全 文 :第3 5卷,第5期 光 谱 学 与 光 谱 分 析 Vol.35,No.5,pp1398-1403
2 0 1 5年5月 Spectroscopy and Spectral Analysis May,2015
ICP-AES Determination of Mineral Content in Boletus Tomentipes
Colected from Different Sites of China
WANG Xue-mei 1,ZHANG Ji 2,LI Tao3,LI Jie-qing1,
WANG Yuan-zhong2*,LIU Hong-gao1*
1.Colege of Agronomy and Biotechnology,Yunnan Agricultural University,Kunming 650201,China
2.Institute of Medicinal Plants,Yunnan Academy of Agricultural Sciences,Kunming 650200,China
3.Colege of Resources and Environment,Yuxi Normal University,Yuxi 653100,China
Abstract P,Na,Ca,Cu,Fe,Mg,Zn,As,Cd,Co,Cr and Ni contents have been examined in caps and sti-
pes of Boletus tomentipes colected from different sites of Yunnan province,southwest China.The elements
were determined using inductively coupled plasma atomic emission spectroscopy(ICP-AES)with microwave
digestion.P,Ca,Mg,Fe,Zn and Cu were the most abundant amongst elements determined in Boletus tomen-
tipes.The caps were richer in P,Mg,Zn and Cd,and the stipes in Ca,Co and Ni.Cluster analysis showed a
difference between Puer(BT7and BT8)and other places.The PCA explained about 77%of the total vari-
ance,and the minerals differentiating these places were P(PC1)together with Ca,Cu,Fe,Mg,As and Ni,
Na(PC2)together with Cd,and Zn(PC3).The results of this study imply that element concentrations of a
mushroom are mutative when colected from the different bedrock soil geochemistry.
Keywords Fungi;Elements;Wild edible mushroom;Multivariate analysis;Bedrock geochemistry
中图分类号:O657.3 文献标识码:A DOI:10.3964/j.issn.1000-0593(2015)05-1398-06
Received:2014-07-13;accepted:2014-10-19
Foundation item:the National Natural Science Foundation of China(31260496,31160409),the Yunnan Provincial Natural Science Foundation
(2011FB053,2011FZ195),and the Science Foundation of the Yunnan Province Department of Education (2012Y380,
2013Z074)
Biography:WANG Xue-mei,(1987—),apostgraduate student in School of Agronomy and Biotechnology,Yunnan Agricultural University
e-mail:wxm1123520@163.com *Corresponding authors e-mail:boletus@126.com;honggaoliu@126.com
Introduction
Mushrooms are highly appreciated for their nutrition val-
ue and medicinal properties as wel as for aroma and delicate
texture worldwide[1-4]. Nevertheless, edible wild-grown
mushrooms have been preferred to cultivated species for their
unique flavor characteristics,natural regional features and
mineral element contents[5,6].The consumption of edible
wild-grown mushroom is 5.6kg of fresh per household yearly
in Czech Republic and 2.5kg per capita in the United States
while higher value was found to be 20~24kg in Liangshan Yi
nationality,China[7-9].
Edible wild-grown mushroom play an important role in
element cycling and transformations[10-12].They are able to
accumulate significant amounts of macro-and micro-elements
that are beneficial to their consumers[13-15].Elevated content
of toxic metals such as As,Hg,Cd and Pb can be found in
mushrooms colected from smelters or roadsides[16,17].Ele-
ment content of mushroom is generaly affected by environ-
mental factors,species,trophic pattern,age of fruiting body
and size of less importance[18,19].Recently numerous studies
were carried out on mineral constituents in edible wild-grown
mushrooms colected from different ecological environments.
Researches have shown the correlation between mineral con-
centration and different soil bedrock geochemistry,for exam-
ple mushrooms growing in serpentine sites contained higher
Cd,Cr and Ni than those from volcanic sites[20-22].
