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Cooking rice in a high water to rice ratio reduces inorganic arsenic content
Andrea Raab,
ab
Christina Baskaran,
c
Joerg Feldmann
b
and Andrew A. Meharg*
a
Received 29th September 2008, Accepted 12th November 2008
First published as an Advance Article on the web 20th November 2008
DOI: 10.1039/b816906c
Total arsenic and arsenic speciation was performed on different rice
types (basmati, long-grain, polished ([white] and wholegrain
[brown]) that had undergone various forms of cooking. The effect of
rinse washing, low volume (2.5 : 1 water : rice) and high volume (6 : 1
water : rice) cooking, as well as steaming, were investigated. Rinse
washing was effective at removing circa. 10% of the total and
inorganic arsenic from basmati rice, but was less effective for other
rice types. While steaming reduced total and inorganic arsenic rice
content, it did not do so consistently across all rice types investi-
gated. Low volume water cooking did not remove arsenic. High
volume water : rice cooking did effectively remove both total and
inorganic arsenic for the long-grain and basmati rice (parboiled was
not investigated in high volume cooking water experiment), by 35%
and 45% for total and inorganic arsenic content, respectively,
compared to uncooked (raw) rice. To reduce arsenic content of
cooked rice, specifically the inorganic component, rinse washing and
high volume of cooking water are effective.
Introduction
Rice is the only staple crop grown under flooded soil conditions.
Under anaerobic conditions, arsenic in soil is converted readily to
arsenite which is mobile, leading to arsenic in rice grain being around
10-fold higher than for other crops.
1
This occurs in soils which have
no or limited anthropogenic contamination. Rice grain arsenic levels
are elevated further when grown in soils subject to anthropogenic
contamination such as: arsenical pesticide use, base and precious
mining and smelting impacted soils, and contaminated water irri-
gated soils.
2–8
Inorganic arsenic, a class 1 non-threshold carcinogen,
9,10
and
dimethyl arsinic acid (DMA) constitute the dominant arsenic species
present in rice while traces of monomethyl arsonic acid (MMA) are
sometimes reported,
11
as well as a residual fraction that is either not
extractable or does not elute from the chromatographic column.
Inorganic arsenic can constitute up to 90% of total arsenic present in
grain, but on average accounts for around 50% of total grain
arsenic.
11
A number of previous studies had suggested that rice cooking was
important to the arsenic content of the cooked grain.
12–18
Some of
these studies focus on how cooking techniques may reduce rice
arsenic content,
12,13
while others focus on how arsenic in cooking
water affects arsenic content of cooked rice.
14–18
Rinsing rice before
washing and then cooking the rice in a high water : rice ratio (6 : 1)
and not allowing the water to evaporate to dryness significantly
reduced the arsenic burden of the rice,
12,13
with one study suggesting
that the arsenic was primarily lost as inorganic arsenic, specifically
arsenite.
12
Previous studies on rice cooking
12–18
had not systematically
looked at: (a) differences between wholegrain (brown) or polished
(white) rice or (b) commonly used cooking techniques such as low
and high water : rice volume and steaming. Similarly, systematic
speciation and/or mass balances are inconsistent or absent between
previous studies.
13–8
Par-boiledricealsoneedstobeconsidereddueto
its widespread utilization. This current study sets out the systematic
determination of the effect of cooking on the concentrations of
arsenic species in rice.
Experimental
Rice samples were purchased from major UK retailers. Two varieties
of basmati, one wholegrain (packed in 1 kg portions, 4 portions were
mixed before use) and one polished (packed in 2 kg portions, 2
portions, mixed before use) were of Indian origin. Wholegrain long-
grain (4 times 1 kg portions, mixed before use) and polished long-
grain (4 times 1 kg portions mixed before use) originated according to
label from more than one country. The same origin was given for the
long-grain easy cook (par-boiled) rice (2 times 2 kg portion, before
use). The easy cook short-grain rice (4 times 1 kg portions mixed
before use) was of Italian origin.
Raw rice was first rinse washed by placing 100 g portions of rice
(packet weight) in an acid washed 800 mL beaker and then adding
600 mL of double distilled deionised (Milli-Q) water. The sample was
allowed to sit for 3 min with routine agitation. The water was dec-
anted and then the process repeated again with another 600 mL of
water. The decanted water was then freeze dried. Dry weight deter-
mination was then made on both the raw and rinsed rice by oven
drying at 80 C until constant weight was reached. The quantity of
freeze dried residue was recorded. Rinse washed rice was used in all
subsequent cooking experiments.
