燃煤电厂的粉煤灰,按照实验方法进行铀的测定,并与激光荧光法进行对比,两种方法测定结果基本一致。
The coal fly ash was a kind of valuable uranium resource.The comprehensive recovery and use of uranium in coal fly ash must be strengthened in order to meet the increasing demands of uranium in nuclear power industry.Therefore,the accurate determination of uranium content in coal fly ash was of great significance.The sample was treated by microwave digestion in nitric acid-hydrofluoric acid-perchloric acid system.An accurate and rapid determination method of uranium in coal fly ash by inductively coupled plasma mass spectrometry(ICP-MS)with microwave digestion was established with ~(187)Re as the internal standard element and ~(238)U as the determination isotope.The sample dissolution conditions were optimized.The acid dosage was selected as follows:5.0 mL of nitric acid,3.0 mL of hydrofluoric acid and 0.50 mL of perchloric acid.The digestion procedures were listed as follows:the digestion power was 800 W;the temperature was increased from room temperature to 150℃ in 15 min and kept for 10 min;then the temperature was increased from 150℃ to 200℃ in 15 min and kept for 30 min.The experimental results showed that the mass concentration of uranium in range of 0.5-20 ng/mL was linear to its corresponding signal intensity with linear correlation coefficient of 0.999 9.The detection limit of method was 0.05μg/g.The proposed method was applied for the analysis of coal fly ash actual sample.The relative standard deviation(RSD,n=6)of the results was 3.2%.The spiked recoveries were between 95% and 104%.Various coal fly ash samples from different coal-fired power plants were determined according to the experimental method.The found results were basically consistent with those obtained by laser fluorescence method.
The coal fly ash was a kind of valuable uranium resource.The comprehensive recovery and use of uranium in coal fly ash must be strengthened in order to meet the increasing demands of uranium in nuclear power industry.Therefore,the accurate determination of uranium content in coal fly ash was of great significance.The sample was treated by microwave digestion in nitric acid-hydrofluoric acid-perchloric acid system.An accurate and rapid determination method of uranium in coal fly ash by inductively coupled plasma mass spectrometry(ICP-MS)with microwave digestion was established with ~(187)Re as the internal standard element and ~(238)U as the determination isotope.The sample dissolution conditions were optimized.The acid dosage was selected as follows:5.0 mL of nitric acid,3.0 mL of hydrofluoric acid and 0.50 mL of perchloric acid.The digestion procedures were listed as follows:the digestion power was 800 W;the temperature was increased from room temperature to 150℃ in 15 min and kept for 10 min;then the temperature was increased from 150℃ to 200℃ in 15 min and kept for 30 min.The experimental results showed that the mass concentration of uranium in range of 0.5-20 ng/mL was linear to its corresponding signal intensity with linear correlation coefficient of 0.999 9.The detection limit of method was 0.05μg/g.The proposed method was applied for the analysis of coal fly ash actual sample.The relative standard deviation(RSD,n=6)of the results was 3.2%.The spiked recoveries were between 95% and 104%.Various coal fly ash samples from different coal-fired power plants were determined according to the experimental method.The found results were basically consistent with those obtained by laser fluorescence method.
引文
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[10]郭国龙,杨丹丹,王春叶.微波消解-电感耦合等离子体原子发射光谱法测定废脱硝催化剂中钨和钛[J].冶金分析,2018,38(1):70-74.GUO Guo-long,YANG Dan-dan,WANG Chun-ye.Determination of tungesten and titanium in waste denitration catalyst by microwave digestion-inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2018,38(1):70-74.
[11]孙秉怡,全葳,卢瑛,等.微波消解-激光荧光法测定土壤样品中微量铀[J].核化学与放射化学,2017,39(4):268-272.SUN Bing-yi,QUAN Wei,LU Ying,et al.Determination of trace uranium in soil samples by microwave digestion-laser fluorescence method[J].Journal of Nuclear and Radiochemistry,2017,39(4):268-272.
[2]周秀林,周文辉.苯基荧光酮分光光度法测定煤灰中微量铀[J].冶金分析,2005,25(2):56-58.ZHOU Xiu-lin,ZHOU Wen-hui.Spectrophotometric determination of trace uranium(VI)in coal ashes with phenyfluorone[J].Metallurgical Analysis,2005,25(2):56-58.
[3]Premadas A,P K Srivastava.Rapid laser fluorometric method for the determination of uranium in soil,ultrabasic rock,plant ash,coal fly ash and red mud samples[J].Journal of Radioanalytical and Nuclear Chemistry,1999:242(1):23-27.
[4]Bal K,Puri,Keemti,et al.Differential pulse polarographic determination of uranium(VI)in complex materials after adsorption of its trifluoroethylxanthate cetyltrimethylammonium ion-associated complex on naphthalene adsorbent[J].Analytical Sciences:the International Journal of the Japan Society for Analytical Chemistry,2002,18(4):427-32.
[5]John G Arnason,Christine N Pellegri,Patrick J Parsons.Determination of total uranium and uranium isotope ratios in human urine by ICP-MS:results of an interlaboratory study[J].Journal of Analytical Atomic Spectrometry,2015,30(1):126-138.
[6]Martina Rozmaric,Astrid GojmeracIvsic,Zeljko Grahek.Determination of uranium and thorium in complex samples using chromatographic separation,ICP-MS and spectrophotometric detection[J].Talanta,2009,80(1):352-362.
[7]Aleksandr Ganeev,Oksana Bogdanova,Ilia Ivanov.Direct determination of uranium and thorium in minerals by time-of-flight mass spectrometry with pulsed glow discharge[J].Rsc Advances,2015,5(99):80901-80910.
[8]Jordana R Wood,Gary A Gill,Li-Jung Kuo.Comparison of analytical methods for the determination of uranium in seawater using inductively coupled plasma mass spectrometry[J].Industrial&Engineering Chemistry Research,2016,55(15):4344-4350.
[9]石变芳,刘达,张小满,等.微波消解-ICP-MS法测定煤炭中汞、铍、砷和铀[J].实验室研究与探索,2016,35(11):4-8.SHI Bian-fang,LIU Da,ZHANG Xiao-man,et al.Determination of mercury,beryllium,arsenic,and uranium in coal samples by inductively coupled plasma-mass spectrometry with microwave digestion[J].Research and Exploration in Laboratory,2016,35(11):4-8.
[10]郭国龙,杨丹丹,王春叶.微波消解-电感耦合等离子体原子发射光谱法测定废脱硝催化剂中钨和钛[J].冶金分析,2018,38(1):70-74.GUO Guo-long,YANG Dan-dan,WANG Chun-ye.Determination of tungesten and titanium in waste denitration catalyst by microwave digestion-inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2018,38(1):70-74.
[11]孙秉怡,全葳,卢瑛,等.微波消解-激光荧光法测定土壤样品中微量铀[J].核化学与放射化学,2017,39(4):268-272.SUN Bing-yi,QUAN Wei,LU Ying,et al.Determination of trace uranium in soil samples by microwave digestion-laser fluorescence method[J].Journal of Nuclear and Radiochemistry,2017,39(4):268-272.