Journal of Food Composition and Analysis 48 (2016) 81–87

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Journal of Food Composition and Analysis

journal homepage: www.elsevier.com/locate/jfca

Essential and non-essential/toxic elements in rice available in the

Portuguese and Spanish markets
Edgar Pintoa,* , Agostinho Almeidab , Isabel M.P.L.V.O. Ferreiraa
a
LAQV/REQUIMTE, Departamento de Ciências Químicas, Laboratório de Bromatologia e Hidrologia, Faculdade de Farmácia, Universidade do Porto, Rua Jorge
Viterbo Ferreira, 228, 4050-313 Porto, Portugal
b
LAQV/REQUIMTE, Departamento de Ciências Químicas, Laboratório de Química Aplicada, Faculdade de Farmácia, Universidade do Porto, Rua Jorge Viterbo
Ferreira, 228, 4050-313 Porto, Portugal

A R T I C L E I N F O A B S T R A C T

Article history: Eighty-six rice samples, representing the most common rice brands sold in Portuguese and Spanish
Received 19 February 2015 markets (either locally produced or imported), were analyzed for their content of 35 essential and non-
Received in revised form 16 January 2016 essential/toxic elements using inductively coupled plasma-mass spectrometry (ICP-MS). The mean
Accepted 19 February 2016
content of essential elements was: 1189 mg/kg (P), 746 mg/kg (K), 294 mg/kg (Mg), 84.7 mg/kg (Ca),
Available online 22 February 2016
13.3 mg/kg (Zn), 8.8 mg/kg (Na), 8.3 mg/kg (Mn), 7.5 mg/kg (Fe), 1.9 mg/kg (Cu), 0.55 mg/kg (Mo), 0.18 mg/
kg (Se) and 0.12 mg/kg (Co). However, significant differences exist between the different types of rice,
Keywords:
with brown rice showing the highest content of most essential elements. The daily intake of essential
Rice
ICP-MS
elements resulting from the average Iberian (Portugal and Spain) per capita consumption of rice was
Essential elements calculated and its contribution to the Recommended Dietary Allowance (RDA) or Adequate Intake (AI)
Non-essential/toxic elements was estimated. Data showed that rice can be an important dietary source of P, Zn, Mn, Cu, Mo and Se but
Dietary intake does not significantly contribute to the daily dietary intake of Ca, Na and Fe. The content of toxic elements
Food composition was very low, indicating that rice can be regarded as a very safe food.
Food analysis ã 2016 Elsevier Inc. All rights reserved.

1. Introduction
Rice (the seeds of Oryza spp., mainly Oryza sativa) is a staple
food for almost two-thirds of the world’s population (Borresen and
Ryan, 2014). Rice plant is cultivated almost worldwide, but China,
India and Bangladesh are the largest rice producing countries. In
Europe, most rice production is located in Italy and Spain, with
both countries accounting for about 80% of the total European
production. Portugal only represents around 6% of the rice
production in Europe (FAOSTAT, 2015a). Rice consumption in
Portugal and Spain has been steadily growing over the last years,
mainly because consumers are switching from high-protein diets
to high-carbohydrate diets as a result of the decreased purchase
power caused by the economic recession. Portugal has one of the
highest per capita consumption of rice in Europe, with approxi-
mately 16 kg (milled equivalent) per year in 2011 (FAOSTAT,
2015b).
Several minerals are necessary for humans to normal function-
ing of the body. Although the adequate intake of most minerals is
usually achieved, low intakes for extended periods of time can
* Corresponding author. Tel.: +351 220 428 500; fax: +351 226093390.
E-mail addresses: ecp@estsp.ipp.pt, edgarpinto7@gmail.com (E. Pinto).
cause deficiency signs. Nowadays, severe cases of iron (Fe) and
selenium (Se) deficiency still exist all over the world, and the
dietary intake of other minerals such as calcium (Ca), magnesium
(Mg), iodine (I) and zinc (Zn) may be inadequate in several
countries (Li et al., 2013; Stein, 2010). The introduction of the
Recommended Dietary Allowances (RDAs), defined as “the levels of
intake of essential nutrients that, on the basis of scientific
knowledge, are judged by the US Food and Nutrition Board to
be adequate to meet the known nutrient needs of practically all
healthy persons” was a very important milestone in human
nutrition science. RDAs are established based on the estimated
average requirements (EAR), taking into consideration the incom-
plete utilization of the ingested nutrient (bioavailability) and
integrating a safety factor to account for inter-individual variability
(FNB/IOM, 2006).
Rice is an important source of energy, vitamins, amino acids,
minerals and other nutrients for humans. The mineral content of
rice is highly influenced by the degree of polishing/milling. During
this process, the bran (i.e., the germ/embryo and the aleurone/
pericarp layers) is removed from the brown rice resulting in white
rice grains (Hansen et al., 2012). Since the outer grain layers are
richer in minerals than the inner core, a significantly lower mineral
content is usually observed in the polished/milled grains (Kumar