In all boiling experiments the quantity of packet weight used was
100 g. Double distilled deionised water was used for the cooking
water. All rice, including par-boiled, was subject to 2.5 : 1 (low
volume) water to rice (packet weight) cooking, where the water was
cooked to dryness. All rice with the exception of par-boiled, were also
subject to 6 : 1 (high volume) water : rice cooking, where the rice was
cooked to eating texture. The residual water was drained off and then
freeze dried.
For the steaming experiments, rinse washed rice (100 g packet
weight) was soaked for 2 h in an acid washed 400 mL beaker with 200
mL of double distilled deionised (Milli-Q) water. On termination of
a
Institute of Biological and Environmental Sciences, University of
Aberdeen, Cruickshank Building, St. Machar Drive, Aberdeen, UK AB4
3UU
b
Department of Chemistry, University of Aberdeen, Meston Building,
Meston Walk, Aberdeen, UK AB24 3UE
c
Foods Standards Agency, Aviation House, 125 Kingsway, London, UK
WC2B 6NH
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soaking, the water was decanted and freeze dried. The steamer was
filled with 200 mL of double distilled deionised (Milli-Q) water and
the soaked rice placed on arsenic and lint-free cotton-cloth. Steaming
time was 2 times 15 min with stirring in between. The residual water
was drained off and then freeze dried.
All cooked rice was then dried at 80 C until constant weight was
reached and then milled using a coffee/spice grinder prior to analysis.
All experiments were conducted with triplicate replication.
For total arsenic analysis 0.5 g dry weight of sample (rice or freeze
dried residual washes or residual liquor) was placed into 50 mL
polypropylene centrifuge tubes and 2.5 mL of Aristar nitric acid and
4 mL of hydrogen peroxide suprapur was added, followed by
microwave digestion using a CEM Mars5 Microwave system. On
digestion the sample was diluted to 25 mL using double distilled
deionised water with rhodium (0.02 mL 10 mg Rh/L) as an internal
standard. CRM NIST 1568a rice powder was used throughout for
the totals determination. Arsenic content was measured using an
Agilent 7500c ICP-MS with hydrogen as the collision/reaction gas.
The ICP-MS operating conditions are given in Williams et al.
1
Samples (rice or freeze dried residual washes or residual liquor) for
speciation analysis were extracted in 1% Aristar nitric acid and 1%
(vol/vol) hydrogen peroxide suprapur using a CEM Mars5 micro-
wave system. The supernatant was used for determination of
extractable arsenic and As-speciation. This oxidises arsenite to arse-
nate, improving chromatographic resolution as arsenate elutes at
some distance to MMA and DMA, where arsenite elutes adjacent to
MMA and DMA. Arsenic species were separated on a Hamilton
PRP 100 anion exchange column using phosphate buffer and the
LC-system was an Agilent 1100 system directly coupled to the Agilent
7500c ICP-MS for arsenic determination. Indium (0.01 mg/kg) in 1%
(v/v) nitric acid was added during the analysis via a T-piece as an
internal standard. CRM NIST 1568a rice powder was used
throughout for speciation determinations. There is no CRM avail-
able for inorganic and organic arsenic in rice, but NIST 1568a has
been used routinely in previous studies as a reference (Table 1).
Solutions (0.1 mL) containing known amounts of DMA (10 to 100
mg/kg) were subjected to LC-ICP-MS under the same conditions as
the supernatants. Peak areas from these measurements were used to
construct a calibration curve. Single species standards DMA, MMA
and As(V) were used for identification of species by retention time.
The supernatants (0.1 mL) were used as they were and injected onto
the column. Peak areas were used for quantification of As-species.
Every 10
th
sample was digested in duplicate and measured. Each
analytical batch contained procedural blanks, spiked samples (for
recovery estimate purposes) and CRM.
Results
The reported mean value and standard error for total arsenic in the
CRM was 0.280 mg/kg 0.007 mg/kg (n¼11) compared to its
certified value of 0.29 mg/kg with a 95% confidence interval of 0.03
mg/kg, so the CRM recovery reported here is well within the 95%
confidence interval. Spike recovery was 103.8% 5.7% (n¼12).
Limits of detection where 0.0004 mg/kg expressed on a sample weight
basis.
Table 1 reports arsenic speciation of the rice flour CRM and
compares the results of this study with those previously published in
the literature as no cereal flour CRM has certified arsenic speciation
reported for it. The results of this CRM analysis from the present
study compare favourably with previously reported studies. Spike
recoveries for arsenate and DMA are 110% 6.2% (n¼5) and 103%
4.3% (n¼5), respectively. Limits of detection for DMA are 0.004
mg/kg when expressed on a flour dry weight basis.
