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Assessment of daily intake of trace elements due to consumption of foodstuffs by adult inhabitants of Rio de Janeiro city

Authors:
  • Instituto de Radioproteção e Dosimetria, Rio de Janeiro, Brazil

Abstract

Concentrations of Al, Cd, Cr, Cu, Mn, Ni, Pb, U and Zn were determined in vegetables (leafy vegetables, fruit, root, grain and cereal), derived products (sugar, coffee, manioc flour, wheat flour, corn flour, and pasta) and animal products (meat, fish, milk) most frequently consumed by adult inhabitants of Rio de Janeiro city. A total of 90 samples were analyzed using inductively coupled plasma mass spectrometry (ICPMS) as the principal method following sample dissolution by dry and wet ashing. Generally, highest contributions for the intake of micronutrients (Cu, Mn, Ni and Zn) arise from bean, rice and wheat flour consumption. Meat, cow milk and the flours, wheat and manioc, are major sources of Al, Cd, Pb and U intake. The daily intake of nine elements via foodstuffs was estimated as: 3.4x10(-4) mg of U, 1.8x10(-3) mg of Cd, 2.8x10(-2) mg of Pb, 2.3x10(-2) mg of Cr, 8.9x10(-2) mg of Ni, 1.12 mg of Cu, 2.5 mg of Mn, 3.5 mg of Al and 4.8 mg of Zn. The intake of toxic elements ranged between 2.7% (Cd) and 30% (U) of the provisional tolerable daily intake and reference dose values indicating that food consumption is, at present, no critical factor for the uptake of these toxic metals, in the population studied here. Concerning micronutrients, the recommended values of daily intake of Cu and Mn are conveniently supplied by the diet; however, for Cr and Zn they are lower than the recommend daily allowance. Due to high metal concentrations and consumption rates, black bean is the foodstuff that provided the highest ingestion rates of Cu, Mn, Ni and Zn (36-60% of the reference dose), being therefore a very important source of micronutrient supply.
Science of the Total Environment 327 (2004)69–79
0048-9697/04/$ - see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2004.01.016
Assessment of daily intake of trace elements due to consumption
of foodstuffs by adult inhabitants of Rio de Janeiro city
E.E. Santos , D.C. Lauria *, C.L. Porto da Silveira
ab,c
Universidade Estadual do Rio de Janeiro, Rio de Janeiro, RJ, CEP 8720551-030, Brazil
a
Instituto de Radioprotecao e Dosimetria, Rio de Janeiro, RJ, CEP 22642-970, Brazil
b
¸˜
Pontifıcia Universidade Catolica do Rio de Janeiro, Rio de Janeiro, RJ, CEP 22453-900, Brazil
c
´´
Received 4 September 2003; accepted 13 January 2004
Abstract
Concentrations of Al, Cd, Cr, Cu, Mn, Ni, Pb, U and Zn were determined in vegetables (leafy vegetables, fruit,
root, grain and cereal), derived products (sugar, coffee, manioc flour, wheat flour, corn flour, and pasta)and animal
products (meat, fish, milk)most frequently consumed by adult inhabitants of Rio de Janeiro city. A total of 90
samples were analyzed using inductively coupled plasma mass spectrometry (ICPMS)as the principal method
following sample dissolution by dry and wet ashing. Generally, highest contributions for the intake of micronutrients
(Cu, Mn, Ni and Zn)arise from bean, rice and wheat flour consumption. Meat, cow milk and the flours, wheat and
manioc, are major sources of Al, Cd, Pb and U intake. The daily intake of nine elements via foodstuffs was estimated
as: 3.4=10 mg of U, 1.8=10 mg of Cd, 2.8=10 mg of Pb, 2.3=10 mg of Cr, 8.9=10 mg of Ni, 1.12
y4y3y2y2y2
mg of Cu, 2.5 mg of Mn, 3.5 mg of Al and 4.8 mg of Zn. The intake of toxic elements ranged between 2.7% (Cd)
and 30% (U)of the provisional tolerable daily intake and reference dose values indicating that food consumption is,
at present, no critical factor for the uptake of these toxic metals, in the population studied here. Concerning
micronutrients, the recommended values of daily intake of Cu and Mn are conveniently supplied by the diet; however,
for Cr and Zn they are lower than the recommend daily allowance. Due to high metal concentrations and consumption
rates, black bean is the foodstuff that provided the highest ingestion rates of Cu, Mn, Ni and Zn (36–60% of the
reference dose), being therefore a very important source of micronutrient supply.
2004 Elsevier B.V. All rights reserved.
Keywords: Dietary intake; Trace elements; Food; Inductively coupled plasma mass spectrometry
1. Introduction
Metals have an impact on human health in many
ways. Some elements, such as Cu, Mn and Zn, are
essential micronutrients with a human requirement
*Corresponding author. Tel.: q55-21-34118101; fax: q55-
21-4422699.
E-mail address: dejanira@ird.gov.br (D.C. Lauria).
of no more than a few milligrams per day. How-
ever, micronutrients may become harmful when
their ingestion rates are too high. Furthermore,
some elements (e.g. Ni and Sn)are likely to be
essential micronutrients, although their positive
role in human nutrition remains to be confirmed
and, other elements have no proven essential func-
tions in humans and are likely to have adverse
70 E.E. Santos et al. / Science of the Total Environment 327 (2004) 69–79
Table 1
Food consumption rates (in kg per year)for adult inhabitants
of Rio de Janeiro City (IBGE, 1998)
Foodstuff Consumption rate
Meat products 19.14
Milk products 48.41
Fish products 3.43
Vegetables and derived products 185.3
Leafy vegetales 2.2
Fruit vegetables 13.6
Root 23.6
Bean 14.0
Cereal 35.0
Fruit 31.2
Wheat flour 27.0
Sugar 26.2
Coffee 2.7
Others 10.0
physiological effects (e.g. Al). In contrast, trace
elements such as Cd and Pb are well known as
toxic if their intake through ingestion or inhalation
is excessive. In addition, a metal can be toxic or
be a micronutrient depending on its chemical form
or speciation (e.g. Cr-VI and Cr-III). Also, defi-
ciencies, excesses, or imbalances in the supply of
inorganic elements from dietary sources can have
an important deleterious influence on human health
(Abrahams, 2002; DEFRA, 2002; WHO, 1996;
OMS, 1980).
