1、第34卷，第2期 2 0 1 4年2月 光谱学与光谱分析 Spectroscopy and Spectral Analysis Vo134，No2，pp548552 February，2014 Determination of Trace Elements in Rape Honey and Its C0rresp0nding Rape Flower and Stem by ICPMS CHEN Hui ，WANG Zhibin ，CHANG Qiaoying ， WANG Wei。，FAN Chun-lin ，PANG Guo-fang 1College of Environmental a
2、nd Chemical Engineering，Yanshan University，Qinhuangdao 066004，China 2Chinese Academy of Inspection and Quarantine，Beijing 100123，China 3College of Chemistry and Environmental Science，Hebei University，Baoding 071002，China Abstract The determination of 10 trace elements including Na，Mg，P，K，Ca，Mn，Zn，Rb
3、，Sr and Ba，in rape honey and its corresponding rape flower and stem gathered from nine sampling sites was carried out by in ductively coupled plasma mass spectrometry(ICP-MS)The contents of K，P，Ca，Mg and Na were obviously higher than Zn，Rb，Mn，Sr and Ba in rape honey，rape flower and rape stemFor the
4、first five elementsK had the highest content，followed by P，Ca，Mg and NaHowever，the order of content for latter five e1e merits was not the same in different matrixesThe contents of K，P and Ca were al1 higher than 1 000 mg kg_。in rape flower and rape stem，while the contents of P，Ca，Mn，Zn and Rb in ra
5、pe flower were slightly higher than in rape stemIt can be concluded that rape flower showed slightly higher concentrating ability for trace elements than rape stemBased on these results，radar chart was firstly applied to research the relation ship of 10 elements in rape honey and its corresponding r
6、ape flower and sternThe aim of the present work was to study the possibility of using trace elements contents in rape flower to trace the geographical and botanical origin of honey instead of rape honeyIt can be found from the radar charts that the stars of rape honey，rape flower and rape stem were
7、similar to each otherThis research not only provides the basic data of trace ele ments in comparative study of rape honey，but also gives scientific basis for tracing the origin of rape honey ac cording to the trace elements in corresponding rape flower that replaces those of rape honey Keywords Rape
8、 honey；Rape flower；Rape stem；ICP-MS；Trace element；Radar map 中图分类号：$8961 文献标识码：A DOI：103964jissn10000593(2014)02054805 Introduction Natura1 honey produced by honeybees from the nectar of plants is considered as a high value-added commodity，and is popular with consumers worldwide not only as a nutrien
9、t but also for its medica1 efficacyThe content of trace elements in honey depends on its botanical and geographical origin，and the range is between 004 and 02 Among them，the main elements components of honey are oxides of K，P，Ca and Na，and there are also many other elements such as Zn， Mg，Mn andBa，w
10、hich areimportantforthe health of human beingsE Bees collect the nectar of plants within a certain region， thus the elements in honey can provide some valuable informa tion about the geographical and botanical origin of honeyAt present，the elements in honey are always used to determine geographical
11、origin of honey and its authenticity州In the Received：20130502，accepted：20130808 Foundation ProjectThe Science and Technology Plan Project of General Administration of Quality Supervision，Inspection and Quarantine of the Peoples Republic of China(2013IK200) Biography：CHEN Hui，(1984一)，PHD Candidate of
12、 College of Environmental and Chemical Engineering，Yanshan University e-mail： happyccch163corn *Corresponding author 第2期 光谱学与光谱分析 549 research of honey tracing，the most important thing is collec ting the authentic honey samples with more detailed informa tion，or else the model for determining the or
13、igin of honey cant be established，and even wrong conclusions might be drawnIn fact，due to various restrictions on the conditions， there are many difficulties in collecting the authentic honey samples for the determination of the origin of honeyNectar of plant is considered to be the main source of t
14、race elements in honeyTherefore，its essential and necessary to determine the trace elements in honey and its corresponding nectar plant and find the relationship between themAnd then，the trace elements in flower could be considered to be applied in deter mining the origin of honeyFrom this perspecti
15、ve，the diffi culty in collecting the authentic honey samples related to the research of honey will be greatly reduced ICP-MS plays an increasingly important role in multi-ele mental analysis with very low detection 1imits。and also a wide linear dynamic range 一 In this study，ten trace elements includ
