Determination of Barium in Purple Clay Products for Food Contact by
Energy Dispersive X-Ray Fluorescence Spectrometry
XU Wei-xuan1, CHEN Wen-bin2, 3*
1. School of Arts, Tiangong University, Tianjin 300387, China
2. Business College, China Academy of Management Science, Beijing 100020, China
3. Shenzhen EDXRF of IoT Technology Ltd., Shenzhen 518017, China
Abstract：The purpose of this paper is to promote the use of additives in purple clay products for food contact in line with national standards. Through instrumental analysis, this paper has established a non-destructive testing method for toxic barium salt added purple clay products, so that the industry can effectively use this technology for purple clay production quality management and material safety assessment. The method is to directly test the samples by energy dispersive X-ray fluorescence spectrometry, establish a set of standard samples with components to complete the function relationship between photon number and content, and carry out a database of comparison and the precision analysis by a large number of purple clay raw ore, mud raw material and purple clay products in various periods. The process is to analyze the consistency of repeated tests under the selected instruments and operating conditions with RSD in 1.75%～4.83%. The relative standard deviations (RSD) of homogeneity of standard samples are 3.10%～5.59%. The relative standard deviations of 10 purple clay samples are 1.23%～12.30%. The test of the specimens with thickness ranging from 1.9 to 14.1 mm shows the change rate between the test value and the real value is -6.94% to 78.44%. The average content of barium in 109 samples of purple clay ore is 0.029 5%. Tests are carried out on three kinds of clay materials without barium carbonate and two kinds of purple clay materials with barium carbonate of about 3‰ and the results show mud materials with barium carbonate, and the test value of barium is 0.380%～0.398%. In the mud without barium carbonate, the test value of barium is 0.016 2% to 0.046 1%. The barium content of 11 purple clay ware samples from 1979 and later is 0.238 8% to 0.387 7%. The actual analysis data of 1 085 purple clay samples show that barium content in purple clay products increased gradually after 1979. The conclusion is that this method has the characteristics of non-destructive, high efficiency, high speed, high accuracy, good consistency of repeated tests and easy operation, and it is more suitable for the determination of barium carbonate additive in food contact violet purple sand compared with the chemical test method. At the same time, through a large number of experimental data, it is found that the beginning of the artificial addition of barium carbonate was about 1979. Since then, the content of barium element in purple clay products has shown a rising trend, indicating that in the absence of effective measurement methods and technical supervision, the behavior of adding barium carbonate could not be substantially controlled.
[1] General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization Administration of the People’s Republic of China（中华人民共和国国家质量监督检验检疫总局，中国国家标准化管理委员会）. GB/T 1614—2011 Barium Carbonate for Industrial Use(GB/T 1614—2011工业碳酸钡). Beijing: Standards Press of China(北京：中国标准出版社)，2011.
[2] Krishna, Supriya, Jaiswal A K, et al. International Journal of Advanced Research in Medicinal Chemistry, 2020, 2(1): 22.
[3] Yang F, Massey I Y. Biometals, 2019, 32(4): 563.
[4] ZHOU Zhi（周 志）. Zhuangshi（装饰）, 2017, 292(8): 12.
[5] National Health and Family Planning Commission of the People’s Republic of China(国家卫生和计划生育委员会). GB 4806.1—2016 National Food Safety Standard-General Ssafety Rrequirements for Food Safety National Standard Food Contact Materials and Pproducts (GB4806.1—2016，食品安全国家标准 食品接触材料及制品通用安全要求). Beijing: Standards Press of China(北京：中国标准出版社)，2016.
[6] National Health and Family Planning Commission of the People’s Republic of China(国家卫生和计划生育委员会). GB9685—2016 National Food Safety Standard-Standards for Uses of Additives of Food Contact Materials and Products(GB9685—2016，食品安全国家标准 食品接触材料及制品用添加剂使用标准). Beijing: Standards Press of China(北京：中国标准出版社)，2016.
[7] Sidnei O Souza, Dayara V L Ávila, Carolina M O Prado, et al. Journal of the Brazilian Chemical Society，2021, 32: 2.
[8] NI Zi-yue, CHEN Da-wei, LIU Ming-bo, et al（倪子月, 程大伟, 刘明博, 等）. Spectroscopy and Spectral Analysis（光谱学与光谱分析），2020, 40(9): 2980.
[9] CHEN Jing-wei, SONG Jiang-tao, CHEN Chao-yang（陈景伟，宋江涛，陈朝阳）. Rock and Mineral Analysis（岩矿测试），2017, 36(4): 382.
[10] Katsifas C S, Zachariadis G A, Current Analytical Chemistry，2019, 15(7): 776.
[11] Rovetta T, Invernizzi C, Licchelli M, et al. X-Ray Spectrometry，2018, 47(2): 159.
[12] Ridolfi S. Insight-Non-Destructive Testing and Condition Monitoring，2017, 59(5): 273.
[13] Cesareo R, Ridolfi S, Brunetti A, et al. Acta Imeko，2018, 7: 8.
[14] Wen R, Zhang Y, Wang D, et al. Analytical Methods，2017, 9(30): 4380.
[15] Buccolieri A, Degl’Innocenti E, Cesareo R, et al. Measurement，2018, 126: 164.
[16] General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization Administration of the People’s Republic of China（中华人民共和国国家质量监督检验检疫总局，中国国家标准化管理委员会）. GB/T 31364—2015 Test Methods for Main Performance of Energy Dispersive X-Ray Fluorescence Spectrometer（GB/T 31364—2015，能量色散X射线荧光光谱仪主要性能测试方法）. Beijing: Standards Press of China(北京：中国标准出版社)，2015.
[17] YIN Ming, LI Jia-xi, et al（尹 明, 李家熙，等）. Analysis of Rocks and Minerals. Volume Ⅱ, Analysis of Rocks, Nonmetal and Ferrous Metal Minerals（岩石矿物分析. 第二分册, 岩石, 非金属和黑色金属矿石分析）. Beijing: Geological Publishing House（北京：地质出版社）, 2011. 285.
[18] XIU Feng- feng, FAN Yong, LI Jun-yu, et al（修凤凤, 樊 勇, 李俊雨, 等）. Rock and Mineral Analysis（岩矿测试），2018, 37(5): 526.
[19] ZHU Ze-wei, SHEN Ya-qin （朱泽伟，沈亚琴）. YiXing Purple Sand Mineral（宜兴紫砂矿料）. Beijing: Geological Publishing House（北京：地质出版社），2009. 11.