The climate of Yunnan province is mild and rainy in sum-
mer and autumn,providing nearly ideal conditions for mush-
room growth,with temperatures ranging between 20and 30
℃[23].There are around 2000species of wild-grown mush-
rooms considered edible to man and over 880species distribu-
ted in Yunnan,China[6].The genus Boletus mushrooms are
commercialy available in many countries and some are used as
medicinal fungi in China[24].144species of Boletus have been
identified edible in Yunnan province,which accounts for 72%
of the species identified in China[25].Boletus tomentipes is an
edible wild-grown mushroom and rich in protein,polysaccha-
ride,amino acid and essential elements[26].Knowledge of ele-
ment concentration in Boletus tomentipes is frequently inade-
quate.The report about comparative analysis of element con-
tent in Boletus tomentipes colected from different sites is
completely lacking.In a study by Li and co-workers(2011),
contents of As,Cd,Cr,Cu,Fe,Hg,Mg,Mn,Ni,Pb,and
Zn in eleven fruiting bodies of Boletus tomentipes were deter-
mined[27].In the present study,the caps and stipes were ex-
amined separately,and the contents of 12minerals(P,Na,
Ca,Cu,Fe,Mg,Zn,As,Cd,Co,Cr and Ni)were deter-
mined and statisticaly evaluated.In addition,we have com-
pared the element concentrations of Boletus tomentipes origi-
nating from different areas of Yunnan province.
1 Materials and methods
1.1 Reagents
Deionized water was used to prepare al aqueous solu-
tions.For the experimental work nitric acid solution and
H2O2were used.Al the glassware were cleaned by soaking
in 10%nitric acid solution for overnight and then rinsed with
deionized water prior to use.
1.2 Samples
Fruiting bodies of Boletus tomentipes were colected from
nine spatialy distant sites in Yunnan province in 2011.The
location and number of samples used in this study are given in
Table 1.Each sample was determined separately then got the
average value.The same developmental stage and wel grown
specimens of Boletus tomentipes were colected and cleaned-up
for substrate debris with a plastic knife.Each sample was
separated into two parts(cap and stipe)and washed with dei-
onized water then dried in an electricaly heated oven at 60℃
to constant weight.Dried samples were homogenized using an
agate mortar and stored in sealed polyethylene bag for analy-
sis.
1.3 Analysis
0.5g of dried and powdered mushrooms were accurately
weighted into the polytetrafluoroethylene(PTFE)pressure
vessels.Then the Blank samples and mushroom samples were
digested under pressure in an automatic microwave digestion
system with 4mL HNO3,2mL H2O2and 3mL deionized
water.The digest was further diluted to 25mL using deion-
ized water.The total minerals content of caps,stipes and
blank solutions were measured in triplicate by inductively cou-
pled plasma atomic emission spectrophotometer(ICP-9000,
Shimadzu,Japan).
Certified reference material(GBW07605)was used to e-
valuate the precision and accuracy of the analytical method.
Discrepancies between certified values and concentrations
quantified were below 10%.The obtained results are given in
Table 2.
Table 1 Location of Boletus tomentipes samples
colected from Yunnan province
Code Location
Number of
samples
BT1 Fuliangpeng,Eshan,Yuxi 10
BT2 Xiaojie,eshan.Yuxi 9
BT3 Tongchang,Yimen,Yuxi 9
BT4 Qianchang,Yaoan,Chuxiong 7
BT5 Tianshentang,Nanhua,Chuxiong 8
BT6 Shaqiao,Nanhua,Chuxiong 7
BT7 Simao,Puer 10
BT8 Nanbanghe,Puer 10
BT9 Zezhou,Qujing 7
Table 2 Values determined for the measured elements using
certified reference material(GBW07605)as sample
(mg·kg-1 dm)
Elements
Certified value
/(mg·kg-1)
Determined
/(mg·kg-1)
Recovery
/%
P 2 840±90 2 758.9±86.5 97
Fe 264±15 244.9±13.6 93
Ca 4 300±400 4 031±386 94
Mg 1 700±200 1 650.1±190 97
Na 44±6 44.4±7.3 101
Zn 26.3±2 25.4±2 97
Cu 17.3±1.8 16.6±1.6 96
As 0.27±0.04 0.28±0.05 104
Cd 0.057±0.01 0.06±0.02 105
Co 0.18±0.02 0.185±0.03 103
Cr 0.8±0.03 0.85±0.02 106
Ni 4.6±0.5 4.2±0.4 91
2 Results and discussion
2.1 Concentration
The average mineral concentrations in cap and stipe of
Boletus tomentipes are listed in Table 3and expressed on a
dry weight basis(mg·kg-1).Edible wild-grown mushroom
9931第5期 光谱学与光谱分析
can be considered as rich in certain minerals such as K,P,
Ca,Mg and Fe,and also rich in trace elements such as Cu
and Zn[10,28-30].As shown in Table 3,al of these elements
concentrations determined in Boletus tomentipes in this study
coincide with those reports mentioned previously.Toxic heav-
y metals such as As and Cd occur in relatively higher concen-
trations when compared to study of Li et al.,which were 0.1
~0.24and 0.16~0.32mg·kg-1 dm for As and Cd,respec-
tively.The average value for trace metals such as Co,Cr and
Ni are lower than Cu and Zn.Samples from Puer prefecture
own the higher contents of P,Fe,Ca and Mg in than other
places(Table 3).
