Cd và Pb trong gạo và ngũ cốc
Trang 1Cadmium and lead contents in rice and other cereal
Shinichiro Shimboa, Zuo-Wen Zhanga,b, Takao Watanabec,
Haruo Nakatsukad, Naoko Matsuda-Inoguchid, Kae Higashikawae,
Masayuki Ikedae,U a
Department of Food and Nutrition, Kyoto Women’s Uni¨ersity, Kyoto 605-8501, Japan
b
Institute of Occupational Medicine, Chinese Academy of Pre¨enti¨e Medicine, Beijing 100050, PR China
c
Miyagi Uni¨ersity of Education, Sendai 980-0845, Japan
d
Miyagi Uni¨ersity, Taiwa-cho 981-3298, Japan
e
Kyoto Industrial Health Association, 67 Nishinokyo-Kitatsuboicho, Nakago-Ku, Kyoto 604-8472, Japan
Received 10 March 2001; accepted 3 April 2001
Abstract
Ž Cereals, especially rice, are a major source of cadmium Cd intake for general Japanese populations In
1998 ᎐2000, rice polished , bread loaf , noodle and wheat flour samples 4113 samples in total were collected in 63 cities all over Japan, and analyzed for Cd by inductively-coupled plasma mass spectrometry Another pollutant
element of lead Pb was determined in parallel The grand geometric mean for Cd in polished raw uncooked rice was 50 ng rg, whereas it was 19 ngrg for flour The value for Pb was 2᎐3 ngrg in rice and flour Calculation for daily
Cd intake via rice, taking advantage of the present findings on Cd contents in rice and wheat together with administrative area-specific daily consumptions of rice and wheat showed that Cd via rice is much more than Cd via wheat and that Cd via rice is highest in an area alongside the sea of Japan among the whole country, the observation being in agreement with the results from a previous food duplicate-based field survey 䊚 2001 Elsevier Science B.V All rights reserved.
Keywords: Cadmium; Cereal products; Flour; Japan; Lead; Rice; Wheat
UCorresponding author Tel.:q81-75-823-0533; fax: q81-75-802-0038.
0048-9697 r01r$ - see front matter 䊚 2001 Elsevier Science B.V All rights reserved.
PII: S 0 0 4 8 - 9 6 9 7 0 1 0 0 8 4 4 - 0
Trang 21 Introduction
Cereals, especially rice that is the staple food
for general Japanese populations, were identified
also as the major source of cadmium intake among
the victims of Itati-itai disease endemic in the
Jinzu River Basin in Japan in the mid 20th
tury Environment Agency, 1972 Rice-originated
Cd intake still accounts for approximately 40% of
total Cd burden almost exclusively via foods of
Ž people in Japan even in recent years Watanabe
et al., 2000
Accordingly, a nation-wide survey was initiated
to clarify Cd levels in rice and other cereal-based
foods which citizens consume everyday and to
examine if there is any difference in the Cd
contents among areas within the country Efforts
were made to collect samples that were actually
to be consumed by the residents of the areas
Lead Pb contents were also investigated in
par-allel The results to be presented in this paper are based on the survey of the largest scale ever published from Japan in an open literature
2 Materials and methods
2.1 Collection of samples
Samples were collected in 1998᎐2000 In
tice, 63 cities prefectural capitals or equivalents
in total from northern-most Hokkaido Island to southern-most Okinawa Islands were selected as sampling sites The locations are shown in Fig 1 The locations are grouped in terms of
administra-Ž tive areas for details, see lines in Fig 1 for
borders between areas , each area consists of four᎐seven prefectures except for Hokkaido and Okinawa in which there is only one prefecture The basic design was such that a volunteer in
Fig 1 Location of sampling sites in Japan Each dot shows one sampling site Lines show Area A Hokkaido , B Tohoku , C
Ž Kanto , D Tokai , E Hokuriku , F Kinki , G Chugoku , H Shikoku , I Kyushu and J Okinawa Each area consists of Ž Ž Ž Ž Ž Ž Ž four ᎐seven prefectures except for Hokkaido area and Okinawa area, each of which is made of one prefecture.
