X- 43 DOI 10. 13822 /j. cnki. hxsj. 2016. 01. 010 2016 38 1 43 ~ 46 51 X- * 214431 X- 6 0. 999 0. 02% ~ 4. 2% X- O657. 34 A 0258-3283 2016 01-0043-04 Determination of As Cu Sb Sn Bi and Pb in Lead Alloy by X-Ray Fluorescence Spectroscopy LU Xiao-bin LI Ying FENG Xiu-mei * LU Wei CHEN Jun Jiangyin Product Quality Supervision and Testing Institute Jiangyin 214431 China Huaxue Shiji 2016 38 1 43 ~ 46 51 Abstract A rapid detection method of As Cu Sb Sn Bi and Pb in lead alloy by X-ray fluorescence spectroscopy was established. The optimum parameters of the detection was established by optimizing the test condition which can effectively avoid the interference of other elements. Calibration curve of the elements was draw using the experience influence coefficient correction method based on the strength and concentration of the interference elements. The experimental results show that As Cu Sb Sn Bi and Pb have a good linear relationship in a certain concentration range and the correlation coefficients of Bi Sb and Sn was above 0. 999. The test results of precision show that the relative standard deviation was between 0. 02% and 4. 2%. The test results of accuracy show that the measured value is consistent with reference value. Key words X-ray fluorescence lead alloy As Cu Sb Sn Bi Pb 1-3 1 GB /T 1. 1 4103 2012 ARL Perform'X 4-8 GB /T 4103. 16 2012 GPY-Ⅱ 9 X- Pb60Sn40 GBW 02401 GBW 02402 GBW 02301 2015-06-11 10-16 X- 1979- E-mail fengxiumei@ jqt-cn. com
44 2016 1 GBW 02302 0. 5 1 YT8801 Bi Lα 2θ 44. 5 ~ 49. 5 8405-2 Pb Kα As Kα ZChSnSbD4-4 ZChSnSbD12-3-10 99. 999% 2θ Bi Lα 99. 999% Pb50Sn50 P10 90% 99. 998% 10% 99. 95% 99. 8% 1. 2 1 Bi Lα 2θ 44. 5 ~ 49. 5 Fig. 1 Bi Lα line for 2θ angle in the range of X- 44. 5 ~ 49. 5 10 20 MPa 22 s 5 s 5 s 9 s 2 2. 1 2 Sb Kα 2θ 18 ~ 20 2 Sn Kα 19. 839 Sb Kα 19. 012-0. 51 18. 502 X- Sn Kα 1 1 Tab. 1 Analysis conditions of lead alloy 40 kv 60 ma Kα Lα 48. 73 48. 77 Bi Lα 2 Sb Kα 2θ 18 ~ 20 Fig. 2 Sb Kα line for 2θ angle in the range of 18 ~ 20 2θ / /s As Kβ 30. 451 0 2 0. 40 20 Bi Lα 47. 361-0. 84 0 0. 15 12 K L Cu Kα 45. 027 0 1 0. 40 12 Kα Pb Lβ 40. 379 0 0 0. 15 12 Kα As Kα Pb Lα 2θ 48. 733 Sb Kα Sn Kα 19. 012 19. 012-0. 51 0 0 0 0. 15 0. 15 12 12 Cu 0. 27 Cu 0. 27 48. 772 0. 039 LiF200 SC PHD 40 ~ 105 As Kβ Pb Lβ2θ 40. 3791 30. 451 2. 2 11 Bi Lα Bi Lα 2θ 47. 361 As Kα 1. 372 X- 2