Total, inorganic and organic arsenic concentrations in raw, washed
and cooked rice are presented in Table 2. Mass balances, i.e.
summation of the individual measured components with respect
to the initial arsenic in raw rice, are also presented. The average
mass balance for all the data the standard error was 100.8 1.3%
(n¼20).
There was variation in the effectiveness of rinse washing in
removing total/inorganic arsenic from raw rice (Table 2). Washing
removed more total arsenic for both the polished (to 87% of raw rice
content) and wholegrain (to 85% of raw rice content) basmati, while
for all other rice percentage arsenic remaining ranged only from
96–99% of raw rice content, including parboiled. It appears that rinse
washing is more effective for basmati rice than for other types of rice,
though more samples would need to be analysed to confirm this.
Virtually all the arsenic lost through washing was inorganic (91% on
average of raw rice concentration), while negligible DMA was lost
(99% on average of raw rice concentration).
Table 1 Performance of CRM speciation compared to previous studies. As
i
refers to inorganic arsenic (arsenate and arsenite). As
o
refers to organic
arsenic (DMA and MMA). Numbers in italics are the standard error of the mean from the current study. Column recovery is the sum of species
expressed as a percentage of total arsenic determined in that solution
Extraction As
o
(mg/kg) As
i
(mg/kg) Pof species (mg/kg) Extraction efficiency (%) Column recovery (%) Reference
2M TFA 180 87 267 95 96 14
Enzymatic digest, pepsin
and pancreatin
159 101 260 * * 14
2M TFA 182 92 274 112 84 19
2M TFA 162 80 240 * * 11
Methanol : water with
sonication
180 109 288 99 * 20
Enzymatic hydrolysis, a-
amylase
171 106 277 * * 21
Ultrasonic & enzy. hydrol.,
protease & a-amylase
143 88 231 99 81 22
1MH
3
PO
4
with sonication 164 102 267 * * 23
1% HNO
3
185 99 284 104 98 This study
324 1 1
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Cooking rice to dryness in a 2.5 : 1 water : rice ratio, for all rice
types, resulted in no loss of arsenic from the cooked grain throughout
for all four rice types. All rice types tested for high volume cooking
(6 : 1 water to rice ratio), that is all the non-parboiled types tested,
considerably reduced both total and inorganic arsenic content. There
was no reduction in organic arsenic content on high volume cooking.
Total arsenic content was reduced to a mean of 65% of raw rice
content following rinsing and high volume cooking (Table 2), ranging
from 55% in whole grain basmati to 72% in polished long-grain. This
reduction was on average 55% for inorganic arsenic content, ranging
from 51% for polished long-grain to 60% for polished basmati. Even
though the rinse washing was ineffective for both types of the long-
grain rice, high volume cooking water reduced inorganic arsenic
content to those of basmati rice, where rinsing was more effective.
This suggests that high volume cooking by itself is enough to reduce
total and inorganic arsenic content, though rinse washing is normally
recommended as part of the preparation of rice per se.
Steaming did reduce mean total and inorganic arsenic content to
83% and 78% of the raw rice values, respectively. However, the effects
were variable, ranging from 91% for wholegrain basmati to 75% for
polished basmati for total arsenic. Percentage inorganic arsenic was
reduced lower compared to total arsenic content, with inorganic
concentrations ranging from 85% in polished long-grain to 60% in
polished basmati. While steaming did reduce total and inorganic
arsenic content it did not do so as effectively or as consistently as high
volume cooking.
Discussion
The most comparable to the present study, though more limited in
cooking treatments and rice types, was a high water rice (6 : 1)
investigation conducted by Mihucz et al.
12
Two Hungarian and one
Chinese rice types, for none of which was it recorded if the rice was
wholegrain or polished, were used in that study. They found a
42–63% reduction in total arsenic in cooked rice, with the cooking
liquor containing most of the removed arsenic from the rice (26–49%),
while the quantity removed by rinse washing was less (8–17%). It was
found that raw rice contained both arsenate and arsenite, and it was
primarily arsenite that was removed from the rice on rinsing and
boiling. Arsenite is uncharged at physiological pHs and hence more
mobile than arsenate or DMA, both of which are anionic. The DMA
findings in that study
12
confirm our results. As the present report only
records total inorganic arsenic, because the extraction process oxidises
arsenite to arsenate, the observation that primarily arsenite was
removed from the rice could not be confirmed.
In another comparable study, three West Bengali samples where
rinse washed and then cooked in a large water volume.