Trang 3Table 1
Number of samples collected, as classified by area
a
Area Number of Number of samples
sampling sites Raw rice b Boiled rice b Bread b Noodle c Flour c Total
a Administrative area; for locations, see Fig 1.
b Approximate equal numbers from kitchens and stores.
c From stores.
charge was identified for a city to collect 10
Ž
polished, either from kitchens of residents or
stores , bread loaf, either from kitchens of
dents or bakeries , noodle thick spaghetti in
Japanese style, from stores and flour wheat flour,
from stores per site In practice, however, this
principle was followed in cases of rice and noodle,
but not always so for bread and flour Three
collectors were assigned for metropolitan Tokyo
The numbers of samples collected are
summa-rized in Table 1, as classified by area;
approxi-mately equal numbers of raw and boiled rice and
bread samples were collected from kitchens and
stores
2.2 Sample pretreatment, analytical instruments and
operation conditions
A portion e.g 2 g fresh weight of raw rice
was wet-ashed by heating in presence of mineral
Ž acids as previously described Watanabe et al.,
1992 until clear residue approx 0.3 ml was
obtained The residue was then diluted to a
volume of 10 ml by addition of deionized water
and the diluted wet-ash was subjected to analysis
for Cd and Pb by inductively-coupled plasma mass
spectrometry ICP-MS
Ž
autosampler was a product of Seiko Instruments
ŽTokyo, Japan The system was operated under the conditions summarized in Table 2 Selection
of isotopes for Cd and Pb determination and
indium In and thallium Tl as internal stan-dards, preparation of calibration curves and other analytical conditions are shown in Table 3 The recovery was approximately 95 and 97% for Cd and Pb, respectively, and the accuracy when ex-amined with bovine liver, typical diet and rice
Ž flour as reference materials was 96᎐118% 104%
on an average for Cd and 96᎐107% 100% for
Pb The detection limit was 0.1 ngrg for Cd and 1
Ž
ngrg for Pb when a signalrnoise ratio of 2 was
taken , which was considered sufficient for Cd determination but marginally so in the case of Pb determination which is to be discussed later
In practice, the autosampler could accommo-date 50 samples in a series The determination of
Ž
Cd and Pb in one series including the input of
operation conditions to the system took 2.5᎐3 h
so that it was possible to measure 100᎐150 sam-ples per day
2.3 Chemicals
Stock solutions Cd and Pb for certified
Trang 4refer-Table 2
ICP-MS operation conditions
quadrupole MS analyzer
Ion sampling Diameter of sampling cone orifice 0.8 mm
Diameter of skimmer cone orifice 0.4 mm
Sampling distance torch-interface 10 mm
element analysis grades were purchased from
Wako Pure Chemicals Osaka, Japan Standard
reference materials of bovine liver NBS 1577b ,
1588 were obtained from the National Institute
Ž
USA , and that of rice flour NIES 10a, 10b and
10c from National Institute for Environmental
Sciences Tsukuba, Japan Deionized water was
prepared by filtration of city water through a
Milipore-Q system Milipore, Molshim, France
2.4 Statistical analysis
Concentrations were expressed on a fresh
weight basis A preliminary analysis on the
dis-tribution of the concentrations showed that
arithmetic standard deviations ASD were often
greater than one-third of the corresponding means
ŽAM , as observed previously Watanabe et al., Ž
1996; Zhang et al., 1996 Thus, a log-normal
Ž distribution was considered Watanabe et al.,
1989, 1996; Zhang et al., 1996 so that geometric
means GM and standard deviations GSD were
taken as representative parameters of
distribu-tion In calculating GM and GSD, the value below the detection limit was assumed as if it were half
the detection limit Student’s unpaired t-test and
analysis of variance ANOVA followed by
ple comparison Scheffe were employed to detect significant differences between or among means, with use of STAT VIEW version 5
3 Results
3.1 Cadmium contents in rice and cereal products
