3 5 Vol. 3 No. 5 2012 10 Journal of Food Safety and Quality Oct., 2012 吴 小 娟, 蔡 健 荣 *, 韩 恩, 周 立 娜, 陈 铭 枫 (, 212013) 摘 要 : 目 的 方 法,, 结 果, ph,,, 0.580 V, 5~100 μg/l(r=0.9965), 0.630 μg/l 结 论 关 键 词 : ; ; ; ; Determination of trace lead in honey with in-situ bismuth film electrode by square wave stripping voltammetry WU Xiao-Juan, CAI Jian-Rong *, HAN En, ZHOU Li-Na, CHEN Ming-Feng (School of Food and Biological Engineering, Jiangsu University, Zhenjiang 212013, China) ABSTRACT: Objective To determine the trace lead in honey with in-situ bismuth film electrode by square wave stripping voltammetry. Methods Using glassycarbon electrode in-situ plated in bismuth (III), replacing in traditional mercury(ii), the trace lead in honey was rapidly detected by square wave stripping voltammetry method. Results Several factors were optimized, including buffer solutions, ph, the concentration of Bi 3+, plating potential and plating time. Sensitive stripping peak of lead was obtained at the potential of -0.580 V in the bismuth film electrode. Under the optimized analytical condition, the stripping peak currents were changed linearly with the concentration of Pb 2+ over range from 5 ~100 μg/l (r=0.9965) with a detection limit of 0.630 μg/l. The result was in accordance with that of graphite furnace atomic absorption spectrometry (GFAAS). Conclusion The established method is rapid and accurate in detecting trace lead in honey. KEY WORDS: electrochemistry; in-situ plating bismuth film; stripping voltammetry; lead; honey,,, [1], ICP [2-5],,,,,,, 基 金 项 目 (30771243) * 通 讯 作 者 :,,, E-mail: Jrcai@ujs.edu.cn
458 3 [6-8] 2000, Wang [9],,,, [10-11],,,, [12], [13], 1 mg/kg,,, 1 实 验 部 分 1.1 主 要 仪 器 和 试 剂 CHI660D ( ); AA240GTA120 ( ); MDS-2002A ( ) : 0.1598 g (, ), 100 ml, 1 g/l Pb 2+ 10 mg/l Pb 2+ Bi 3+ : 0.0580 g (, ), 250 ml, 100 mg/l Bi 3+ 5 mg/l Bi 3+ Hg 2+ : 0.1618 g (, ), 100 ml, 1 g/l Hg 2+ 5 mg/l Hg 2+, (,, ) (1 5),,, 1.2 电 化 学 检 测 ( 3 mm),,, 1.0 0.3 0.05 μm Al 2 O 3 ; 1 mol/l 5 min Bi 3+ Pb 2+,, 0.9 V 180 s,, 30 s,, : 0.9~0 V, : 0.005 V, : 0.025 V, : 15 Hz, 25 1.3 样 品 预 处 理 0.5 g,, 6 ml, 180,,, 2 ml 1 ml,, 180 30 min,, 25 ml 1.4 石 墨 炉 原 子 吸 收 光 谱 法 检 测 GB 5009.12-2010 : 283.3 nm, 0.2~1.0 nm, 5~7 ma, 120, 20 s; 450, 15~20 s, 1700~2300, 4~5 s, 2 结 果 与 讨 论 2.1 检 测 条 件 的 优 化 2.1.1 电 极 的 选 择 0.2 mol/l ph 4.5, 50 μg/l, Pb 2+,,, Bi 3+ Hg 2+ 400 μg/l, Pb 2+, 2.1.2 支 持 电 解 质 的 选 择 0.1 mol/l HCl, 0.1 mol/l KCl, 0.1 mol/l (ph=4.5), 0.1 mol/l (ph=4.5) 0.2 mol/l (ph=4.5), 50 μg/l, 400 μg/l Bi 3+ 0.2 mol/l (ph=4.5),, 2.1.3 ph 的 选 择 Bi 3+,
5, : 459 0.2 mol/l, 50 μg/l, Bi 3+ 400 μg/l, ph 3~6, 1, ph 3~5,,, ph, ph=5 3,, 0.9 V, Fig. 3 3 Effects of plating potential on the peak current 1 ph Fig.1 Effects of ph on the peak current 2.1.4 铋 浓 度 的 选 择 50 μg/l, Bi 3+ 0~600 μg/l, 2, Bi 3+ 0~200 μg/l,, Bi 3+,,, 200 μg/l 2.1.6 沉 积 时 间 的 选 择 4 (0~600 s),,,, 180 s Fig. 4 4 Effects of plating time on the peak current 2.2 工 作 曲 线 2 Bi 3+ Fig. 2 Effects of the concentration of Bi 3+ on the peak current 2.1.5 沉 积 电 位 的 选 择 1.3~ 0.7 V,, 5~100 μg/l Pb 2+ Pb 2+ : Y (μa)=0.3483x (μg/l)+ 0.1215(r=0.9965) IUPAC : L= 0.630 μg/l(n=21)