The amount of metal ingested by man is
straightly related to alimentary habits and their
content in foodstuff. Metal concentrations in food-
stuff depend on soil characteristics, such as content
of organic matter, pH and clay mineralogy, which
can affect the bioavailability of elements. For
example, higher soil-to-plant concentration ratios
have been observed in Brazilian oxisols than in
soils from temperate climates. This finding has
been related to the dystrophic characteristics of
this type of soil (Wasserman, 1998). Vegetables
and animals can take up high amount of metals
from contaminated soils, as well as from contam-
inated water and polluted air. Besides environmen-
tal pollution, a matter of concern is the addition
of chemical products as fertilizers, fungicides,
insecticides and herbicides to crops. These prod-
ucts may contain several metals and their additions
can increase the metal amounts in soil and water.
Furthermore, the physical and chemical forms in
which they are dispersed can increase the metal
availability for plants and so increase the metal
concentrations in vegetables (Barnard et al., 1997;
Fernıcola, 1983).
´
The knowledge of metal concentrations in food-
stuff can provide important information on the
impact of the use of chemical products in crops
and on levels of environmental pollution in farms.
Furthermore, such a survey may indicate local
foodstuffs that are important to supply essential
metals for population groups. Information on these
topics is scarce, especially when dealing with
developing countries. Thus, a first study on trace
element concentrations (Al, Cd, Cu, Cr, Mn, Ni,
Pb, U and Zn)in the most frequently consumed
foodstuffs by inhabitants of Rio de Janeiro city
was performed, aiming to verify metal levels and
variations, and to make a preliminary estimate on
intake doses of micronutrients and toxic metals for
this population. The estimated intakes of essential
elements were compared to the Recommended
Daily Allowances (NRC, 1989), while the esti-
mated intakes of potentially toxic elements are
compared to the Provisional Tolerable Weekly
Intake (PTWI)and to the Reference Dose, RfD
(EPA, 2001; WHO, 1993).
2. Materials and methods
2.1. Selection and food sampling
The most consumed animal products, vegetables
and derived products were selected using the data-
base from the ‘Brazilian Institute of Geography
and Statistics (IBGE, 1998)’, which compiles aver-
age consumption rates for various food types in
the main Brazilian cities (Table 1). For acquiring
samples by market-basket survey, representative
food distribution centers were chosen according to
the buying habits of different social classes from
Rio de Janeiro city. In these centers, the main
trademarks of the vegetable-derived products were
surveyed (Santos et al., 2002). All samples were
bought in two seasonal periods (rainy and dry
seasons), comprising a total of 90 samples of 29
different vegetables, vegetable-derived and animal
products. The amount of each product was chosen
71E.E. Santos et al. / Science of the Total Environment 327 (2004) 69–79
Table 2
Typical 3
s
ICPMS method detection limits (3
s
-MDL)
obtained for some elements in this work. Data expressed as
mg kg of dry ash and calculated for a sample dilution factor
y1
of 100. Based on the fresh weight of foodstuff, these values
are lower by a factor of 100 or more
Element 3
s
-MDL (mg kg )
y1
Al
*
2
Cd 0.2
Cr 0.06
Cu 1
Mn 0.01
Ni 0.1
Pb 0.02
U 0.001
Zn 0.1
The MDL of Al refers to ICPOES methodology.
*
according to its fresh mass to ash mass relation-
ship, in order to obtain approximately 20–30 g of
ashes. The analyzed foodstuffs were: bean (black);
cereal (rice); roots (potato, carrot, onion, manioc);
fruit vegetables (tomato, chayote, pumpkin); leafy
vegetables (lettuce, watercress, cabbage, cauliflow-
er, kale, spinach)and fruits (orange, banana, apple,
pineapple, papaya); farinaceous (wheat flour, corn
flour, manioc flour, pasta); sugar; coffee and ani-
mal products (chicken, fish, beef and cow milk).
2.2. Sample pretreatment and analysis
The samples were washed and shelled, when
necessary, air-dried and then weighed for the deter-
mination of the fresh mass. After drying in oven
at 80 8C during approximately 16 h, the samples
were then ashed during 24 h in an oven at 400
8C. To assess the possible loss of volatile elements
(e.g. Zn, Cd, Pb)under these conditions, two
certified reference materials were treated in the
same way. Coffee was prepared as ‘ready for
drinking’ by percolating6lofhotwater through
183 g of powder coffee; the filtered solution was
then evaporated and the residue ashed as described
before. Milk samples (1l)were evaporated and
the remaining residue also ashed. For metal deter-
minations, 0.200 g-samples of ash were dissolved
with 10 ml of 65% nitric acid (Merck, Suprapur).