http://dx.doi.org/10.1016/j.jfca.2016.02.008
0889-1575/ ã 2016 Elsevier Inc. All rights reserved.
82 E. Pinto et al. / Journal of Food Composition and Analysis 48 (2016) 81–87
et al., 2010). Therefore, a wide variability between the different
commercially available rice brands is expected to exist.
Due to its large consumption, the accurate determination of
the elemental composition of rice is of utmost importance for
estimating the population’s dietary intake of nutrients and their
exposure to toxic elements. Based on this background, the aim
of the present work was to determine the content of a wide
range of elements (essential and non-essential/toxic elements)
in rice commercially available in the Portuguese and Spanish
markets. The contribution of dietary rice consumption for the
daily intake of essential and non-essential/toxic elements was
also estimated.
2. Material and methods
2.1. Samples
Rice samples were obtained from several supermarkets located
in Porto (Portugal) and Vigo (Spain) cities in May 2014. A total of
86 rice samples from different types were analyzed: white rice
(n = 56), parboiled rice (n = 13), brown rice (n = 11) and wild rice
(n = 6). Wild rice (Zizania spp.) was also included in this study due
to its close similarity to Oryza spp. The brand, country of origin and
type of rice for each sample is listed in Table S1 (Supplementary
material).
2.2. Reagents
High purity HNO3 (
69% w/w, TraceSELECT1, Fluka, L’Isle
d’Abeau Chesnes, France) and H2O2 (
30% v/v, TraceSELECT1,
Fluka, Seelze, Germany) were used as received. The internal
standard solution was prepared by appropriate dilution of the
AccuTraceTM (AccuStandard1, New Haven, CT) ICP-MS-200.8-IS-1
(100 mg/mL of Sc, Y, In, Tb and Bi) solution. Calibration standards
were prepared from the 10 mg/mL multi-element ICP-MS standard
solution (PlasmaCAL SCP-33-MS, SCP Science, Baie-d’Urfé, Quebec,
Canada), from the 100 mg/mL multi-ion chromatography standard
solution (AccuSPEC, SCP Science, Baie-d’Urfé, Quebec, Canada) and
from the 1000 mg/mL Hg standard solution (TraceCERT1, Sigma–
Aldrich, Buchs, Switzerland). All solutions were prepared using
ultrapure water (>18.2 MV cm at 25  C) obtained with a Milli-Q RG
(Millipore, Billerica, MA) water purification system.
2.3. Instrument and apparatus
A Milestone (Sorisole, Italy) MLS 1200 Mega high performance
microwave digestion unit equipped with an HPR-1000/10 S rotor
was used for closed vessel acid digestion of the samples.
Inductively coupled plasma-mass spectrometry (ICP-MS) analy-
ses were performed using an iCAPTM Q instrument (Thermo Fisher
Scientific, Bremen, Germany), equipped with a MicroMist
nebulizer, a baffled cyclonic spray chamber (peltier-cooled), a
standard quartz torch and a two-cone design (sample and
skimmer cones). High purity (99.9997%) argon (Gasin II, Leça
da Palmeira, Portugal) was used as the plasma source. The ICP-MS
instrument operational parameters were as follow: RF power—
1550 W; plasma gas flow—14 L/min; auxiliary gas flow—0.8 L/min;
nebulizer flow rate—0.95 L/min. The following elemental isotopes
(m/z ratios) were monitored for analytical determinations: 7Li, 9Be,
23
Na, 24Mg, 27Al, 31P, 39K, 44Ca, 47Ti, 51V, 52Cr, 55Mn, 57Fe, 59Co, 60Ni,
65
Cu, 66Zn, 75As, 79Br, 81Br, 82Se, 85Rb, 88Sr, 95Mo, 107Ag, 111Cd, 118Sn,
121
Sb, 137Ba, 139La, 140Ce, 202Hg, 205TI, 208Pb, 232Th and 238U; 45Sc,
