Current mitigation techniques for Arsenic and Cadmium contaminated paddy

soils in Korea
Won-Il Kim , Anitha Kunhikrishnan
1

Chemical Safety Division, Department of Agro-Food Safety, National Academy of Agricultural

Science, Wanju-gun, Jeollabuk-do 565-851, Republic of Korea
*
Corresponding authors email: wikim721@korea.kr (WI Kim)

Abstract
Managing low concentrations of arsenic (As) and cadmium (Cd) together in rice (Oryza sativa L.) plants is
challenging and recently different strategies are being developed for mitigating As and Cd loading into the rice
grains. Water management affects the bioavailability of As and Cd in the soil and hence their
accumulation in rice grains and grain yields. This study investigated the effect of water management and
the use of soil amendments on As and Cd accumulation in brown rice. We also conducted rice washing experiment to
study the effect of washing by deionized water on the removal rate of inorganic As in polished rice. A field plot
experiment was conducted with five water management regimes [Flooded, alternate wetting drying (AWD 60 and
40)) and row (R-60 and R-40)] using two rice cultivars (Indica and Japonica). In another field experiment, the effect
of soil amendments, phosphate, silicate and rice husk biochar on As and Cd accumulation in brown rice was
investigated. All the four treatments significantly reduced the concentration of As in brown rice with R-40 showing
the least concentration with no noticeable differences between the cultivars. However, increasing Cd concentrations
were noticed in row and AWD treatments compared to the flooded treatment. While phosphate reduced As
accumulation in SK cultivar, silicate increased As concentration in both the cultivars. Biochar increased As
concentration in SK cultivar with no significant change in HK cultivar, but the trend was opposite for Cd. Silicate
significantly decreased the Cd accumulation only in SK cultivar. The inorganic As levels in polished rice after three
washings were reduced to 37-57% of those in raw rice samples. Although water management and addition of
amendments like phosphate and silicate offer some promising solutions, additional field studies and other
management strategies are required to control both As and Cd in paddy soils and rice grains.

As and Cd reduced by %
Keywords
Introduction
Heavy metal(loid) contamination in paddy soils is one of the most serious problems facing rice production and
soil management in Asian countries. Among agricultural food products, rice (Oryza sativa L.) is one of the most
widely consumed staple cereal foods in the world constituting about 89% of the diet of people in Asian countries. In
many East and South Asian countries including Bangladesh, Japan, Indonesia, and Korea, the accumulation of
metal(loid)s, particularly arsenic (As) and cadmium (Cd), in rice ecosystems and its subsequent transfer to the human
food chain is a major environmental issue. In Korea, rice is the most common crop grown on agricultural land. The
cultivated land in Korea is around 21%, and of that 61% is paddy fields. Large areas of agricultural land, including
paddy fields, have been contaminated by metal(loid)s including As and Cd via effluent from mine tailings and other