Table 3 Elements content(mg·kg-1 dm,mean)of Boletus tomentipes
colected from nine different sites in Yunnan province in 2011
Elements BT1 BT2 BT3 BT4 BT5 BT6 BT7 BT8 BT9
P Cap 7 402 5 870 5 880 8 015 7 274 6 604 10 560 8 752 5 910
Stipe 5 801 3 895 3 916 5 724 4 924 4 465 8 379 7 342 2 459
Fe Cap 603 315 714 827 968 740 2 345 1 841 897
Stipe 1 159 295 1 991 753 858 895 3 573 4 904 3 258
Ca Cap 209 58 65 404 615 368 558 961 272
Stipe 324 59 101 433 1 257 372 739 1 242 567
Mg Cap 957 806 848 972 966 949 1 617 1 280 1 011
Stipe 933 625 632 741 736 780 1 426 2 011 773
Na Cap 220 150 317 66 78 335 163 157 38
Stipe 182 110 254 87 84 261 172 193 32
Zn Cap 261 108 141 163 177 133 129 146 119
Stipe 155 82 122 82 111 87 84 91 62
Cu Cap 112 51 49 46 61 60 136 321 22
Stipe 63 32 33 31 269 28 115 123 13
As Cap 1.01 0.03 2.24 1.96 1.73 1.54 4.87 10.81 3.49
Stipe 1.21 0.11 1.97 0.96 1.67 3.37 3.96 13.38 5.65
Cd Cap 0.46 0.42 0.38 3.15 1.13 0.48 0.59 0.48 1.2
Stipe 0.31 0.27 0.37 2.04 0.59 0.4 0.43 0.42 0.6
Co Cap 0.47 0.16 1.14 0.65 1.65 0.6 0.5 1.89 0.24
Stipe 0.64 0.21 2.55 0.82 2.14 0.84 0.65 2.51 0.58
Cr Cap 6.44 8.7 22.2 18.5 21.09 35.77 23.07 19.81 17.36
Stipe 14.06 5.37 27.32 18.01 25.11 23.46 22.05 58.97 34.24
Ni Cap 1.73 0.49 1.59 2.23 2.04 2.27 3.12 4.62 2.3
Stipe 2.07 0.59 3.56 1.93 2.39 2.34 3.32 7.16 5.2
2.2 Cap to stipe elements content
Data on the concentrations of elements such as P,Mg,
Zn and Cd are found at greater in cap than stipe while an op-
posite feature could be observed for Ca,Co and Ni.Analo-
gously,the situation was occurred in Boletus edulis and Suil-
lus grevilei colected from Poland[14,31].The value for other
elements(Fe,Na,Cu,As,and Cr)between cap and stipe
has no certain regularity.
2.3 Cluster analysis
The available data on mineral elements of cap and stipe
were analyzed by cluster analysis(CA),respectively.Fig.1
(a)and 1bdepict CA dendrogram results,which did show
some difference and similarity of minerals composition of Bo-
letus tomentipes colected from different sites in Yunnan prov-
ince.The CA diagram divided al sites into two main fractions
for both cap and stipe,which reflect the relationship between
element and site’s ecology.The first fraction separated ele-
ment composition of caps colected from Puer(BT7and BT8)
while the second fraction included two subfractions with
strongest similarity.The analogous situation occurred in sti-
pes except for Qujing located in the northeast of Yunnan.
2.4 Principal component analysis
Principal component analysis results showed that about
77% of information regarding the elements’compositional
variability of caps and stipes of Boletus tomentipes colected in
Yunnan can be described by three principal components(Ta-
ble 4).The factor loadings for 12chemical elements are given
in Table 5.The PCA did indicate on some interdependence a-
mong minerals of caps determined with P,Ca,Cu,Fe,Mg,
As and Ni(PC1),next including Na and Cd(PC2),and Zn
(PC3).As for stipes,first factor strongly influenced is by
variables describing Fe,Mg,As,Cr and Ni.The second fac-
tor is loaded by Zn and Na,and the third by Cu(Table 5).
The differences between caps and stipes could be attributed to
0041 光谱学与光谱分析 第35卷
mechanism in different part of mushroom.