Cd concentrations in rice raw and boiled ,
bread loaf, noodle and flour wheat flour are summarized in Table 4 in terms of GM and GSD; the number of samples analyzed are given in Table 1 The grand GM concentrations are 49.7
ngrg for raw rice, 22.4 ngrg for boiled rice, 15.5
ngrg for bread, 4.31 ngrg for noodle and 19.3
ngrg for flour Because 100 g raw rice should give
Ž
212 g boiled rice when cooked Resources
Coun- cil, Science and Technology, 2000 , the ratio in
GM between raw and boiled rice, 49.7r22.4 or 2.2, appeared to be reasonable
Analysis of Cd contents for possible inter-area
Trang 5Table 3
ICP-MS analysis conditions for cadmium and lead
Ž
Accuracy AM"ASD in grg, ns5
Bovine liver NBS 1577b
Ž
Ž
Ž
Typical diet NBS 1548a
Ž
Ž
Ž
Rice flour NBS 1588
Ž
Ž
Ž
Rice flour NIES 10a
Ž
Ž
Ž
Rice flour NIES 10b
Ž
Ž
Ž
Rice flour NIES 10c
Ž
Ž
Ž
variation by ANOVA showed that there was a
significant P-0.01 variation in all cereals and
cereal products except for flour P)0.10
Anal-ysis by multiple comparison disclosed that, in the
case of raw rice, there were a number of pairs of
areas between which the difference was
cant P-0.05 Further perusal showed that the
Cd contents in raw rice collected in area E
Žlocated alongside the coast of the sea of Japan;
Fig 1 , 70.1 ngrg as GM, tended to be higher
than the values for rice samples from other areas
Similar statistical comparison of Cd contents in boiled rice gave only one pair of areas in which the Cd contents were significantly different, but the value for area E was highest of all by simple comparison, being on line with the observation with Cd in raw rice When statistical evaluation was made separately for boiled rice samples brought from kitchens and for those bought from
Ž
stores, inter-area difference was significant P -
0.01 in the former samples but not in the latter
ŽP)0.10 Further comparison in area E showed
Trang 6Table 4
Cadmium in rice, bread, noodle and flour
Area Cadmium GM in ng rg GSD in
d
d
d
d
c
a
Administrative area; for locations, see Fig 1.
b
All measures were above the detection limit of 0.1 ng rg fresh weight of samples.
cUUandU for P
-0.01 and 0.05, respectively NS for P)0.10.
dGMs with the same superscript letters are significantly Pw -0.05 by multiple comparison Scheffe different from each other Ž x when compared between areas.
that the value tended to be greater for
brought boiled rice 31.9 ngrg 1.76 as GM GSD
x
for 52 samples than for store-bought boiled rice
w28.3 ngrg 1.58 for 41 samples , although theŽ x
difference was statistically insignificant P)0.10
In contrast, no significant difference P)0.10
was detected when the multiple comparison test
was applied to wheat products, such as bread,
noodle or flour Although ANOVA showed
sig-nificant difference in GMs as discussed above, the
ratio of the largest GM over the smallest was
1.13, 1.56 and 1.25 for bread, noodle and flour,
respectively., whereas the ratio was 1.63 for raw
rice
3.2 Lead contents in rice and cereal products
Pb contents in rice and other cereal products
are summarized in Table 5 Grand GM values for
the products studied are in a range from 1.5 ngrg
for boiled rice to 3.2 ngrg for bread ANOVA
Ž disclosed significant differences P-0.01 for all
cases except for noodle for which P-0.05 among
the 10 areas The multiple comparison, however,
identified only one or two pairs of areas for which
the inter-area difference was statistically
cant P-0.05 It should be noted that the
mea-sures were below the detection limit in
tial numbers of cases Table 5 For example, raw rice samples with measures below the limit counted as many as 946 among the total of 1198,
or 79% The ratio was similarly high for boiled
rice 78% and flour 67% , although lower for
bread 29% and noodle 19%
3.3 Inter-site difference in Cd in raw rice
Cereal samples, especially raw rice samples,
Ž were collected in two or more sites or by two or
more collectors in several prefectures Compar-isons were made to examine if Cd contents in raw