13
Total
arsenic, not speciation, was determined. The rinse washing step was
more exhaustive, involving 5–6 rinses until the rinse water discarded
was clear, the traditional Indian preparation, rather than the double
rinse wash step used in the experiments reported here. The rinse wash
step removed 28% of the arsenic compared to raw rice. Combined
rinse washing and large volume (6 : 1 water : rice) reduced arsenic up
Table 2 Summary of As
T
(total), As
i
(arsenate and arsenite) and As
o
(DMA and MMA) concentrations, in rice cooked in various ways. Percentage of
As
T
,As
i
and As
o
concentrations in the processed rice compared to raw rice are shown in parenthesis. Mass balances were obtained by summing the rice
with rinse wash and cooking liquor. Note all rice was rinse washed with the exception of raw rice. Data are the averages of 3 replicates. Numbers in italics
are the standard deviation (s.e.) of the mean
Rice type Cooking technique As
T
(mg/kg) s.e. As
i
(mg/kg) s.e. As
o
(mg/kg) s.e. Mass balance (%) s.e.
Polished basmati Raw 162 393 118 1
Raw washed 141 (87) 586 (92) 219 (106) 1 (96) (6)
2.5 : 1 water to rice 141 (87) 190 (92) 318 (106) 1 (93) (2)
6 : 1 water to rice 103 (64) 556 (60) 518 (100) 1 (98) (6)
Steamed 122 (75) 861 (66) 215 (83) 2 (103) (3)
Wholegrain basmati Raw 131 889 318 1
Raw washed 111 (85) 380 (90) 116 (89) 3 (88) (5)
2.5 : 1 water to rice 119 (85) 382 (90) 121 (89) 2 (97) (5)
6 : 1 water to rice 72 (55) 348 (54) 219 (106) 1 (96) (3)
Steamed 119 (91) 12 76 (85) 322 (122) 2 (100) (19)
Polished long-grain Raw 229 2138 158 2
Raw washed 222 (97) 13 131 (95) 559 (102) 3 (103) (13)
2.5 : 1 water to rice 238 (97) 6144 (95) 20 50 (102) 6 (110) (5)
6 : 1 water to rice 165 (72) 270 (51) 353 (91) 2 (113) (1)
Steamed 177 (77) 4107 (78) 252 (90) 1 (99) (4)
Wholegrain long-grain Raw 314 9183 14 87 2
Raw washed 311 (99) 18 157 (86) 386 (99) 2 (104) (11)
2.5 : 1 water to rice 324 (99) 7165 (86) 3109 (99) 2 (108) (5)
6 : 1 water to rice 219 (70) 5102 (56) 987 (100) 5 (104) (3)
Steamed 280 (89) 5156 (85) 24 76 (87) 6 (102) (4)
Italian parboiled Raw 211 5157 254 3
Raw washed 203 (96) 7149 (95) 354 (100) 4 (100) (5)
2.5 : 1 water to rice 211 (96) 7157 (95) 454 (100) 2 (97) (9)
Long-grain parboiled Raw 186 2115 256 3
Raw washed 180 (97) 199 (86) 257 (102) 1 (104) (1)
2.5 : 1 water to rice 163 (97) 10 86 (86) 13 39 (102) 6 (95) (12)
AVERAGE of ALL RICE
TYPES
Raw washed (93) (2) (91) (2) (99) (2) (99.2) (2.6)
2.5 : 1 water to rice (93) (2) (91) (2) (99) (2) (100.0) (2.9)
6 : 1 water to rice (65) (4) (55) (2) (99) (3) (102.8) (3.8)
Steamed (83) (4) (78) (5) (96) (9) (101.0) (0.9)
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to 58% of the raw rice content. This is compared to an average of 35%
removal (maximum of 45%) or total arsenic reported in the current
study (Table 1). The increased efficiency of removal for the Indian
rice of that study
13
may be due to more exhaustive rinse washing, or
due to the intrinsic nature of the rice used in that study.
Other studies have been conducted on the effects of cooking rice on
arsenic content, but have focused on the impact of arsenic contami-
nated cooking water on rice arsenic burdens.
14–18
While relevant to
S.E. Asian and US scenarios where cooking and drinking water is
arsenic contaminated, they are not relevant to many parts of the globe.
It was found here that cooking rice in a large volume of water (6 : 1,
water : rice) had the greatest effect with regards to lowering arsenic
levels in cooked rice. Specifically, it preferentially reduced the inor-
ganic arsenic content by 45% of that in the raw rice, when combined
with rinse washing. It is recommended that to reduce total and
inorganic arsenic content of rice, that rice is rinse washed and cooked
in a 6 : 1 water to rice ratio. Exhaustive rinse washing, as practised in
India, may reduce arsenic content even further when combined with
large cooking water volume.
Acknowledgements
This project was funded by a Food Standards Agency grant C01049.
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