Table 4 Eigenvalues of correlation matrix
and related statistics
PC
Cap Stipe
1 2 3 1 2 3
Eigenvalue 5.953 1.823 1.472 5.636 1.990 1.707
Total variance/%49.606 15.190 12.270 46.967 16.585 14.223
Cumulative/% 49.606 64.796 77.067 46.967 63.552 77.776
3-D plot of the PCA loadings is ilustrated in Fig.1(c)
and(d).As can be read from the two figures,some sites
tend to cluster together,such as BT7and BT8or BT1,BT4,
BT5and BT9,which is agree with the result of cluster analy-
sis.Caps of Boletus tomentipes colected from Shaqiao(BT6)
clearly overwhelmed others due to Na and Cd[Fig.1(c)].
Based on the greatest variance in mineral composition of P,
Ca,Cu,Fe,Mg,As and Ni,BT8could be separated from
other sites[Fig.1(d)].This configuration og cluster inter-
correlations could be explained by diversity of bedrock geo-
chemistry or climate.
Table 5 The values of the coefficients
of principal components
Element
Cap Stipe
PC1 PC2 PC3 PC1 PC2 PC3
P 0.807 -0.267 -0.047 0.519 0.291 0.247
Na -0.126 0.887 0.088 0.156 0.685 -0.561
Ca 0.910 -0.046 0.026 0.772 -0.013 0.596
Cu 0.842 0.148 0.397 0.397 0.374 0.786
Fe 0.916 -0.058 -0.211 0.893 -0.198 -0.245
Mg 0.839 -0.125 -0.230 0.895 0.040 -0.045
Zn -0.060 -0.188 0.803-0.123 0.862 0.035
As 0.904 0.065 0.077 0.939 -0.185 -0.212
Cd -0.070 -0.768 -0.244-0.183 -0.486 0.409
Co 0.598 0.212 0.351 0.602 0.421 0.097
Cr 0.314 0.499 -0.611 0.935 -0.131 -0.125
Ni 0.959 -0.005 0.022 0.907 -0.216 -0.238
Fig.1 (a)Cluster analysis diagram of the elements concentration similarity for the caps of Boletus tomentipes;(b)Cluster analysis
diagram of the elements concentration similarity for the stipes of Boletus tomentipes;(c)PCA results in the three dimen-
sional space:plot of loadings of the first three principal components for the caps of Boletus tomentipes;(d)PCA results in
the three dimensional space:plot of loadings of the first three principal components for the stipes of Boletus tomentipes
1041第5期 光谱学与光谱分析
3 Conclusion
This survey of element contents in Boletus tomentipes
showed high levels of P,Fe,Ca and Mg.Distribution of min-
erals in different parts of Boletus tomentipes is unevenly,
probably due to the presence of hymenophore in the caps.The
cluster analysis mainly showed the presence of two element
groups.Puer that located in south of Yunnan was separated
from other sites which lie in the central of Yunnan.Principal
component loading for mushroom samples extracted three
components explained about 77% of the total variance.The
obtained results from this study indicate that there is a direct
relationship between the element contents in mushroom sam-
ples and bedrock geochemistry.
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2041 光谱学与光谱分析 第35卷
ICP-AES法测定中国不同产地绒柄牛肝菌中矿质元素含量
王雪梅1,张 霁2,李 涛3,李杰庆1,王元忠2*,刘鸿高1*
1.云南农业大学农学与生物技术学院,云南 昆明 650201
2.云南省农业科学院药用植物研究所,云南 昆明 650200
3.玉溪师范学院资源环境学院, 云南 玉溪 653100
摘 要 采用微波消解处理样品,以电感耦合等离子体发射光谱法(ICP-AES)测定了采自云南省不同地点
的绒柄牛肝菌菌盖和菌柄中的12种矿物质元素(P,Na,Ca,Cu,Fe,Mg,Zn,As,Cd,Co,Cr,Ni)含量。
结果显示:绒柄牛肝菌中P,Ca,Mg,Fe,Zn,Cu的含量较高,其中菌盖中的P,Mg,Zn,Cd较高,而菌柄
中的Ca,Co,Ni较高;聚类分析结果显示,采用普洱地区的样品与其他地区的样品差异较大;主成分分析
结果显示,前三个主成分的累计贡献率为77%,其中第一主成分中的P,Ca,Cu,Fe,Mg,As,第二主成分
中的Ni,Na以及第三主成分中的Cd和Zn对区分不同地点的样品贡献较大。结果表明采自不同生境地的食
用菌元素含量差异较大。
关键词 真菌;元素;野生食用菌;多元统计分析;土壤背景值
(收稿日期:2014-07-13,修订日期:2014-10-19)
3041第5期 光谱学与光谱分析