After 72 h of digestion in a closed polypropylene
tube at 90 8C in a heating block, the solutions
were then evaporated to approximately 1 ml and
then completed with ultra-pure water (18 MV
cm), obtained by passing double-distilled water
through a Milli-Q system (Millipore, Bedford,
MA, USA), until a final volume of 20 ml. Indium
and thallium were added as internal standards to
all samples, blanks and standard solutions, at a
concentration of 20 mg l of each one. Analyses
y1
were performed by inductively coupled plasma
mass spectrometry (ICPMS)using an ELAN 6000
instrument (PerkinElmer-Sciex, Norwalk, NY,
USA)equipped with the standard spray chamber
(Ryoton )and a cross-flow nebulizer. Calibration
was performed in the TotalQuant mode using a
57-element standard solution (20 mg l of each
y1
element)prepared by adequate mixing and dilution
in 2% HNO of three standard solutions (Perkin–
3
Elmer, no. 2, 3, 5). Elemental determinations were
performed using the most abundant and less inter-
fered isotopes (Cr, Cr, Mn, Ni, Ni, Cu,
52 53 55 60 62 63
Cu, Zn, Zn, Cd, Pb, U)and samples
65 66 68 111 208 238
were always analyzed in triplicates. More details
on the ICPMS analytical procedure used were
published elsewhere (Godoy et al., 2001). Typical
3
s
method detection limits (MDLs), calculated in
the conventional way from the standard deviation
of 10 reagent blanks and the analytical sensitivity
(instrument response factor), are shown in Table
2. These data refer to ashed samples; calculated
for fresh samples, these MDLs are lower by a
factor of 100, at least, depending on the ‘fresh
mass to ash mass’ relationship of the sample
(Vasconcellos et al., 1999). Aluminum was deter-
mined by inductively coupled plasma optical emis-
sion spectrometry (ICPOES)at 396.152 nm using
a Plasma-1000 instrument (PerkinElmer, Nor-
walk, NY, USA)operated under standard condi-
tions. The MDL for this element is also included
in Table 2.
Method validation (accuracy and repeatability)
was performed by analyzing two certified reference
materials, IAEA-140 TM (Sea Plant)and NBS
1575 (Pine Needles), together with the foodstuff
samples. Within the uncertainty of the
TotalQuant method here used, typically 10–20%,
no significant differences between the certified and
the here reported concentrations were observed,
showing that the used simplified methodology fits
72 E.E. Santos et al. / Science of the Total Environment 327 (2004) 69–79
Table 3
Analytical results obtained on two certified reference materials. All concentrations expressed in mg kg
y1
Element IAEA-140yTM (Sea plant)NBS 1575 (Pine needles)
Certified value (A)Measured value (B)ByA(%)Certified value (A)Measured value (B)ByA(%)
Al 1184"265 1295"491 109 545"30 549"47 101
Cd 0.537"0.037 0.581"0.015 108 (-0.5)0.22
Cr 10.4"0.8 11.7"0.3 112 2.6"0.2 2.5"0.2 96
Cu 5.05"0.28 5.79"0.07 115 3.0"0.3 3.8"0.4 127
Mn 56.1"2.4 58.2"0.6 104 675"15 747"49 111
Ni 3.79"0.41 3.23"0.50 85 (3.5)4.0 114
Pb 2.19"0.28 1.99"0.19 91 10.8"0.5 9.86"0.96 91
Zn 47.3"2.0 48.9"0.7 103 –
U 0.730"0.083 0.732"0.08 100 0.020"0.004 0.017"0.006 85
Values in parentheses are not certified.
for the purpose of this study (Table 3). Further-
more, the agreement of data for Zn, Cd and Pb
suggests that the convenient sample ashing proce-
dure here used did not result in significant losses
for these more volatile elements.
2.3. Data analysis
For each metal, the distribution of the combined
data of the food category was verified by the curve
of accumulated frequency (Miller and Miller,
1989). As usually observed in environmental sam-
ples, concentrations of the metals were better
represented by the lognormal distribution for which
the central tendency is represented by the geomet-
ric mean (Wayne, 1990). When the number of
samples was less than three, the geometric average
was determined considering the similarity with
other results. For the total daily intake evaluation,
the weighted average for each metal in each food
category was calculated, and then multiplied by
the respective consumption rate (IBGE, 1998).
3. Results and discussion
3.1. Concentrations of Al, Cd, Cu, Cr, Mn, Ni, Pb,
U and Zn in foodstuffs
The results obtained for the geometric mean,
maximum and minimum concentration are pre-
sented in Table 4. Reflecting their expected abun-
dance in soils, the highest concentration in
foodstuffs consumed by the adult inhabitants of
Rio de Janeiro were observed for Al, Zn, Mn and
Cu, respectively; the smallest concentrations were
measured for uranium. The foodstuffs that pre-
sented the highest concentrations of metals were:
black beans (Al, Mn, Ni, Cu and Zn); spinach,
meat, watercress and lettuce (Al); banana and
coffee (Cr); manioc flour, coffee and cow milk
(Pb); spinach and coffee (Cd); and pasta (U). For
all types of foods, a relatively large variability in
metal concentration values was observed, even
within the same kind of food.
Most of perishable agricultural food supplied to
markets in Rio de Janeiro is from neighboring
farming land, while the least perishable ones are
from other Brazilian states or even imported (as
white flour). Then, the large concentration value
variability can be caused by the differences in the
chemical and physical properties of the different
farming soils, by the climatic differences of the
producing areas or even due to the use of phos-
phate fertilizers (Wasserman, 1998).
The mean concentrations of Cd, Cu, Pb and Zn
(Table 4)were compared with the maximum limits
of tolerance for metals in foodstuffs recommended
by the Brasilian Ministry of Health (1998): 0.2
mg kg for Cd; 10 mg kg for Cu; 0.5 mg
y1y1
kg for Pb and 50 mg kg for Zn. In general,
y1y1
metal concentrations were below these recom-
mended values. However, important exceptions
were observed for Cu and Zn in black bean and
Cu in rice. At present, there are no recommended
maximum limits of tolerance in Brazil for the other
elements here studied (Al, Mn, Cr, Ni and U).