89
Y, 115In and 159Tb were used as internal standards. The
instrument was tuned daily for maximum signal sensitivity and
stability as well as for low oxides and doubly charged ion
formation using the Tune B iCAP Q solution (Thermo Fisher
Scientific; 1 mg/L of Ba, Bi, Ce, Co, In, Li and U in 2% HNO3 + 0.5%
HCl). Limits of detection (LOD) were estimated from 10 measure-
ments of the blank solution (2% v/v HNO3) and are presented in
Supplementary material (Table S2).
2.4. Samples pretreatment
Rice samples were homogenized by grinding in a blender and
sieved through a nylon sieve of 1 mm mesh size before acid
digestion. The high-pressure microwave digestion rotor accom-
modates 10 PTFE vessels. Of these 10 vessels, eight were samples,
one was a blank, and one was the certified reference material
IRMM 807 or BCR 679. This configuration was kept unchanged in
each digestion procedure. Powdered samples (500 mg) were
weighed into the microwave oven PTFE vessels and 4 mL of HNO3
(
69% w/w) plus 1 mL of H2O2 (
30% v/v) were added to each
vessel. The mixture was heated using the following microwave
program: 250 W for 1 min, 0 W for 2 min, 250 W for 5 min, 400 W
for 5 min, and 600 W for 5 min. After cooling, samples solutions
were diluted to 25 mL in decontaminated volumetric flasks with
ultrapure water. All solutions were analyzed by ICP-MS. All
samples were analyzed in triplicate. Results were expressed as
mg/kg, on a dry weight (dw) basis.
2.5. Estimated daily intake of elements
The Estimated Daily Intake (EDI) of essential elements resulting
from rice consumption was calculated based on the elemental
content (Celements; mg/kg dw basis) and the average per capita daily
consumption of rice (DCrice), using the following formula:
EDI ¼ C elements  DCrice
where EDI is expressed in mg/day and DC was assumed to be
35.5 g/person/day for Iberian (Portugal and Spain) consumers
(FAOSTAT, 2015b). The obtained values where compared with RDA
(Recommended Dietary Allowance) or AI (Adequate Intake) as
suggested by FNB/IOM (2006). Cobalt was not considered since no
RDA or AI have been established.
2.6. Provisional tolerable weekly intake
The Provisional Tolerable Weekly Intake (PTWI) of non-
essential/toxic elements resulting from rice consumption was
calculated based on the elemental content (Celements; mg/kg dw
basis), the average per capita weekly consumption of rice (WCrice)
and the individual’s body weight (bw), using the following
formula:
C elements  WCrice
PTWI ¼
bw
where bw was assumed to be 70 kg and WC was assumed to be
248.5, which was derived by multiplying the number of days in a
week (i.e., 7) by 35.5 that is the daily per capita rice consumption
for Iberian (Portugal and Spain) consumers (FAOSTAT, 2015b). The
obtained values where compared with the PTWI values published
by JECFA (2011).
2.7. Quality control
For quality control purposes, the certified reference material
(CRM) IRMM 807 (rice flour, supplied by EC Institute for Reference
Materials and Measurements, Geel, Belgium) and BCR 679 (white
cabbage, supplied by EC Institute for Reference Materials and
Measurements, Geel, Belgium) were analyzed under the same
conditions as for the samples. The average recoveries obtained in
the CRM analysis are presented in Table 1.
 E. Pinto et al. / Journal of Food Composition and Analysis 48 (2016) 81–87 83