rice varied between or among the sites even in case the sites are located rather close to each other, i.e in the same prefecture In practice, two sets of samples were available in seven prefec-tures, three sets in three prefectures and five sets
Ž
in one prefecture Hokkaido Island which is the
largest prefecture in space Difference was
ex-amined by Student’s t-test when only two sample
sets were available in one prefecture and by ANOVA in case more than two sets were ex-amined The statistical evaluation showed no
nificant difference P)0.10 in eight prefectures
Žincluding Hokkaido Island out of the 11, sug- gesting that within-prefecture difference was not substantial in most cases
Trang 7Table 5
Lead in rice, bread, noodle and flour
Area Lead GM in ng rg GSD : -DL
A 1.8 1.32 ;110 1.3 1.83 ; 98 4.9 2.26 ;7 2.8 2.28 ; 7 2.4 1.97 ; 19
d
B 2.3 1.87 ;147 1.7 2.25 ;143 3.2 2.48 ; 44 3.2 2.58 ; 14 3.4 2.00 ;31
C 2.4 2.02 ; 82 1.6 2.11 ; 86 3.8 2.63 ; 12 2.4 3.02 ; 23 3.6 2.54 ; 17
d
D 1.9 1.64 ; 89 1.5 1.98 ; 75 2.1 2.03 ;28 2.9 2.20 ; 10 2.5 1.83 ; 28
E 2.0 1.89 ; 82 1.6 2.12 ; 67 3.1 1.82 ; 9 3.9 2.25 ; 1 1.9 1.50 ; 29
F 2.3 1.90 ;144 1.5 1.95 ;141 2.8 2.47 ; 39 3.0 2.02 ; 10 3.0 2.34 ; 38
G 2.3 2.04 ; 69 1.2 1.60 ; 70 3.7 2.06 ; 7 3.2 2.02 ; 6 2.1 1.70 ; 28
d
H 3.0 2.51 ; 27 1.3 1.65 ; 40 3.4 1.68 ; 3 3.7 2.09 ; 1 2.5 1.85 ; 14
I 2.5 2.25 ;144 1.6 1.95 ;166 3.5 2.94 ; 43 2.8 2.23 ; 18 2.7 2.11 ; 49
d
J 2.0 1.88 ; 52 1.2 1.45 ; 56 1.8 2.15 ;22 1.7 2.38 ; 10 1.8 1.49 ;26
Total 2.2 1.93 ;946 1.5 1.96 ;941 3.2 2.47 ;214 2.9 2.34 ;100 2.7 2.06 ;279
a
Administrative area; for locations, see Fig 1.
b
The number of measures below the detection limit -DL of 1 ngrg fresh weight of samples.
cUUandU for P
-0.01 and 0.05, respectively.
dGMs with the same superscript letters are significantly Pw -0.05 by multiple comparison Scheffe different from each other Ž x when compared between areas.
In a further step, Cd contents in raw rice were
classified by prefecture and GM values for
indi-vidual prefectures were compared among each
area Because area A and J consist of one
prefec-ture each, the comparison was made for eight
areas of B᎐I The results showed that the
within-Ž area difference was significant P- 0.01 by
ANOVA in six areas out of the eight, whereas it
was insignificant P)0.10 for two areas of C and
H; area C embraces several large cities including
Tokyo and area H has only limited rice
produc-tion because the land is mountainous, so that rice
is imported from other areas in Japan to these
two areas Combining this observation with the
findings on the within-prefecture difference, it is
apparent that detection of geographical
differ-ence in Cd contents in raw rice relates to the
Ž dimensions of the regions e.g city, prefecture or
area considered for comparison
4 Discussion
The present study showed that the grand GM
for Cd in rice consumed in Japan was
approxi-mately 50-ngrg raw rice with significant variation
Ž depending on the areas rice from area E probably
being higher than others whereas Cd contents were lower in three wheat-based food materials
of bread loaf 16 ngrg , noodle 4 ngrg and flour
Ž19.3 ngrg Table 4 with less remarkable inter- Ž
Ž area variation as shown by the absence of pairs
of areas with significant difference The observed
GM of 50 ngrg for raw rice is in general agree-ment with the results of a nation-wide mass
ŽMinistry of Agriculture, Forestry and Fishery,
2000 when the difference between the geometric
Žthe present study and arithmetic means is taken into account
Pb levels in cereals including rice and wheat
were much lower 2᎐3 ngrg and levels in many
samples were below the detection limit Table 5 Thus, the observed GM values for Pb should be taken as semi-quantitative and not strictly quanti-tative This limitation may explain why the ratio
in GM of raw rice over boiled rice 2.2r1.5s1.5 does not agree with the expected value of 2.1
ŽResources Council, 2000 When compared with the levels in late 1980s
Trang 8Ž53 ng Cdrg rice, Watanabe et al., 1989 and.