wastes generated by closed or abandoned mines (Kim et al., 2007; Kwon et al., 2013; Yang et al., 2006) and thus
results to the uptake of metal(loid)s by rice plants, posing a significant public health risk to the local community.
Rice contains high concentrations of As relative to other crops and chronic exposure to As has the potential to cause
several forms of cancer and various other serious negative health effects in humans. However, the toxicity of As
depends heavily on its chemical environment, with the inorganic forms of As (As(III) and As(V)) being the most
toxic, while the other organic forms of As [monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA)], are
generally considered to be mostly non-toxic. Therefore, the potential toxicity of As depends not only on the total As
concentration, but also on the species of As present in a given food sample [4].
While As is immobilized under oxidizing conditions and solubilized under reducing conditions these trends are
the opposite in Cd. Prolonged submergence to keep paddy soils under reducing conditions has been shown to
successfully decrease Cd concentration in rice grains. However, it leads to an increased uptake of As. Managing low
concentrations of As and Cd together in rice plants has always been a serious issue and there is an urgent need to
develop strategies for reducing As and Cd loading into the rice grains. Numerous studies have reported that water
management affects Cd (Kikuchi et al. 2008) and As (Somenahally et al. 2011; Spanu et al. 2012) bioavailability in
soils and their subsequent uptake by rice. When a paddy field is flooded and the soil has a low redox potential, any
Cd present in the soil combines with sulphur (S) to form CdS which has a low solubility in water (Bingham et al.
1976). Thus, flooding during the growing season, especially during later stages of plant growth, can effectively
reduce Cd concentrations in rice grains (Arao et al. 2009). In contrast, anaerobic conditions in paddy soil lead to the
reduction in arsenate to arsenite which enhances the bioavailability of As to rice plants. Therefore, growing rice
aerobically results in a significant decline in As accumulation in rice (Li et al. 2009). However, both Cd and As can
occur together as contaminants in paddy fields, and they can accumulate simultaneously in rice plants (Williams et
al. 2009). To help reduce water consumption during rice cultivation there has been considerable interest in expanding
the aerobic cultivation practices employed in upland rice to lowland environments where anaerobic, paddy
cultivation is traditional (Bouman et al. 2005). However, the reduced yields and pest control problems associated
with aerobic cultivation need to be addressed (Kreye et al. 2009). One major recent advance in rice water
management is termed alternate wetting and drying (AWD) (Price et al. 2013). AWD combines the beneficial aspects
of both aerobic and anaerobic cultivation. INCLUDE ROW
Compared with water management, the potential effects of soil amendments on As and Cd accumulation
have also been studied. Our results demonstrate that applying Si to the growth medium markedly decreased As
concentrations in the shoots and roots and total As uptake by rice seedlings (Guo et al 2005; 2007). The use of
biochar to reduce the mobility and bioavailability of heavy metal(loid)s in contaminated soils has attracted much
attention in recent years. However, the effect of biochar addition on the mobility of As was inconsistent among
different laboratory studies (Beesley and Marmiroli, 2011; Beesley et al., 2011). Studies showed that washing rice
before cooking reduced the total/inorganic As compared to raw rice (Mihucz et al., 2007; 2010).
With all these points taken into consideration, our study investigated the effect of water management and
the use of soil amendments (phosphate, silicate and rice husk biochar) on As and Cd accumulation in brown rice in
two rice cultivars grown in Korea. A rice washing experiment was also conducted to study the effect of washing by
deionized water on the removal rate of inorganic As in polished rice. A field plot experiment was conducted with five
water management regimes [Flooded, alternate wetting drying (AWD 60 and 40)) and row (R-60 and R-40)] using
two rice cultivars (Indica and Japonica). In another field experiment, the effect of soil amendments, phosphate,

silicate and rice husk biochar on As and Cd accumulation in brown rice was investigated.

Materials and Methods

The experimental site was located in a conventional agricultural field near Hangzhou city,
Zhejiang province, east China. Two rice cultivars were compared, Zhongxiang No. 1 (A16)
with low Cd accumulation in the brown rice and
Indonesia (A159) with high Cd accumulation. The field was contaminated from mining
effluent. Total As and Cd in soil. A field plot experiment was conducted with five water management regimes
[Flooded, alternate wetting drying (AWD 60 and 40)) and row (R-60 and R-40)] using one rice cultivar of Indica
variety and another rice cultivar of Japonica variety.
1. Flood: 10 cm flood maintained during season
2. 2. AWD/40:Field flooded or 7-10 d, then allowed to dry until it reaches 40% of field capacity and
then re-flooded to 10 cm. Dried at R7 stage.
3. AWD/60:Field flooded for 7-10 d, then allowed to dry until it reaches 60% of field capacity and
then re-flooded to 10 cm. Dried at R7 stage.
4. Row/60:Planted on beds; watering by furrows until soil in beds reaches 60% of field capacity.
Dried at R7 stage.
5. Row/40:Planted on beds; watering by furrows until soil in beds reaches 40% of field capacity.
Dried at R7 stage.
AWD flooding the soil and then allowing to dry
down before being reflooded

The total As and Cd concentrations in brown rice samples were analysed using ICP-MS after microwave digestion.
In another field experiment, the effect of soil amendments, phosphate, silicate and rice husk biochar on As and Cd
accumulation in brown rice was investigated. Application rate. Gongju field was used. Contaminated with. A rice
washing experiment was also conducted to study the effect of washing by deionized water on the removal rate of
inorganic As in polished rice. Four polished rice samples were collected from local markets and washed for three
times using deionized water. The samples were dried, finely ground and As species in rice was quantified using
HPLC-ICP-MS following hot block digestion.
Four water management treatments were laid out in a
randomized complete block design, replicated three times.
Treatments were: (i) Flood (continuously flooded control), (ii)
AWD/40F (flood), (iii) AWD/60, and (iv) AWD/40, where
AWD represents alternate wetting and drying followed by the
percent of saturated volumetric water when fields were
re-flooded. For the AWD/40F treatment water was managed
the same as the AWD/40 management until the plants
reached the reproductive growth stage; after which a flood
was maintained until the field was drained for harvest.
For the AWD water treatments, the plots were
irrigated to a flood depth of 10 cm and the water was allowed
to subside via evapotranspiration and percolation until soil
moisture reached the critical moisture level for that treatment
(60 and 40% of saturated volumetric water measured at
5 cm depth) when the plots were reflooded. In the Flood treatment,
water was maintained at 10-cm.