Table 1 2013; NFA, 2013; THL, 2013; UiO, 2012; USDA, 2014) were used for
Recoveries of the certified reference material (CRM) IRMM 804 and BCR 679
comparative purposes. For this purpose, the average content of
(mean  SD; n = 3).
each element was calculated considering the reported value of
Element Certified value (mg/kg) Determined value (mg/kg) Recovery (%) each National Food Database. For non-essential/toxic elements,
IRMM 804 results obtained were compared with available literature data
Mn 34.2  2.3 34.5  1.1 100.7  1.1 (Antoine et al., 2012; Batista et al., 2010; Ekholm et al., 2007; Li
Zn 23.1  1.9 22.8  0.7 98.7  3.1
et al., 2013; Parengam et al., 2010).
Cu 2.74  0.24 2.63  0.11 96.1  4.0
As 0.049  0.004 0.053  0.003 108.6  6.7
Cd 1.61  0.07 1.54  0.04 95.7  2.6 3.1. Essential elements
Pb 0.42  0.07 0.45  0.03 106.0  7.2
3.1.1. White rice
BCR 679
The content of essential elements in white rice (WR) was in the
P 3307  241 3204  52 96.9  1.6
Mg 1362  127 1338  85 98.2  6.2 following order: P > K > Mg > Ca > Zn > Na > Mn > Fe > Cu > Mo > Se >
Ca 7768  655 8057  605 103.6  7.8 Co. This type of rice showed a significantly lower content of P and K
Mn 13.3  0.5 13.4  0.2 100.4  1.2 compared to the other types of rice studied (Fig. 1A). The obtained
Zn 79.7  2.7 79.0  1.1 99.1  1.3
values were well within reported ranges, except for K, Ca and Na,
Fe 55.0  2.5 52.4  5.3 95.3  9.6
Cu 2.89  0.12 2.85  0.02 98.6  0.6
which showed a lower content (483  227 vs. 1027  243 mg/kg for
Mo 14.8  0.5 15.1  0.2 101.7  1.3 K, 32  18 vs. 87  28 mg/kg for Ca and 8.7  4.4 vs. 29.6  20.7 mg/
Ni 27.0  0.8 26.7  0.2 98.8  0.9 kg for Na). No data are available for Mo and Co content in WR, thus
Cr 0.6  0.1 0.65  0.03 108.3  4.5 it was not possible to compare the results (Table 2).
Sr 11.8  0.4 12.0  0.14 101.4  1.2
Ba 10.3  0.6 10.1  0.33 98.1  3.2
Cd 1.66  0.07 1.73  0.03 104.1  2.0 3.1.2. Parboiled rice
Sb 0.0206  0.0026 0.0239  0.0023 116.0  11.1 The content of essential elements in parboiled rice (PR) was in
Hg 0.0063  0.0014 0.0051  0.0012 81.7  18.5 the following order: P > K > Ca > Mg > Na > Fe > Zn > Mn > Cu > Mo >
TI 0.0030  0.00003 0.0032  0.0004 107.7  13.6 Se > Co. Zn was significantly lower than in the other types of rice
studied (Fig. 1B). The obtained values were well within reported
2.8. Statistical analysis ranges, except for Mn and Na, which showed a lower content
(5.6  1.3 vs. 10.1 1.0 mg/kg for Mn and 8.9  2.4 vs.
Data exploration, descriptive statistics calculation and ANOVA 25.2  13.9 mg/kg for Na). No data are available for Mo and Co
were performed with IBM SPSS Statistics for Windows, version content in PR, thus it was not possible to compare the results
22.0 (IBM Corp., Armonk, NY). Significant differences were (Table 2).
assumed at p < 0.05. For mathematical calculations, results below
the LOD were assumed as the LOD divided by the square root of 2, a 3.1.3. Brown rice
commonly used procedure for data imputation (Succop et al., The content of essential elements in brown rice (BR) was in the
2004). following order: P > K > Mg > Ca > Mn > Zn > Fe > Na > Cu > Mo > Co >
Se. BR showed a significantly higher content of P, K, Mg, Mn and Fe
3. Results than the other types of rice (Figs. 1A and B). The obtained values
were well within reported ranges, except for Ca and Na, which
Eighty-six (86) rice samples were analyzed for their content in showed lower levels (64  9 vs. 105  17 mg/kg for Ca and 9.1  5.0
35 elements. The results are summarized in Table 2 (essential vs. 34.1  22.7 mg/kg for Na). No data are available for Mo and Co in
elements) and Table 3 (non-essential/toxic elements). For essential BR, thus it was not possible to compare the results (Table 2).
elements, data from important National Food Databases (Canada,
Czech Republic, Denmark, Finland, France, Iceland, Italy, 3.1.4. Wild rice
Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and The content of essential elements in wild rice (WiR) was in the
USA) (ANSES, 2012; BDA, 2008; BEDCA, 2006; CNF, 2015; Database, following order: P > K > Mg > Ca > Zn > Na > Fe > Mn > Cu > Mo > Co >
2013; DTU, 2009; ETHZ, 2014; INSA, 2010; ISGEM, 2003; NEVO, Se. WiR showed a significantly higher content of Zn and Cu