73E.E. Santos et al. / Science of the Total Environment 327 (2004) 69–79
Table 4
Trace element concentrations in some foodstuffs most frequently consumed in Rio de Janeiro city: (geometric mean)and range
Foodstuff Consumption nAl Cu Mn Zn Cd Cr Ni Pb U
(kg year )
y1
(mg kg )
y1
(mg kg )
y1
(mg kg )
y1
(mg kg )
y1
(mgkg )
y1
(mgkg )
y1
(mgkg )
y1
(mgkg )
y1
(mgkg )
y1
Cauliflower 0.01 2 (4.1)(0.2)(2.2)(3.2)(1.7)(21)(26)(7.5)(0.002)
2.0–6.2 0.1–0.4 1.5–3.3 2.1–4.8 1.0–3.0 17–27 12–59 3.0–19 -0.002–0.003
Cabbage 0.96 4 (1.8)(0.2)(4.4)(1.9)(2.1)(23)(37)(0.4)(0.01)
1.4–2.2 0.1–0.2 1.6–7.6 1.2–3.2 0.4–6.9 15–38 14–130 -0.003–53 -0.001–0.1
Kale 0.38 3 (8.6)(0.2)(6.1)(2.6)(7.0)(40)(61)(0.17)(0.13)
5.3–17 0.2–0.3 1.7–18 1.7–3.7 5.0–10 21–61 37–91 -0.01–37 -0.004–1.0
Lettuce 0.63 4 16 (0.2)(4.1)(2.5)(4.0)(45)(38)(31)(0.3)
6.4–30 0.1–0.3 2.3–8.0 1.4–7.4 2.4–9.7 7.8–120 19–72 17–75 0.03–1.1
Spinach 0.01 3 (24)(0.4)(3.1)(2.8)(10)(41)(41)(47)(1.1)
14–31 0.3–0.4 1.9–5.1 1.9–4.2 2.0–30 17–70 29–77 40–61 0.3–3.0
Watercress 0.13 3 (17)(0.6)(4.0)(4.2)(6.5)(34)(51)(21)(1.2)
13–21 0.3–1.2 3.0–5.1 3.2–6.3 3.8–12 30–36 47–58 19–23 0.7–3.7
Chayote 2.7 3 (0.2)(0.1)(0.6)(0.3)(0.02)(2.4)(1.8)(0.01)(0.01)
0.02–0.9 0.06–0.2 0.4–0.9 0.2–0.5 -0.006–0.3 1.3–5.5 0.1–11 -0.002–0.02 -0.0006–0.04
Pumpkin 1.9 2 (0.8)(0.2)(1.5)(1.2)(3.5)(9.4)(88)(0.3)(0.08)
0.07–1.5 0.06–0.4 0.7–3.1 0.93–1.6 1.9–6.6 5.9–15 41–190 -0.006–16 0.03–0.1
Tomato 5.4 4 (3.3)(0.4)(1.3)(1.3)(2.5)(9.5)(25)(0.02)(0.1)
1.6–7.1 0.3–4.5 0.9–1.7 1.0–1.9 1.3–4.4 3.8–32 12–52 -0.002–13 0.05–0.4
Carrot 3.7 4 (2.7)(0.3)(1.4)(1.6)(2.0)(9.9)(2.3)(10)(0.04)
2.1–4.6 0.2–0.4 0.8–2.2 0.8–3.3 0.6–7.0 2.5–59 1.3–20 0.2–72 -0.002–0.2
Manioc 0.7 4 (5.40)(0.7)(2.9)(2.9)(3.7)(5.5)(260)(0.8)(0.09)
2.7–15 0.5–0.8 1.8–5.1 1.2–13 3.0–5.0 3.5–15 130–510 -0.004–170 0.05–0.2
Onion 4.1 4 (0.2)(0.4)(1.8)(1.0)(2.5)(3.5)(13)(0.03)(0.02)
0.02–0.9 0.3–0.5 0.8–3.1 0.6–1.5 1.1–7.0 2.0–6.8 4.0–29 -0.003–1.0 -0.001–0.3
Potato 12.6 4 (0.93)(1.2)(1.3)(2.4)(5.3)(10)(13)(0.23)(0.01)
0.3–3.5 0.7–2.0 1.1–2.0 1.6–4.5 2.2–10 10 1.2–100 -0.008–10 -0.002–0.009
Apple 2.8 3 (0.9)(0.3)(0.7)(0.8)(0.3)(9.7)(62)(4.4)(0.02)
0.7–1.0 0.2–0.5 0.4–1.1 0.06–21 -0.008–9.2 7.6–12 -0.02–87 0.02–27 -0.002–0.009
Banana 6.1 2 (0.9)(0.4)(5.4)(2.3)(0.02)(230)(2.3)(0.3)(0.003)
0.8–1.4 0.2–0.9 3.8–7.7 0.4–14 -0.02–0.03 200–270 -0.03–190 -0.01–6.0 -0.0002–0.004
Orange 8.1 2 (2.6)(0.4)(0.4)(1.3)(0.1)(84)(59)(21)(0.7)
0.6–4.5 0.2–0.8 0.2–0.8 0.2–8.6 -0.03–0.3 12–590 12–290 9.0–44 (0.3–1.0)
Pineapple 1.7 1 (1.4)(0.4)(1.1)(0.2)(0.02)(3.5)(0.02)(0.01)(0.06)
Rice 33.8 6 (2.6)(2.3)(0.03)(2.8)(5.0)(26)(150)(0.2)(0.2)
0.9–14 0.4–61 0.0011–11 0.3–19 0.4–54 5.8–300 17–990 -0.002–90 -0.001–2.0
Black bean 13.6 4 (20)(17)(34)(45)(0.6)(23)(1300)(0.03)(0.3)
1.3–116 7.7–80 1.3–190 22–240 -0.05–9.0 8.8–69 1100–1600 -0.02–0.04 -0.01–3.0
Manioc flour 2.6 3 (2.6)(0.6)(6.8)(5.0)(1.5)(88)(280)(380)(0.6)
2.3–2.9 0.5–0.7 4.6–11 4.4–5.9 1.2–2.3 23–798 194–417 279–502 0.2–1.4
Wheat flour 16.7 3 (6.1)(0.9)(15)(5.0)(5.9)(22)(62)(0.2)(1.2)
74 E.E. Santos et al. / Science of the Total Environment 327 (2004) 69–79
Table 4 (Continued)
Foodstuff Consumption nAl Cu Mn Zn Cd Cr Ni Pb U
(kg year )
y1
(mg kg )
y1
(mg kg )
y1
(mg kg )
y1
(mg kg )
y1
(mgkg )
y1
(mgkg )
y1
(mgkg )
y1
(mgkg )
y1
(mgkg )
y1
3.4–1.1 0.1–1.8 7.2–59 0.8–10 1.0–20 5.2–48 14–141 -0.02–16 0.3–4.8
Corn flour 1.6 3 (5.7)(1.0)(3.1)(9.0)(0.8)(18)(42)(3.3)(0.01)
1.3–10 0.8–1.4 2.4–4.2 8.0–10 0.7–1.0 5.9–117 27–85 -0.09–20 -0.004–0.02
Pasta 4.7 3 (1.8)(1.9)(6.7)(12)(6.6)(6.3)(75)(2.0)(2.1)
1.2–2.3 1.0–3.3 4.0–11 7.2–19 4.6–13 29–94 52–138 -0.003–489 1.0–3.3
Meat 30.6 4 (17)(0.4)(0.2)(21)(1.6)(52)(20)(34)(1.0)
11–23 0.3–0.6 0.1–0.3 5.6–40 0.8–3.7 32–154 10–47 15–81 0.2–5.3
Milk 48 3 (0.1)(0.06)(0.06)(0.09)(1.1)(0.8)(5.0)(140)(0.5)
0.07–0.1 0.001–0.012 0.05–0.07 0.05–0.1 0.03–5.0 0.4–1.7 1.1–12 46–397 0.1–0.7
Fish 3.4 3 (8.3)(0.2)(0.3)(7.6)(3.0)(25)(32)(37)(1.5)