mid-1990s 53 ng Cdrg rice , the present
observa-tion of 50 ng Cdrg rice suggests that there have
been essentially no changes or only slight
reduc-tion in Cd contents in rice in Japan during the
Ž past 10 years In contrast, Pb contents in rice 2᎐3
ngrg appear to show a gradual decrease from
the levels of approximately 5 ngrg both in late
1980s Watanabe et al., 1989 and in mid-1990s
ŽZhang et al., 1996
Cd and Pb contents in rice available in various
parts of the world were previously reviewed, and
it was summarized that Cd contents in rice
avail-able in Japan is substantially higher than the
levels in rice from surrounding Asian countries
Že.g 15᎐30 ngrg or outside Asia e.g 20᎐30 Ž
ngrg for rice available in Europe; Watanabe et
al., 1989, 1996 , whereas the reverse is actually
the case for Pb contents in rice from Japan when
compared with rice from other parts of Asia
ŽWatanabe et al., 1989, 1996; Zhang et al., 1996
With regard to Cd in flour, both high values of 43
ngrg Wolnik et al., 1983 or 8᎐77 ngrg Muller
et al., 1996 for flour in Europe and low values of
12᎐17 ngrg Watanabe et al., 1998 or 15 ngrg
ŽZhang et al., 1998 for flour in China were re-
ported The present observation of 19 ng Cdrg
flour is not only closer to the latter levels, but
further in agreement with the values for whole
Ž wheat grain of 40᎐50 ngrg Cd Bruggemann and
Kumpulainen, 1995; Chaudri et al., 1995; Mench
et al., 1997; Conti et al., 2000 or 20᎐100 ngrg
ŽLorenz et al., 1986 , because Cd in wheat grain is
higher in bran and lower in albumen so that Cd
Ž
in flour after milling is much lower e.g approx
40% than that in the whole grain Zhang et al.,
1997
The inter-area difference in Cd contents in rice
samples was substantial among raw samples, less
so among kitchen-bought boiled rice and
insig-nificant among store-bought boiled samples This
observation may deserve discussion because the
findings are probably related to the marketing
system of rice in Japan In everyday life, each
Ž
family typically non-farming urban family in the
case of the present study will purchase rice from
local stores to cook mostly by boiling in the
kitchens; in the stores, both locally harvested rice
as well as nation-widely marketed rice are avail-able In contrast, store-bought boiled rice is sup-plied by food processing industries, which will predominantly utilize widely marketed rice rather than local rice because they cook rice by a great batch Thus, kitchen-bought boiled rice samples will probably reflect local conditions better than the store-bought counterparts
A similar consideration can be applied to ex-plain rather homogeneous Cd and Pb contents in
wheat-based food materials Tables 4 and 5 Whereas, the rate of self-sufficiency is nearly
Ž 100% in the case of rice production and
there- fore, supply , the rate for wheat is as low as 8% as
Ž the 3-year average for 1995᎐1997 Ministry of
Agriculture, Forestry and Fishery, 1999 The lat-ter low rate indicates that the malat-terials for wheat-based products such as bread and noodle
Žincluding flour are imported from abroad as- sumedly in large batches, and therefore, the metal level in the products will not be related to local conditions where they are consumed
When the present observation on raw rice is compared with the values reported in literature
ŽTable 6 following the flow of time, it appears likely that there has been no substantial changes
in Cd contents in rice in the past 12 years, whereas
Pb contents may have been decreasing gradually The methods of analysis employed were, however, not the same, i.e flameless atomic absorption was
Table 6 Cadmium and lead contents in raw polished rice, reported in literature
a
Reference Element concentration ng rg
Rivai et al., 1990 21 ᎐99 Watanabe et al., 1992 41 Watanabe et al., 1993 46 Watanabe et al., 1996 56
a Geometric means.