Table 2
Content (mean  SD, mg/kg) of 12 essential elements in the analyzed rice samples.

Element White rice (n = 56) Parboiled rice (n = 13) Brown rice (n = 11) Wild rice (n = 6)

Our data National Food Our data National Food Our data National Food Our data National Food Databases
Databases Databases Databases
P 958  214 1117  150 1432  208 1525  233 2929  262 2912  346 2273  379 3540  461
K 483  227 1027  243 1315  116 1578  278 2292  295 2278  217 1908  103 3948  559
Mg 225  63 279  72 215  50 295  35 1064  87 1092  159 561  98 1553  376
Ca 32  18 87  28 370  272 223  145 64  9 105  17 238  170 175  61

Zn 13.5  3.4 13.7  3.3 6.1  1.4 8.3  3.4 15.9  2.3 18.0  2.1 24.7  4.6 54.1  9.8
Na 8.7  4.4 29.6  20.7 8.9  2.4 25.2  13.9 9.1  5.0 34.1  22.7 10.1  2.6 59.3  18.6
Mn 7.5  1.9 9.9  1.1 5.6  1.3 10.1  1.0 21.5  4.4 23.1  2.3 5.5  0.8 12.1  1.1
Fe 6.8  1.5 7.3  2.5 8.6  1.9 9.4  4.1 14.0  2.1 13.3  5.2 7.8  1.2 17.3  4.2
Cu 1.8  0.6 2.1  0.4 2.0  0.6 2.2  0.9 1.6  0.4 1.9  0.6 3.3  1.9 3.8  2.0

Mo 0.58  0.29 – 0.39  0.13 – 0.38  0.14 – 0.33  0.02 –

Se 0.20  0.19 0.12  0.03 0.10  0.05 0.05  0.02 0.03  0.02 0.03  0.02 0.12  0.04 –
Co 0.12  0.09 – 0.09  0.06 – 0.10  0.04 – 0.17  0.07 –
84 E. Pinto et al. / Journal of Food Composition and Analysis 48 (2016) 81–87

Table 3
Content (mean  SD, mg/kg) of 13 non-essential/toxic elements in the analyzed rice samples.

Element White rice (n = 56) Parboiled rice (n = 13) Brown rice (n = 11) Wild rice (n = 6)

Our data Literature data Our data Literature data Our data Literature data Our data Literature data
Br 9.40  28.6 10.7  28.3 4.05  1.59 – 2.06  1.11 3.39  6.42 2.80  0.83 –
Ti 2.02  0.67 – 2.76  0.93 – 5.84  1.14 – 3.29  0.51 –
Rb 1.77  1.45 4.75  2.12 1.70  0.73 12.1  7.4 3.35  1.06 7.55  4.17 2.08  0.52 –
Al 0.53  0.53 8.17  2.27 0.37  0.19 – 1.12  0.34 13.5  3.33 0.31  0.17 –
As 0.17  0.06 0.13  0.04 0.16  0.05 0.10  0.04 0.21  0.05 0.17  0.01 0.18  0.03 –
Sr 0.20  0.14 1.93  0.35 0.34  0.17 – 0.68  0.17 2.83  0.68 0.24  0.12 –
Cr 0.11  0.05 0.08  0.04 0.08  0.03 – 0.10  0.05 0.16  0.14 0.13  0.08 –
V 0.10  0.08 0.04  0.02 0.07  0.01 0.006  0.005 0.09  0.02 0.06  0.02 0.11  0.02 –
Ba 0.07  0.06 – 0.03  0.01 – 0.17  0.04 – 0.05  0.03 –
Ni 0.06  0.04 0.25  0.08 0.13  0.05 – 0.09  0.06 0.29  0.09 0.14  0.10 –
Cd 0.011  0.010 0.014  0.004 0.005  0.003 0.011  0.005 0.010  0.007 0.014  0.003 0.009  0.006 –
Pb 0.003  0.002 – 0.003  0.002 – 0.005  0.004 – 0.002  0.002 –

Fig. 1. Content of essential (A–C) and non-essential/toxic (D–F) elements in white, parboiled, brown and wild rice. Data presented as mean  SD. Different letters (a–d) in the
bars of each element indicate significant differences between types of rice at p < 0.05. * the error bar is not shown because the standard deviation is too high.