3.7–13 0.2–0.2 0.2–0.4 3.7–11 1.5–4.3 18–32 13–50 24–49 0.7–2.4
Sugar 25 3 (1.2)(0.01)(0.005)(0.003)(2.1)(5.0)(-0.2)(3.8)(-0.1)
0.9–2.4 0.0007–0.03 0.002–0.010 0.0004–0.02 0.3–9.0 3.5–6.5 -0.2 2.7–5.4 -0.1
Coffee 2.7 3 (5.6)(2.3)(11)(20)(12)(200)(575)(179)(2.1)
1.6–9.6 1.3–3.2 9.5–13 16–29 5.0–19 175–230 299–1350 230–308 1.5–3.2
75E.E. Santos et al. / Science of the Total Environment 327 (2004) 69–79
Furthermore, when comparing our data with
those reported in the literature for the same food-
stuff, the concentration values of Al, Cr, Ni, Pb
and Cd are below or in the lower range to those
published elsewhere (Elpo and Freitas, 1995;
MAFF, 1997; Muller et al., 1998; Ramalho et al.,
¨
1997; Sakuma et al., 1989; Toro et al., 1994;
Tsoumbaris and Tsoukali-Papadopoulou, 1994a;
Voutsa and Samara, 1998; Zhang et al., 1996). For
Zn and Cu, concentrations are similar to those
reported in literature (Tsoumbaris and Tsoukali-
Papadopoulou, 1994a; Ramalho et al., 1997; Toro
et al., 1994; Sakuma et al., 1989; Bahemuka and
Mubofu, 1999; Barbera et al., 1993; Voutsa and
´
Samara 1998), however, concentrations of Mn are
higher (Toro et al., 1994; Tsoumbaris and Tsoukali-
Papadopoulou 1994a; Tripathi et al., 2002; Voutsa
and Samara, 1998).
3.2. Daily intake of Al, Cd, Cu, Cr, Mn, Ni, Th, U
and Zn
For the daily intake evaluation, the weighted
average for each metal in each food category was
calculated, and then multiplied by the respective
consumption rate (IBGE, 1998). In the following,
the estimated daily intake for some elements solely
due to food consumption will be discussed.
3.2.1. Aluminum
The estimated daily intake for aluminum was of
3.5 mg day , which is much lower than the
y1
Provisional Tolerable Weekly Intake (PTWI),
whose values is 7 mg kg of body weight,
y1
corresponding to 70 mg day for a 70-kg adult
y1
(FAOyWHO, 1989)and falling in the range of
values reported in literature, 1.9–12 mg day
y1
(Biego et al., 1998; MAFF, 1997; Schaller et al.,
1995; Tripathi et al., 2002). The highest contribu-
tors for aluminum intake are meat, bean, rice and
wheat flour, with 1.51 mg day , 0.74 mg day ,
y1y1
0.28 mg day and 0.24 mg day , respectively.
y1y1
Percentage distributions of different foodstuffs in
daily dietary intake of the examined elements are
shown in Fig. 1.
3.2.2. Cadmium
The daily intake of cadmium was estimated as
1.8=10 mg, that represents approximately 2.6%
y3
of the RfD, whose established value is 0.001 mg
day of body weight, equivalent to 0.07 mg
y1
day for a 70-kg adult (EPA, 2001). This value
y1
is still much lower than the recommended PTWI
of 0.48 mg week (equivalent to 0.07 mg
y1
day )for a 70-kg adult (WHO, 1989). Compar-
y1
ing our value for the daily intake of cadmium with
those reported in literature (0.004–0.084 mg
day ), it can be observed that the intake of this
y1
metal by the inhabitants of Rio de Janeiro city
seems to be much lower (Biego et al., 1998;
Cuadrado et al., 1995; Louekari and Salminen,
1986; Tahvonen and Kumpulainen, 1993; Tsoum-
baris and Tsoukali-Papadopoulou, 1994b). The
biggest contribution to the intake of this element
comes from rice, wheat flour and potato consump-
tions, with 4.6=10 mg day (28%),
y4y1
2.7=10 mg day (16%)and 1.8=10 mg
y4y1y4
day (11%), respectively, as also shown in Fig.
y1
1.
3.2.3. Lead
The daily intake of lead was estimated as
2.8=10 mg, which is approximately 11% of the
y2
PTWI value of 1.7 mg week (equivalent to 0.25
y1
mg day )for a 70-kg adult as established by
y1
WHO (1993). Its value falls in the range of data
(0.007–0.23 mg day )reported in literature (Bar-
y1
bera et al., 1993; Ikeda et al., 2000; Louekari and
´
Salminen, 1986; MAFF, 1997; Watanabe et al.,
2000). Milk contributes with approximately 72%
for the lead intake by the here studied population
(Fig. 1). Some contamination from metal vessels
used to transport milk to the processing industry
could be a possible reason for relatively high Pb
concentration in milk sample (Murta et al., 1993).