X- 45 2 Tab. 2 Reference value of the standard samples % c i = a 0 + a 1 I i + n a j I j 0. 014 0. 024 1. 96 65. 72 16. 09 15. 97 a 0 + a 1 I i a j I j 0. 056 0. 027 59. 02 0. 354 40. 54 0. 013 0. 007 5 2. 88 76. 22 15. 02 5. 69 0. 018 1. 32 7. 87 86. 61 0. 020 6. 72 1. 20 11. 81 80. 27 0. 003 4 0. 127 0. 000 9 1. 73 30. 12 0. 065 0. 27 4. 69 99. 999 0. 000 1 0. 000 1 99. 999 0. 000 1 0. 000 1 48. 8 51. 1 0. 069 4. 09 / / n n a. b. 3 As 15 α 16 Fig. 3 Calibration curve of As element 2. 2. 1 2. 2. 2 3 Tab. 3 Linear range and correlation coefficient of each element w /% As 0. 01 ~ 0. 069 Pb Sb AI 3. 57 10-8 3. 55 10 7 Bi 0. 01 ~ 0. 13 Pb AI - 7. 9 10-8 Cu 0. 01 ~ 6. 72 Pb 0. 01 ~ 76. 22 Sn MC - 0. 002 9 Sb 0. 01 ~ 16. 09 Pb Sn MC 0. 017 33 0. 002 60 Sn 0. 01 ~ 86. 61 Pb MC 0. 017 0 As y = 0. 061 50x - 0. 038 52 0. 985 0 Bi y = 0. 092 72x + 0. 179 5 0. 999 7 Cu y = 0. 020 36x - 0. 046 53 0. 993 0 Pb y = 0. 094 29x - 0. 643 97 0. 998 0 Sb y = 0. 417 33x - 0. 014 2 0. 999 0 Sn y = 0. 51x + 0. 072 0. 999 8 a j AI Addtive intensity 2 3 3a b As 3a 3b a. b. 4 Sb Fig. 4 Calibration curve of Sb element MC Multiplicative concentration c i = a 0 + a 1 I i 1 + n a j c j
46 2016 1 i j a j a 0 + a 1 I i 1 + n a j c j 2 X- 3 Sb 4a 4b Sb 4a 4b X- 2. 3 9 4 0. 04% ~ 5. 8% 1. - J. 2005 14 6 22-24. 2. J. - 4 2010 46 10 1 213-1 215. Tab. 4 Test results for precision 3. ICP-AES w /% J. 2008 25 6 1 143-1 150. 1 0. 048 4 0. 079 8 10. 01 5. 39 0. 086 2 84. 40 4 2 0. 045 3 0. 080 6 10. 06 5. 38 0. 087 9 84. 36. GB /T 4103. 1 2012 3 0. 049 6 0. 083 7 10. 06 5. 36 0. 088 3 84. 37 1 S. 4 0. 047 4 0. 074 7 10. 04 5. 34 0. 085 4 84. 43 2012 1-16. 5 0. 048 5 0. 077 1 10. 09 5. 36 0. 862 0 84. 35 5 6 0. 047 4 0. 074 1 10. 07 5. 38 0. 087 0 84. 34. GB /T 4103. 2 2012 7 0. 052 4 0. 075 7 10. 03 5. 37 0. 088 0 84. 39 2 S. 8 0. 049 1 0. 078 2 10. 06 5. 38 0. 087 0 84. 44 2012 1-16. 0. 048 3 0. 088 7 10. 06 5. 38 0. 087 0 84. 38 6 0. 002 0. 003 0. 025 0. 016 0. 001 0. 037 4. 2% 3. 4% 0. 25% 0. 30% 1. 2% 0. 04% 3 S. 2. 4 7. GB /T 4103. 5 2012 5 S. 5 5 8 /% 5. 8 1. 2 2. 6 0. 24 0. 50 0. 19 3 X-. GB /T 4103. 3 2012. GB /T 4103. 6 2012 5 6 S. Tab. 5 Test results for accuracy 9 0. 049 0. 087 0. 081 84. 34 10. 05 5. 41 0. 052 0. 088 0. 079 84. 14 10. 10 5. 40. GB /T 4103. 16 2012 0. 003 0. 001 0. 002 0. 20 0. 05 0. 01 16 S. 2012 1-7. 51
QuEChERS - 51 GC-ECD produce J. J. AOAC Int. 2003 86 2 421-431. 12 8. QuEChERS / - J. 2013 32 10 1237-1241. 9 LEHOTAY S J KOK A D HIEMSTRA M et al. Validation of a fast and easy method for the determination of residues from 229 pesticides in fruits and vegetables 1 GUILLARME D CASETTA C BICCHI C et al. High throughput qualitative analysis of polyphenols in tea samples by ultra-high pressure liquid chromatography coupled to UV and mass spectrometry detectors J. J. Chromatogr. A 2010 1 217 44 6 882-6 890. 