compared to the other types of rice (Fig. 1B). The obtained values
were lower than the reported ranges, except for Ca and Cu that
were well within the reported ranges. No data are available for Mo,
Se and Co in WiR, thus it was not possible to compare the results
(Table 2).
3.2. Non-essential/toxic elements
Antimony, beryllium, cerium, lanthanum, lithium, mercury, tin,
thallium, thorium and uranium were all undetectable in the
analyzed rice samples. Silver (Ag) was detected only in 17 of the
86 rice samples analyzed, which were mainly from the WR group.
The mean Ag content in WR samples was 0.003 mg/kg.
3.2.1. White rice
The content of non-essential/toxic elements in WR was in the
following order: Br > Ti > Rb > Al > As > Sr > Cr > V > Ba > Ni > Cd > Pb.
WR showed a significantly lower content of Ti compared to the
other types of rice (Fig. 1D). The obtained values were well within
reported ranges for Br, As, Cr, V and Cd and below reported ranges
for Rb (1.77  1.45 vs. 4.75  2.12 mg/kg), Al (0.53  0.53 vs.
8.17  2.27 mg/kg), Sr (0.20  0.14 vs. 1.93  0.35 mg/kg) and Ni
(0.06  0.04 vs. 0.25  0.08 mg/kg). No data are available for Ti, Ba,
Ni and Pb in WR, thus it was not possible to compare the results
(Table 3).
3.2.2. Parboiled rice
The content of non-essential/toxic elements in PR was in the
following order: Br > Ti > Rb > Al > Sr > As > Ni > Cr > V > Ba > Cd > Pb.
Few data are available on the content of these non-essential/toxic
elements in PR. The only reported values found were for Rb, As, V
and Cd. The obtained values were below reported ranges for Rb
(1.70  0.73 vs. 12.1 7.4 mg/kg) and Cd (0.005  0.003 vs.
0.011  0.005 mg/kg) and above reported ranges for As
(0.16  0.05 vs. 0.10  0.04 mg/kg) and V (0.07  0.01 vs.
0.006  0.005 mg/kg) (Table 3).
3.2.3. Brown rice
The content of non-essential/toxic elements in BR was in the
following order: Ti > Rb > Br > Al > Sr > As > Ba > Cr > Ni  V > Cd > Pb.
BR showed a significantly higher content of Al, Sr and Ba compared
to the other types of rice (Fig. 1D and E). The obtained values were
 E. Pinto et al. / Journal of Food Composition and Analysis 48 (2016) 81–87 85