460 3 2.3 干 扰 实 验 50 μg/l Pb 2+, 5%, : Fe 3+ (100 ) Cl - (300 ) K + (200 ) Na + (100 ) CrO 2-4 (100 )(n=5) 2.4 样 品 测 定 与 回 收 率 实 验 5 Pb 2+ Fig. 5 Standard curve of lead ion 1.3 3 3,, 1 GFAAS t, n 1=2, =0.05, t 4.303, t 2.000, t <t(, f), Table 1 表 1 蜂 蜜 样 品 中 铅 的 测 定 和 回 收 率 (n=3) Determination of lead and the recovery in honey samples(n=3) (μg/g) (μg/g) RSD (%) GFAAS (μg/g) (μg/g) (μg/g) (%) 0.188 0.172 0.185 0.264 0.279 0.298 0.227 0.218 0.217 0.182±0.008 4.68 0.188 0.5 0.280±0.017 6.08 0.271 0.5 0.221±0.06 2.50 0.227 0.5 0.628 0.642 0.618 0.839 0.699 0.859 0.796 0.827 0.666 89.5 103.7 108.5 3 结 论,,,,,,,,,,,, 参 考 文 献 [1],. [J]., 2006, 18(5): 6 10. [2] Duran C, Gundogdu A, Bulut VN, et al. Solid-phase extraction of Mn(II), Co(II), Ni(II), Cu(II), Cd(II) and Pb(II) ions from environmental samples by flame atomic absorption spectrometry (FAAS)[J]. J Hazard Mater, 2007, 146(1 2): 347 355. [3] Pohl P. Determination of metal content in honey by atomic absorption and emission spectrometries[j]. Trends Anal Chem, 2009, 28(1): 117 128. [4] Ioannidou MD, Zachariadis GA, Anthemidis AN, et al. Direct determination of toxic trace metals in honey and sugars using inductively coupled plasma atomic emission spectrometry[j]. Talanta, 2005, 65(1): 92 97. [5] Zhu ZL, Liu JX, Zhang SC, et al. Determination of Se, Pb, and Sb by atomic fluorescence spectrometry using a new flameless, dielectric barrier discharge atomizer[j]. Spectroch Acta Part B, 2008, 63(3): 431 436. [6] Sanna G, Pilo MI, Piua PC, et al. Determination of heavy metals in honey by anodic stripping voltammetry at microelectrodes[j]. Anal Chim Acta, 2000, 415(1 2): 165 173. [7] Li YH, Liu XY, Zeng XD, et al. Simultaneous determination of ultra-trace lead and cadmium at a hydroxyapatite-modified carbon ionic liquid electrode by square-wave stripping voltammetry[j]. Sensor Actuat B Chem 2009, 139(2): 604 610. [8] Babkina SS, Ulakhovich NN. Amperometric biosensor based on denatured DNA for the study of heavy metals complexing with DNA and their determination in biological, water and food samples[j]. Bioelectrochemistry, 2004, 63(1 2): 261 265. [9] Wang J, Lu JM, Hocevar SB, et al. Bismuth-Coated Carbon Electrodes for Anodic Stripping Voltammetry[J]. Anal Chem,
5, : 461 2000, 72(14): 3218 3222. 作 者 简 介 [10],,,. [J]., 2008, 36(2): 177 181. [11],,. [J]., 2002, 30(9): 1092 1095. [12] Alghamdi AH. Applications of stripping voltammetric techniques in food analysis[j]. Arab J Chem, 2010, 3 (1) : 1 7. [13] GB 14963-2003, [S]. ( 责 任 编 辑 : 张 宏 梁 ) 吴 小 娟,,,, E-mail: xiaojuan_wu@sina.cn 蔡 健 荣, 男, 教 授, 博 士 生 导 师, 主 要 从 事 农 产 品 无 损 检 测 技 术 收 获 机 器 人 技 术 研 究 E-mail: jrcai@ujs.edu.cn ˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆˇˆ,, 2009 2011, 2012,,,,,,, 2013,, 2012 12 31 Email www.chinafoodj.com Email tougao@chinafoodj.com