2 XU Xiao-min YU Cun HAN Jian-long et al. Multi-residue analysis of pesticides in tea by online SEC-GC /MS J. J. Sep. Sci. 2011 34 2 210-216. 3 PANG Guo-fang FAN Chun-lin ZHANG Feng et al. High-throughput GC /MS and HPLC /MS /MS techniques for the multiclass multiresidue determination of 653 pesticides and chemical pollutants in tea J. J. AOAC Int. 2011 94 4 1 253-1 296. 4 HUANG Zhi-qiang LI Yong-jun CHEN Bo et al. Simultaneous determination of 102 pesticide residues in Chinese teas by gas chromatography-mass spectrometry J. J. Chromatogr. B 2007 853 2 154-162. 5 YANG Xin XU De QIU Jian et al. Simultaneous determination of 118 pesticide residues in Chinese teas by gas chromatography-mass spectrometry J. Chem. Pap. 2008 63 1 39-46. 6 HU Yan-yun ZHENG Ping HE You-zhao et al. Response surface optimization for determination of pesticide multiresidues by matrix solid-phase dispersion and gas chromgatography J. J. Chromatogr. A 2005 1 098 1 / 2 188-193. 7 ANASTASSIADES M LEHOTAY S J STAJNBAHER D et al. Fast and easy multiresidue method employing acetonitrile extraction / partitioning and dispersive solid-phase extraction for the determination of pesticide residues in using gas and liquid chromatography and mass spectrometric detection J. J. AOAC Int. 2005 88 2 595-614. 10. DPX-Q / 102 J. 2015 34 2 236-242. 11 GONZ LEZ-CURBELO M HERN NDEZ-BORGES J. Determination of pesticides and their metabolites in processed cereal samples J. Food Addit. Contam. Part A Chem. Anal. Control. Expo. Risk Assess. 2011 29 1 104-116. 12 KANRAR B MANDAL S BHATTACHARYYA A. Validation and uncertainty analysis of a multi-residue method for 42 pesticides in made tea infusion and spent leaves using ethyl acetate extraction and liquid chromatography-tandem mass spectrometry J. J. Chromatogr. A 2010 1 217 12 1 926-1 933. 13. - 13 J. 2009 19 2 263-265. 14 GUAN Ya-qin TANG Hua CHEN Da-zhou et al. Modified QuEChERS method for the analysis of 11 pesticide residues in tea by liquid chromatography-tandem mass spectrometry J. Anal. Methods 2013 5 12 3 056-3 067. 15 CHEN Hong-ping YIN Peng WANG Qing-hua et al. A modified QuEChERS sample preparation method for the analysis of 70 pesticide residues in tea using gas chromatography-tandem mass spectrometry J. Food Anal. Methods 2014 7 8 1 577-1 587. 16. FPD J. 2011 28 3 270-272. 46 10. YS /T 483 2005 X- S. 2005 1-7. 11. X- J. 2012 6 15 34-39. 12 24 D. 2012. 13 J. 2006 5 3 36-38.. X- 16. X-. X 2008. J. 2014 13 11 61-62. 14. X- 9 J. - 2015 51 1 114-116. 15. X- D.