3.2.4. Copper
The copper intake was estimated as 1.12 mg
day , which is compatible with the daily supply
y1
needs for adults established by the WHO (1996),
0.7 mg day for men and 0.8 mg day for
y1y1
women, and with the recommended dietary allow-
ances of 0.9 mg day for adults. Furthermore,
y1
the intake value is in the range of values (0.6–1.3
mg day )reported for populations of Japan and
y1
the Philippines (Dang, 1998). However, intake of
76 E.E. Santos et al. / Science of the Total Environment 327 (2004) 69–79
Fig. 1. Contribution of important foodstuffs to the daily dietary intake of trace elements by inhabitants of Rio de Janeiro city.
this element by Rio de Janeiro inhabitants is lower
than the range values (1.2–4.8 mg day )reported
y1
for France and Germany (Biego et al., 1998;
Bratter et al., 1995). Black bean are the biggest
¨
contributor to the intake with 6.3=10 mg
y1
day (60%), followed by rice with 2.1=10
y1y1
mg day (20%)(Fig. 1).
y1
3.2.5. Chromium
The daily intake for this element, estimated in
the present work (2.3=10 mg), is lower than
y2
the RfD of 1.5 mg kg body weight (equivalent
y1
to 105 mg day )and also below the daily intake
y1
recommended by the US National Council (NRC,
1989)for Cr : 0.05 to 0.2 mg. The estimated
3q
value falls in the low-range of values reported in
literature (0.013–0.085 mg day )(Anderson and
y1
Koslovsky, 1985; Anderson et al., 1993; Biego et
al., 1998; Dang, 1998; FAA, 2002; ICDA, 1996;
Kumpulainen, 1992; Schuhmacher et al., 1993).
Meat is the biggest contributor for Cr intake with
4.4=10 mg day (23%)followed by banana
y3y1
3.8=10 mg day (20%)and rice 2.4=10
y3y1y3
mg day (13%)(Fig. 1).
y1
77E.E. Santos et al. / Science of the Total Environment 327 (2004) 69–79
3.2.6. Nickel
The daily intake of nickel was estimated as
8.9=10 mg, which is much lower than the RfD
y2
of 0.02 mg day kg of body weight, equivalent
y1y1
to 1.4 mg day for a 70-kg man (EPA, 2001).
y1
The RDA value of this element is not yet estimat-
ed. The estimated daily intake value (0.089 mg)
falls in the low range of values reported in litera-
ture (0.04–0.7 mg day )(Biego et al., 1998;
y1
Tsoumbaris and Tsoukali-Papadopoulou, 1994b;
Shiraishi et al., 1988). Black beans contribute with
56% (4.8=10 mg day )and rice supplies 16%
y2y1
(1.4=10 mg day )of the total amount of Ni
y2y1
ingested via the studied foodstuffs (Fig. 1).
3.2.7. Manganese
The daily ingestion of manganese was calculated
as 2.5 mg, which corresponds to 24% of the RfD
(9.8 mg day ; EPA, 2001)and which is in the
y1
low-range of the RDA of 2.55.0 mg day . This
y1
daily intake is comparable with the reported values
of 2.2 to 4.6 mg day (Biego et al., 1998; Buchet
y1
and Lauwerys 1983; Fardy et al., 1992; Muncu
and Aras, 1988; Nkwenkeu et al., 2002; Tripathi
et al., 2000). Once more, black bean is the food-
stuff that has the largest contribution to ingestion,
1.3 mg day (52%), followed by wheat flour,
y1
0.67 mg day (28%)(Fig. 1).
y1
3.2.8. Zinc
The daily intake of zinc was estimated as 4.8
mg, being lower than the RDA value (15 mg
day )and others reported in literature, 9.0–18
y1
mg day (Biego et al., 1998, for France; Tsoum-
y1
baris and Tsoukali-Papadopoulou, 1994b, for
Greece; Shiraishi et al., 1988; Bratter et al., 1995;
¨
Dang, 1998). Bean and meat are the largest con-
tributors to zinc intake, both with 1.7 mg day
y1
(36%)(Fig. 1).
3.2.9. Uranium
The estimated ingestion rate of uranium was
3.4=10 mg day , which is lower than the RfD
y4y1
of 1.0=10 mg day kg , equivalent to 0.07
y3y1y1
mg day for an adult. Reported values range
y1
from 7=10 to 2.2=10 mg day (Dang et
y4y3y1
al., 1990; Hamilton, 1972; Fisenne et al., 1987).
Meat, milk and wheat flour are the biggest con-
tributors for uranium ingestion with 25%, 21%
and 17%, respectively.
4. Conclusion
Although the number of samples analyzed is
still small, the data give a first picture of metal
concentration levels in foodstuffs frequently con-
sumed by Rio de Janeiro inhabitants. With the
exception of manganese, concentrations values are
generally lower or close to those reported in
literature for the same foodstuff, giving so far no
evidence that metal contamination via consumed
food is an important input route for toxic metals
here in Rio de Janeiro city. Concerning the micro-
nutrient metals reported, the recommended doses
for the daily intake of copper and manganese are
conveniently supplied by the diet; however, for
chromium and zinc they are below the recommend
daily allowances. Due to the relatively high metal
concentrations in black bean and their traditionally
high consumption rate, this foodstuff is responsible
for the estimated highest rates of ingestion of Al,
Cu, Mn, Ni and Zn, being, therefore a very
important source of micronutrients for the inhabi-
tants of Rio de Janeiro city and, obviously, for
other populations with similar dietary habits. This
study will be continued to increase its statistical
basis.