16、ing Na，Mg，P，K，Ca，Mn，Zn，Rb，Sr and Ba，i“ rape honey and its corresponding rape flower and stem，which gathered from nine sampling sites were firstly determined by ICP_MsThe aim of this study was to research the relation- ship of trace elements between rape honey and rape flower The results will provide
17、 the basic data for the research of rape honeyMore importantly，this study attempted to provide an evidence of the possibility on the application of trace elements in rape flower for honey tracingWe also predict that similar calculations could be undertaken for other honey samples 1 Experimental 11 I
18、nstruments and apparatus An Agilent 7700X ICP-MS(Agilent Technologies，Ja pan)instrument equiped with standard glass concentric nebu lizer，quartz double-pass spraychamber and nickel sampler and skimmer cones was used in this experimentThe 7700X in strument can operate the collision cellin either no g
19、as mode or helium collision modeFor the digestion pretreatment of sam ple，a MARS 6 microwave reaction system(CEM Corpora tion，USA)was usedMillipore MilliQ water purification system(Waters Corporation，Milford，MA，USA)was used to obtain the deionized water 12 Reagents and solutions Nitric acid(65 ，ww，M
20、OS grade)and hydrogen per oxide(30 ，ww，MOS grade)were purchased from BICR (Beijing，China)Deionized water with a resistivity of 182 MQ was used for al1 solutionsThe elements standard solu tions were prepared by multi-element calibration standards so lution(Agilent Technologies，USA)The mass concentrat
21、ion range for calibration curve of the elements Na，Mg，P，K and Ca was 00510 mgL一 whereas that for the elements Mn，Zn，Rb，Sr and Ba was 05100igLThe method was validated using one reference material，named GSB-7一tea (GBW10016，China) Rape honey and rape flower samples were collected in March，201 3，and fro
22、m local beekeepers in nine sampling sites in Yangxian，Shaanxi province，ChinaRape flower samples were taken from 10 cm of the top of the plant with stem 13 Sample preparation The honey samples were liquefied at 50and homoge nized in an ultrasonic bath for at least 3O min prior to analy sisRape flower
23、(with stem)samples were washed with dei onized water，and then let them dry naturallyThe rape flow er was taken off from stem，and they were chopped into small pieces，respectively Rape honey，rape flower and rape stem samples were prepared in the following procedure：1000 0 g of sample was accurately we
24、ighed and placed into PTFE digestion vessel and 5 mL of nitric acid(65 ，ww，MOS grade)and 3 m1 0f hy_ drogen peroxide(30 ，ww，MOS grade)were addedFor each digestion set，one reagent blank solution and CRM sam pie were prepared in the same wayThe sample was digested using a MARS 6 microwave reaction sys
25、tem according to the procedure in Table 1After the vessels were cooled down， the digests were transferred to a volumetric flask and diluted t0 50 nO_ with deionized water Table 1 Procedures of microwave digestion Table 2 ICP-MS operating conditions and measurement parameters Parameters lues RF power
26、 RF matching Sample depth Carrier gas Plasma gas Nebulizer pump sctemp Reaction cel1 He gas Number of replicates Interna】standard Isotopes 1 55O W 165 V 80 mm 11 Lmin-1 15 Lmin一1 01 rps 2 degC 43 mLmin一1 3 Sc4 ，Ge ，Rh ，In ，Tb 0 Na船，Mg24，P ，K ，Ca们，Mn ， Zn66，Rb85，SrSS，BalS7 If the concentration of ele
27、ment in the 50 mL sample solu 550 光谱学与光谱分析 第34卷 tion was out of the range of calibration curve，the sample so lution was diluted again with deionized water 14 ICP Ismethod In this study，only the He mode was usedTypical daily instrumental parameters are given in Table 2 Method performance could be fou
28、nd in our previous workE11_ 2 Results and Discussion 21 The contents oftrace elementsin rape honey，rapeflower andrape stem As mentioned previous，trace elements in honey were mainly from its corresponding nectar plantThe range of con tents and average values of Na，Mg，P，K，Ca，Mn，Zn， Rb，Sr and Ba in rap
29、e honey，rape flower and rape stem were 1isted in Table 3It can be found from Table 3 that the con tents of trace elements in nectar plant were much higher than in rape honeyThe average contents of these ten trace ele ments in the rape flower and rape stem collected from nine sampling sites were 4962
30、1 and 52806 times that in rape honey，respectivelyIt is obvious that the contents of Sr in rape honey had the biggest differences in both rape flower and rape stern The contents of the tested elements in each matrix were also comparedIn rape honey samples，the contents of K，P， Ca，Mg and Na were obviou
31、sly higher than Zn，Rb，Mn，Sr and Ba，and the decreasing sequence of the former five ele ments 1evels was as follows：KPCaMgNaThe cases in rape flower and rape stem were similar to rape honeyThe average content of K in rape honey，20104 mgkg_。，was far above the values of other elementsThe average value o