well within reported ranges for Br, As, Cr, V and Cd and below
reported ranges for Rb (3.35  1.06 vs. 7.55  4.17 mg/kg), Al
(1.12  0.34 vs. 13.5  3.33 mg/kg), Sr (0.68  0.17 vs.
2.83  0.68 mg/kg) and Ni (0.09  0.06 vs. 0.29  0.09 mg/kg)
(Table 3).
3.2.4. Wild rice
The content of non-essential/toxic elements in WiR was in the
following order: Ti > Br > Rb > Al > Sr > As > Ni > Cr > V > Ba > Cd > Pb.
No data are available for these elements in WiR, thus it was not
possible to compare the results (Table 3).
4. Discussion
Phosphorus was the most abundant essential element in the
four types of rice analyzed (WR, PR, BR and WiR). The P content
profile observed was BR > WiR > PR > WR, being all significantly
different (Fig. 1A). Phosphorus is present in significant amounts in
the rice bran. Thus, polishing is expected to significantly reduce the
P content of the rice (Canan et al., 2011), which explains the
significantly lower P content of WR found in the present study. The
same content profile was observed for K (BR > WiR > PR > WR), Mg
(BR > WiR > PR  WR), Mn (BR > PR  WR  WiR) and Fe (BR > PR 
WR  WiR), which indicates that these elements are also present in
significant amounts in the outer layers of rice (Fig. 1A and B).
A significantly higher content of Ca was found in PR and WiR,
with the first one showing the highest values (Fig. 1A). It is well-
established that the parboiling process significantly increases the
content of Ca in rice. However, the wide range of Ca content
obtained in the analyzed PR (from 11 to 1028 mg/kg) indicates that
parboiling conditions, such as soaking time and temperature,
greatly influence the Ca content of PR (Prom-u-thai et al., 2010).
Besides their total content in food, the bioavailability of K, Ca,
Mg, Mn, Fe, Zn is a key aspect in mineral nutrition. Dietary
constituents such as phytic acid in cereals and fiber in vegetables
and fruits can have a negative impact on their bioavailability, by
decreasing its intestinal absorption (Kumar et al., 2010; Suliburska
and Krejpcio, 2014). Furthermore, with regard to Fe, protein-rich
foods such as meat, fish and poultry are good sources of heme Fe,
which is highly bioavailable. On the other hand, plant-based foods
(e.g., vegetables, fruits and whole grains) can be an important
source of nonheme Fe, which is less bioavailable (Lönnerdal and
Hernell, 2013).
No significant differences were observed between the content
of both Mo and Se in the different types of rice (Fig. 1C). However, it
must be highlighted that within the group WR, Basmati and Risotto
showed a mean Mo content 2–3 times higher than the other WR
(data not shown). For Se content, the wide range observed in the
WR group (from 0.01 to 2.80 mg/kg) was mainly due to Basmati
rice, which showed a Se content 4–10 fold higher than the other
WR (data not shown).
When compared to National Food Databases, the obtained
values for WR, PR and BR were well within the reported ranges for
most elements. The exceptions were K, Ca and Na in WR, Mn and
Na in PR and Ca and Na in BR; for these elements, the obtained
values were lower than those reported by the National Food
Databases. It can be seen that the Na content in WR, PR and BR is
lower than the Na content reported by National Food Databases.
This is a good news for consumers because nowadays there is a
demand for food with lower salt content and rice can be regarded
as one. However, it should be pointed out that a wide range of Na
content was found in the considered National Food Databases (10–
80 mg/kg) and that a Na content similar to ours have sometimes
been observed. For the other elements (K and Ca in WR, Mn in PR
and Ca in BR), a significant lower content was in fact observed in
this study compared to the National Food Databases. Since these
are essential elements, the Iberian consumer must be aware that
rice can be providing less essential elements than previously
reported by National Food Databases and that a careful re-
evaluation of rice elemental content should be carried out by food
organizations to update its actual contribution to consumers’ diet.
For WiR, the obtained values were below the reported ranges,
except for Ca and Cu. However, few National Food Databases show
the content of essential elements in this type of rice and those that
show this information display a huge variation between each
other’s.
The most abundant non-essential/toxic element in both WR
and PR was Br while in BR and WiR it was Ti. BR showed a
significantly higher content of Ti, Rb, Al, Sr and Ba. Again, this can
be due to the fact that rice bran contains a significant amount of
these elements and when polishing occurs the content of these
elements is reduced in the final product (i.e., WR). A large variation
in the content of Br (0.32–201.45 mg/kg) was observed in WR. This
was mainly due to Basmati rice, which showed a 7- to 10-fold
higher content of Br than the others WR (data not shown).
No significant differences were observed between the content
of As, Cd and Pb in all the four types of rice. Arsenic was the most
abundant toxic element with a mean content of 0.17, 0.16, 0.21 and
0.18 mg/kg for WR, PR, BR and WiR, respectively (Fig. 1E). Rice
contamination by As is a well-known problem and extensive
literature exists on the content of both organic and inorganic As
species in different types/varieties of rice (Norton et al., 2012).
Organic As species are virtually non-toxic while inorganic species
can be highly toxic (Nielsen, 2013). According to EFSA report on

Table 4
Estimated daily intake (EDI) of essential elements considering the average Iberian (Portugal and Spain) per capita consumption of rice (35.5 g/person/day).

Element EDI (expressed as % of the RDA/AI) RDA/AI (mg/day)

WR PR BR WiR

Male Female Male Female Male Female Male Female Male Female
P 4.9 7.3 14.9 11.5 700
K 0.4 1.0 1.7 1.4 4700
Ca 0.11 1.3 0.2 0.9 1000
Mg 1.9 2.5 1.8 2.4 9.0 11.8 4.8 6.2 420 320
Mn 11.7 14.9 8.6 11.0 33.3 42.5 8.5 10.8 2.3 1.8
Zn 4.3 6.0 1.8 2.5 5.1 7.0 8.0 10.9 11 8
Fe 3.0 1.4 3.8 1.7 6.2 2.8 3.5 1.5 8 18
Na 0.02 0.02 0.02 0.02 1500
Cu 7.0 8.0 6.4 13.0 0.9
Mo 46.0 29.6 30.3 25.9 0.045
Se 13.2 6.8 1.6 8.0 0.055