Acknowledgments
The authors acknowledge gratefully the contri-
butions of Maria L. P. Godoy and Maurıcio Dupim
´
in ICPMS and ICPOES measurements. We wish
to thank Prof. Dr Norbert Miekeley for valuable
comments on the paper. This work received finan-
cial support from the Instituto de Radioprotecao e
˜
¸
Dosimetria (IRD)yComisao Nacional de Energia
˜
Nuclear, Brazil.
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Trace elements are dangerous to human health and there is a rising concern about the quality of processed foods in some parts of the world, especially in Iraq. The chemical composition (total sold, moisture, and ash) and concentrations of trace elements in canned fish (Skipjack tuna, Sardines, Tuna fish, Sardines, and Mackerel) from the Kalar market, Iraq were determined by using an inductively coupled plasma-optical emission spectrometer. The ranges obtained for the elements in mg/kg were as follows: Se (0.025–0.77), As (0.02–1.07), B (0.05–0.7), Ag (0.04–0.83), Ba (0.05–0.975), Mg (29.8–37.5), Mn (0.97–2.09), Cu (0.91–3.09), and Zn (5.12–11.7). The studied canned fishes pose no risk with respect to the estimated daily intake of Se, As, B, Ag, Ba, Mg, Mn, Cu, and Zn. The total target hazard quotients for the studied metals from individual fish species (except Fme, Fma, and Fsh) were more than one, which was responsible for noncarcinogenic risks. The target carcinogenic risk value for arsenic was also higher than the standard (10-4) set by the United States Environmental Protection Agency. It revealed that the consumption of canned fish causes a chronic cancer risk to humans.
... Arsenic concentration varied among the analyzed foodstuffs. This might be owing to variances in arsenic absorption and accumulation capacities, and changes in the development periods and rates of the dietary items (Islam et al. 2014b), and climatic variations for the vast areas of food production in Bangladesh (Santos et al. 2004). All cereals, vegetables, fruits, fish, eggs, milk, and meat samples tested had mean arsenic amounts below the acceptable limit (0.5 mg/ kg) (Codex 2001; Table 1). ...
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The presence of highly poisonous arsenic (As) elements in food concerns humans and animals. In Bangladesh, arsenic-contaminated groundwater is frequently utilized for agricultural irrigation. This is a significant source of arsenic pollution in the human food chain. For the first time, we investigated the presence of total arsenic in various foodstuffs obtained from 30 distinct agricultural eco-zones of Bangladesh to understand human exposure to arsenic through the food chain in Bangladesh. The greatest and lowest As concentrations were reported in fish among the examined dietary items (0.55 mg/kg, fw) and fruit (0.0068 mg/kg, fw), respectively. The results show that arsenic consumption from daily diet and food with drinking water was estimated to be 0.0352 mg/day for rural residents and 0.2002 mg/day for urban residents, respectively. The highest target hazard quotients (THQ) of arsenic in the fish samples surpassed the allowable limit (> 1), proving that fish are the primary dietary items influencing the possible danger to health. However, the target cancer risk (TR) from nutritional arsenic consumption was likewise higher than tolerable. A value of 10⁻⁴ indicates that Bangladeshi people are continuously exposed to arsenic, which has carcinogenic and non-carcinogenic dangers. Overall, our results highlight that people in Bangladesh are exposed to hazardous levels of arsenic throughout the food chain, which should be addressed to ensure the country’s food safety.
... This study evaluates the dietary exposure of metals and metalloids via the ingesting of vegetables and fish item in the daily diet of the adult people. The EDIs of metals and metalloids (As, Ni, Cu, As, and Pb) were assessed based on the mean concentration of every element in every food and the particular ingesting rate (Santos et al., 2004). The EDI of the considered metals and metalloids from the ingestion of fish and vegetables are presented in Tables 3 and 4. In fish and vegetable species, total values of EDI exhibited the downward order of Mn > Cu > Pb > As > Cr > Ni and Mn > Cu > Ni > Cr > Pb > As, respectively. ...
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This study was intended to assess heavy metal contents and sources in commonly consumed vegetables and fish collected from the Jashore district of Bangladesh and to evaluate the probable human health risks via the ingesting of those vegetables and fish species. A total of 130 vegetable and fish samples were analyzed for As, Mn, Cu, Cr, Ni, and Pb concentration by an atomic absorption spectrophotometer. Metals and metalloids like As, Pb, and Cr in vegetable species were greater than the maximum allowable concentration (MAC), while Pb and Cu in fish species exceeded the MAC. Pollution evaluation index values were ranges from 0.40-10.35 and 1.53-2.78 for vegetable and fish species, respectively, indicating light to serious pollution. Lactuca sativa followed by Cucurbita moschata, Amaranthus gangeticus for vegetables and Channa punctate, Oreochromis mossambicus, followed by Dendrobranchiata for fish are the most contaminated food items. The positive matrix factorization model showed that As (81.9%), Ni (48%), Cr (49.6%), Mn (46%), Pb (44.3%), and Cu (44.4%) for vegetable species and As (86.9%), Ni (90.5%), Mn (67.6%), Pb (65.3%), Cr (57%) and Cu (46.2%) for fish species were resulting from agrochemical, atmospheric emission, irrigation, contaminated feed, and mixed sources. The self-organizing map and principle component analysis indicates three spatial patterns e.g., As-Mn-Cu, Pb-Cr, and Ni in vegetables and As-Mn-Cr, Cu-Ni, and Pb in fish samples. The THQ values for single elements were less than 1 (except As for vegetables and Pb for fish species) for all food items but the HI values for all of the vegetables (2.18E+00 to 2.04E+01) and fish (1.07E+00 to 9.39E+00) samples were exceeded the USEPA acceptable risk level (HI>1E+00). While the cancer risks only induced by As for all vegetables and fish species, which exceeded the USEPA safe level (TCR>1E-04). Sensitivity analysis indicates that metal concentration was the most responsible factor for carcinogenic risk.
... The estimated daily intake (EDI) of metals was calculated based on the metal concentrations in crops and the consumption of the respective food crop, as described in [39,41]. ...