Trang 9Ž used in early day studies Saito et al., 1988;
Watanabe et al., 1989, 1992, 1993; Rivai et al.,
1990 , whereas it was ICP-MS in recent studies
ŽWatanabe et al., 1996; Zhang et al., 1996 as in
the present study
Possible health implication of dietary Cd intake
among general Japanese populations has been
discussed in a separate paper Ikeda et al., 2000a
In this connection, it may be worthy to note that
dietary Cd intake is almost the exclusive source of
Cd intake Ikeda et al., 2000b and that rice
accounts for approximately 40% of total dietary
Cd intake Watanabe et al., 2000 In a very sharp
contrast, dietary Pb intake of Japanese
popula-Ž tions is among the lowest of the world Zhang et
al., 2000 rice accounting for less than 20% of the
total dietary intake, although Pb intake via
respi-ration of general air is comparable to that via
food Ikeda et al., 2000b
Taking advantage of the published data on
daily consumption of various food items including
Ž rice and wheat products Ministry of Health and
Welfare, 2000 , it is possible to estimate the daily
intake of Cd and Pb via two staple cereals of rice
and wheat The estimation was made by
multipli-cation of daily consumption with Cd and Pb
con-tents in the cereals Both data on the rice and
Ž wheat consumption Ministry of Health and
Wel-
fare, 2000 and that on Cd and Pb contents in rice
and wheat Table 4 are available not only for the
whole country of Japan but for individual
admin-Ž
istrative areas for geographical locations, see Fig
1 , the estimation was made for the whole country
Žshown in the average column in Table 7 as well
Ž
as for individual areas the minimum and the maximum values among the 10 areas are shown
as a range in Table 7
On the whole country basis, Japanese people
take 1.8 times more rice 165 grday than wheat Ž91 grday as raw material, taken as bread, noodle
etc on a weight basis, and this difference is further expanded to 4.7 times when Cd intake is
Ž compared 8.2 grday from rice vs 1.8 grday
from wheat because Cd contents are much higher
in rice 50 ngrg than in wheat 19 ngrg When the daily Cd intake by Japanese women is
ŽWatanabe et al., 2000 ; the value for men should
be somewhat higher than this level because men
take more food than women , daily intake of 8.2 and 1.8 g Cdrday via rice and wheat, respec-tively, accounts for 32 and 7% of the total dietary
Cd intake Pb contents are more or less similar in rice and in wheat, and contribution of the two cereals as sources of dietary Pb intake is
tially in proportion of the cereal intake Table 7
It is further possible to make calculation for each administrative area The calculation on the
area basis Table 8 shows that the Cd intake via rice is the highest in area E in agreement with the
Ž previous observation in a field survey Watanabe
et al., 2000 ; this high value is due to the facts that both rice intake and Cd content in rice are high in this area Cd intake via wheat is smaller
Table 7
Intake of cadmium and lead via rice and wheat
Ž
Element content ng rg
a
Cadmium
Lead
a Cited from Ministry of Health and Welfare 2000
Trang 10Table 8
Cadmium intake via rice and wheat in various areas
a
a For locations, see Fig 1.
b
Ž Intakes of rice and wheat are cited from Ministry of Health and Welfare 2000 , and Cd contents in rice and wheat are cited from the raw rice and flour columns in Table 4.
c
The average value for Kanto I and Kanto II areas Ministry of Health and Welfare, 2000
d
The average value for Kinki I and Kinki II areas Ministry of Health and Welfare, 2000
e
The value for southern Kyoshu Ministry of Health and Welfare, 2000
than that via rice Table 7 , but relatively higher
Ž
in the two most urbanized areas of C in which
Žwhere Osaka, Kobe and Kyoto are , presumably
Ž with more consumption of bread and noodle
Ta-
ble 8 No area-specific data of comparison on Pb
via rice and that via wheat are presented, because
cereal-based Pb intake is limited with small
inter-area variations Table 7
The present analysis made it clear that
varia-tion in Cd contents in raw rice is significant
among prefectures even when they belong to the
same administrative area Thus, it is apparently
desirable to make estimation of cereal-based Cd
intake for each prefecture The data on cereal
consumption on the prefecture basis are,
how-ever, not available unfortunately
Acknowledgements
A part of this work was supported by research
grants-in-aid from the Environment Agency, the
Government of Japan to S.S for 1998 to 2000
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