RDAs (Recommended Dietary Allowances) and AIs (Adequate Intakes) may both be used as goals for individual intake. RDAs are in regular type and AIs in bold type.
86 E. Pinto et al. / Journal of Food Composition and Analysis 48 (2016) 81–87
Table 5
Provisional Tolerable Weekly Intake (PTWI) of toxic elements considering the
average Iberian (Portugal and Spain) per capita consumption of rice (35.5 g/person/
day).
Element PTWI (expressed as % of the established PTWI) PTWI (mg/kg bw)
WR PR BR WiR
Al 0.2 0.1 0.4 0.1 1000
As 5.0 6.4 5.0 5.4 15a
Cd 0.6 0.2 0.5 0.5 7 Acknowledgments
Pb 0.04 0.04 0.07 0.03 25a
a
Former values (withdrawn because they are no longer considered health-
protective). Currently, no PTWI values are established (JECFA, 2011).
arsenic, where 600 rice samples were analyzed for their content of
inorganic and total As, inorganic As represents approximately 70%
of the total As content. Thus, we can assume that from the 0.17, 0.16,
0.21 and 0.18 mg/kg of total arsenic observed in WR, PR, BR and
WiR, respectively, about 0.12, 0.11, 0.15 and 0.13 mg/kg is inorganic
As. If we consider this, the obtained values are in close agreement
with the values of inorganic As obtained by EFSA in its scientific
report (EFSA, 2014).
Table 4 shows the EDI (expressed as % of the RDI/AI) considering
the average Iberian (Portugal and Spain) per capita consumption of
rice. Estimates are for adults aged 19–50 years. Overall, rice can be
an important dietary source of P, Zn, Mn, Cu, Mo and Se. For these
elements, rice can provide more than 5% of the RDI/AI. However,
the contribution is highly dependent on the type of rice. BR is a
richer source of essential elements. For instance, for P, BR accounts
for almost 15% of the RDI whereas PR and WR only contribute with
7.3% and 4.9%, respectively. However, both PR and WR can be
important dietary sources of other essential elements. PR provides
the highest contribution for Ca, accounting for 1.3% of the AI. WR
contributes significantly to Se intake, providing as much as 13.2% of
the RDI. WiR can be an important dietary source of Cu (it can
provide about 13% of the RDI). The four types of rice can be a
significant source of Mo (providing at least 25.9% of the RDI). Rice
does not significantly contribute to the daily dietary intake of Fe, Ca
and Na. The estimates show that a person consuming 35.5 g/day of
WR (the most widely consumed type of rice) gets less than 3%
(males) and 1.4% (females) of the RDI for Fe, about 0.1% of the AI for
Ca and less than 0.1% of the RDI for Na.
For comparison purposes, the Provisional Tolerable Weekly
Intake (PTWI) values obtained for Al, As, Cd and Pb were compared
with the current PTWI values established by the Joint FAO/WHO
Committee on Contaminants in Foods (JECFA, 2011). Table 5 shows
our PTWI values (expressed as % of the established PTWI)
considering once again the average Iberian (Portugal and Spain)
per capita consumption of rice. Overall, rice does not importantly
contribute for the PTWI of Al, Cd and Pb. On the contrary, for As,
which was the worst case, rice consumption may represent about
5.5% of the PTWI. However, it should be pointed out that the
established PTWI value for As (15 mg/kg bw) is only for inorganic
As. Since total As was measured and organic As species are
relatively non-toxic, the actual toxicological relevance of As levels
should be lower. Despite that, these results corroborate EFSA
report, which found that there is a “significant contribution of rice
to the dietary exposure to inorganic As” (EFSA, 2014). For the
remaining elements (Al, Cd and Pb), rice only accounts for less than
0.6% of their PTWI (Table 5).
5. Conclusion
Overall, the obtained results showed that: (1) BR contains, on
average, higher amounts of essential elements like P, K, Mg, Mn and
Fe; (2) PR is particularly rich in Ca; (3) WR contains higher levels of
Mo and Se; and (4) WiR is a richer source of Cu and Zn. Additionally,
the content of non-essential/toxic elements in the different types
of rice analyzed (WR, PR, WR and WiR) was very low, indicating
that the most common rice brands sold in Portuguese and Spanish
markets (either locally produced or imported) can be regarded as
very safe. The present study contributes to the knowledge of the
content of both essential and non-essential/toxic elements in
poorly studied types of rice such as PR and WiR.
This work received financial support from the European Union
(FEDER funds through COMPETE) and National Funds (FCT)
through project Pest-C/EQB/LA0006/2013. The work also received
financial support from the European Union (FEDER funds) under
the framework of QREN through Project NORTE-07-0124-FEDER-
000069.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jfca.2016.02.008.
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