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... In order to determine the estimated daily intake (EDI), two categories of target populations were considered according to age: adults and children. The EDI were expressed for each trace element according to the following equation [34][35][36][37]: ...
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The determination of several trace elements, including thorium and the lanthanides in coal and coal ashes applying total dissolution and ICP-MS, was studied. The procedures mere rested with reference materials (Bituminous Coal NIST 1632a and Fly Ash NIST 1633a). For coal samples, chemical ashing with HNO3, HF, and HClO4 produces reasonable results. Regarding coal ash samples, some difficulties related to the determination of rubidium, cesium, thorium, and the lanthanides were found and a proposed solution is discussed. Finally, coal, bottom, electrostatic precipitator (ESP), and fly ash samples from a Brazilian coal-fired power plant were analyzed and an enrichment of Mn, Zn, Ge, As, Se, Mo, Cd, Sb, Ag, Pb, Bi, and U in ny ash was observed. The values obtained for refractory elements, such as thorium, cerium, and scandium, in the ESP samples were compared with those obtained by INAA, with good agreement between both results. The use of a large number of elements (57) during the instrument calibration allows the use of the TotalQuant mode as a routine method, instead of the traditional. quantitative method, aiming at a trace element environmental monitoring program.
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Book
This book represents another attempt to educate analytical chemists in the use of simple statistics. It is an easy-to-read overview of the topics with which every analytical chemist should be familiar. The early chapter on errors in analysis, significance testing, and quality control are well written. A good introduction to these topics is provided in the first 100 pages. Chapter 6 on nonparametric methods is quite useful; it provides justification and incentive to learn and use these methods. Chapter 7 covers very large and useful topics such as experimental design, optimization, and pattern recognition. Fractional factorial designs and principle component analysis are only mentioned, not discussed in detail. This book can be easily read and can heighten one's awareness of many important topics from statistics to chemometrics. Because it comes complete with a number of good exercises (no programs), the author also recommend it as a textbook for a short course.
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Four heavy metals (cadmium, copper, lead and zinc) were determined in some green vegetables cultivated along the sites of the Sinza and Msimbazi rivers. Atomic absorption spectrophotometry was used to estimate and evaluate the levels of these metals in the vegetables. The contributions of the vegetables to the daily intake of the heavy metals from the vegetables were determined. The results showed the following ranges (mg/100 g): 0.01–0.06, 0.25–1.60, 0.19–0.66, and 1.48–4.93 for cadmium, copper, lead and zinc, respectively. Some vegetables contained high levels beyond the permissible levels given by FAO and WHO for human consumption. When the mean levels of cadmium, copper, lead and zinc (0.20, 7.95, 3.95 and 33.75 mg per kg, respectively) were taken into account, the daily intake contribution of these metals was found to be 21.60 μg, 858.60 μg, 426.60 μg and 3.65 mg for cadmium, copper, lead and zinc, respectively.
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Fifty representative foods sampled Australia-wide from each of the State capitals were analysed for manganese by instrumental neutron activation analysis. Calculated daily intake of manganese for Australian diets was compared with recommendations by US authorities for the safe and adequate dietary intake of this essential trace element. The contribution of tea to adult daily intakes was determined.
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The daily intake of uranium (238U) by an urban Indian adult population was estimated by the analysis of a duplicate diet, drinking water, and air samples using neutron activation and radio-chemical separation. The uranium intake through food is 0.55 g which is much larger than that from drinking water and air, at 0.09 and 0.01 g, respectively. The total daily dietary intake of uranium, calculated from the concentrations measured in the individual food ingredients and their daily consumption (based on the national survey), is found to be 2.2 g which is a factor of 3.5 higher than that based on a duplicate urban diet. The maximum contribution to the daily intake is found to be from cereals. The lower intake by the urban population is most likely due to their lower food consumption.
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A duplicate diet meal study was carried out with a group of university students living in a hostel, in order to estimate the intake of Zn, Cd, Co, Cu, Fe, Mn, Ni and Pb. Zn, Cu, Fe, Mn and Ni were determined by flame atomic absorption spectrophotometry and Cd, Co and Pb by graphite furnace atomic absorption spectrophotometry after a nitric acid wet digestion procedure. The estimated intake values from the contents of breakfast, lunch, dinner and drinks were compared with the values of the Provisional Tolerable Daily Intake (PTDI) in the case of Cd and Pb, Recommended Dietary Allowances (RDA) of Co, Fe and Zn and Estimated Safe and Adequate Dietetic Daily Intake (ESADDI) of Cu and Mn. Neither excessive intake of Pb and Cd nor deficiencies in Zn, Co, Fe, Mn or Ni were observed, but Cu intake was lower than the ESADDI.Orale Aufnahme von Cadmium, Cobalt, Kupfer, Eisen, Blei, Nickel. Mangan und Zink mit der Kost von UniversitätsstudentenBei einer Gruppe von in Wohnheimen lebenden Universitätsstudenten wurden die aufgenommenen Mahlzeiten untersucht, um die Aufnahme von Zn, Cd, Co, Cu, Fe, Mn, Ni und Pb zu bestimmen. Zn, Cu, Fe, Mn und Ni wurden mittels Flammenatomabsorptionsspektrophotometrie bestimmt, Cd, Co und Pb durch Graphitofenatomabsorptionsspektrophotometrie nach nassem Aufschluß mit salpetriger Säure. Die ermittelten, mit Frühstück, Lunch, Dinner und Getränken aufgenommenen Werte wurden im Falle von Cd und Pb verglichen mit den Werten der Provisional Tolerable Daily Intake, im Falle von Co, Fe und Zn mit denen der Recommended Dietary Allowances und im Falle von Cu und Mn mit den Werten der Estimated Safe and Adequate Dietetic Daily Intake (ESADDI). Es wurden weder überhöhte Aufnahmen von Pb und Cd, noch unzureichende Aufnahmen von Zn, Co, Fe, Mn oder Ni festgestellt; die Zufuhr von Cu war niedriger als die Werte nach ESADDI.