32、f K was 35，43，106 and 152 times that of P，Ca，Mg and Na，respectivelyThe contents of Zn in rape honey from two sampling sites were higher than from other seven sites，and the average content of Zn was 141 mgkgThe average values of Rb，Mn，Sr and Ba in rape honey were under 10 mgkg On the other hand，there
33、 were no obvious differences in the average contents for the ten elements investigated in rape flower and rape stem could be foundThe average contents of KP and Ca exceed 1 000 mgkgin themThe range con tents of Mg was 3438351449 and 3945767888 mg kg- in rape flower and rape stem，respectivelyThe aver
34、age content of Na was lower than 70 mgkg一 while the aver age values of Zn，Rb，Mn，Sr and Ba were under 10 mg kg in both rape flower and rape stemThe comparison of ten studied elements showed that the contents of P，Ca，Mn， Zn and Rb in rape flower were slightly higher than in rape stemThe average conten
35、ts of K，Na，Sr and Ba were very near in rape flower and rape stem，except for that the con tents of Mg in rape stem were higher than in rape stemIt can be concluded that both rape flower and rape stem could con centrate the trace elements，and rape flower showed slightly higher concentrating ability fo
36、r trace elements than rape stem This conclusion was similar to the research of Wu et atE Table3 Determination results ofrape honey，flower and stem(N=9，mg- ) 22 Relationship of trace elements in rape honey，rape flower and rape stem Radar charts is broadly applied to evaluate the multivari ate data，an
37、d could be conveniently used to study the relation ship between different samples In the present study，the ten investigated elements were taken as variables，each axis represents one elements and the length of ray means the aver age content in related samplesAt 1ast，all of the points were 第2期 光谱学与光谱分
38、析 551 88 sr 85 Rb 88 Sr 85 Rb (a) Rape honey 23 Na 55 Ma Rapeflower 23 Na 88 Sr 85 Rb (c) 3l P 39 K 3l P 39 K 31 P 39 K 55 Mn Fig1 Radar chart of rape honey(a)，rape flower(b)and rape stem(c) 1 2 3 connected，and then the radar charts for rape honey，rape flower and rape stem can be obtainedThey were s
39、hown in Fig1(a)，(b)and(c)，respectivelyIt can be found that the stars of radar charts for rape honey，rape flower and rape stem were similar to each otherAt the same time，the radar charts also show the contents of trace elements in rape flower and rape stem were higher than in rape honey，and this fits
40、 with that mentioned earlierFor the elements of rape honey， rape flower and rape stem researched in the present study，the content of trace elements in rape flower，instead of the con tent of elements in rape honey，can be applied to determine the botanical and geographical origin of honey 3 Conclusion
41、 Many researchers have focused on the determination of the origin of honey from different aspects，while related re search has not been reported so much in ChinaElement pro files c0uld Dmvide sufficient information to characterize the honey samples from different originsThe determination of elements
42、in honey and its corresponding nectar plants by ICP- MS has not been reportedIn this research，ten elements with relatively high contents in rape honey，rape flower and rape stem were firstly determined by ICP_MSAmong the ten test ed elements，the contents of K，P，Ca，Mg and Na were higher than Mn，Zn，Rb，
43、Sr and Ba in each matrixThe con centrating ability for trace elements for rape flower was slight higher than rape sternThis study revealed that the contents of trace elements in rape flower might be employed for deter mining the origin of honey according to the radar charts of trace elements for rap
44、e honey and its corresponding nectar plantsThe results and some conclusions of this study could be generally applied to study the trace elements in other honey sample and its corresponding nectar plantsIts hoped that this research could help researchers overcome the difficulties in collecting the au
45、thentic honey samples，and then promote the study of honey in China Acknowledgments：We also acknowledge the contribution of Mr：Xin-Min Chen from Yang Xian，Shaanxi province of China for collecting the rape honey and rape flower samples Ankalm EFood Chemistry，1998，63(4)：549 Madejezyk M，Baralkiewicz n A
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49、hina Journal of Chinese Materia Medica，2013，38(2)：154 应用ICP-MS测定油菜蜜、油菜花和油菜杆中微量元素 陈 辉 ，王志斌 ，常巧英 ，王 伟。，范春林 ，庞国芳 1燕山大学环境与化学工程学院，河北秦皇岛066004 2中国检验检疫科学研究院，北京100123 3河北大学化学与环境科学学院，河北保定071002 摘要应用电感耦合等离子体质谱(ICP-MS)定了收集于9个采样点的油菜蜜及其蜜源油菜花和油菜杆 中Na，Mg，P，K，Ca，Mn，Zn，Rb，Sr和Ba等1O种元素。在油菜蜜、油菜花和油菜杆中K，P，Ca，Mg和 Na等五种元素含量均明显高于zn，Rb，Mn，Sr和B