Results and Discussion

Water management
Compared to the flooded treatment, AWD and row treatments significantly reduced the concentration of As in brown
rice with R-40 showing the least concentration. However, no noticeable differences between the rice varieties were
observed. In the case of Cd, the trend was opposite; increasing Cd concentrations were noticed in row and AWD
treatments compared to the flooded treatment. Between the varieties
Uptake of Cd and As has been shown to differ with rice cultivars (Norton et al. 2009; Hu et al. 2013a). Several
studies have indicated that Cd uptake is significantly higher in Indica cultivars than in Japonica cultivars grown in Cd
contaminated soils (He et al. 2006).

Hu et al. 2013a; b. With increasing irrigation

from aerobic to flooded conditions, the soil
HCl-extractable As concentrations increased significantly
and the HCl-extractable Cd concentrations
decreased significantly. These trends were consistent
with the As and Cd concentrations in the straw, husk
and brown rice.
The intermittent and
conventional treatments produced higher grain yields
than the aerobic and flooded treatments.
Yang et al. 2009. Observed that alternate wetting and moderate soil drying reduces Cd in rice grains and
increases grain yield.
Recently Linquist et al. (2015) noticed Relative to the flooded control treatment and depending on the AWD
treatment, yields were reduced by <113%; water-use efficiency was improved by 1863%, global warming
potential (GWP of CH4 and N2O emissions) reduced by 4590%, and grain As concentrations reduced by up to
64%.
As and Cd in rice grains
Yield
Difference in cultivars
Effect of amendments
While phosphate reduced As accumulation in SK cultivar, silicate increased As concentration in both the cultivars.
Biochar increased As concentration in SK cultivar with no significant change in HK cultivar, but the trend was
opposite for Cd. Silicate significantly decreased the Cd accumulation only in SK cultivar.

As and Cd in rice
Effect of amendments
Yield
Difference in cultivars

Phosphate
Silicate
Biochar
Effect of washing arsenic polished rice-inorganic As
The inorganic As levels in polished rice after three washings were reduced to 37-57% of those in raw rice samples.

Cd and As concentrations in different plant parts

Cd concentrations in straw of both cultivars increased in
all treatments as plant growth proceeded but decreased
at maturity under flooding, particularly in cultivar A159
(Fig. 3). In both cultivars, the Cd concentrations in
straw of the aerobic and intermittent flooding treatments
were significantly higher than those of the control and
flooded plots from panicle initiation to maturity. In
contrast to a high Cd accumulation in A159 grains,
A159 straw showed a lower Cd concentration at maturity
than A16 in the aerobic and intermittent flooding
treatments. Total straw As concentrations decreased at
early growth stages but increased at the grain filling
stage of A16 with the exception of the aerobic treatment
in which the increase was observed at panicle initiation
(Fig. 3). In A159, this increase was found at panicle
initiation. Overall, straw As concentrations in the four
water regimes followed the sequence aerobic<intermittent<

control<flooded.
Root Cd concentrations increased over the whole growth
period with significantly increased concentrations in the
aerobic and intermittent over the control and flooded plots
(Fig. 4). The aerobic irrigation regime gave the highest root
Cd concentrations followed by intermediate>control>
flooded for both rice varieties. Root As concentrations
showed the opposite trend to Cd. Arsenic decreased at early
growth stages but increased slightly at the filling stage. Root
As followed the sequence aerobic<intermittent<control<
flooded under the different water management treatments
(Fig. 4).
Brown rice and husk Cd concentrations showed the same
trend, i.e. aerobic>intermittent>control>flooded (Fig. 5).
The flooding treatment and the control led to slightly or
significantly higher brown rice and husk As than the aerobic
or intermittent (Fig. 5). Cultivar A16 had lower Cd concentrations
but higher As in the brown rice than A159. Arsenic
concentrations in both varieties followed the sequence
roots>straw>husk>grain and Cd gave roots>straw>
grain>husk (Figs. 3, 4 and 5).
3.3 Effects of water management on grain yields
The different water regimes influenced the grain yields of
both cultivars. The grain yields of both varieties in the
control plots were higher than the other treatments. A significant decrease in yield was
observed in R-40 treatment. In other treatments, slight decrease was noticed when
compared to control.
those in the aerobic and flooding treatments (Fig. 6). The
two varieties did not differ significantly in grain yield except
for the flooded plots in which A159 had higher grain yields
than A16.

Conclusion
Arsenic and Cd contamination threatens food security, safety and quality, as well as the long-term
agricultural sustainability of rice crops.

References
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[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
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[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
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[1] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[1] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[1] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)

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[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[1] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[1] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[1] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[1] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[1] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[1] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)
[2] Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA. Variation in
paddy rice related to dietary exposure. Environ. Sci. Technol. 39: 5531-5540 (2005)

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