Arsenic in Crops:

As contaminated
groundwater is used for drinking and irrigation purposes. From the contaminated crops and
fodder, As gets its entry into the food chain (Tripathi et al., 2007; Meharg et al., 2009). Food and
water are basic daily requirements for humans. The food requirements (quantity) and food
choices (rice, wheat, vegetables, fruits, fish, chicken, etc.) vary in different regions of the world,
at different ages and with different sexes and also during different seasons. With more and more
research focused on to evaluate the impact of As contamination around the world, it has come to
light that the As infiltration affects a number of crop plants, sea animals, fruits, vegetables and
consequently, finds way into commercial food products prepared from As contaminated raw
material (Zhao, Stroud, Eagling, Dunham, McGrath, & Shewry, 2010; EFSA, 2009; Zavala &
Duxbury, 2008). Hence, the risk of As-exposure becomes pertinent not only to people living in
As contaminated regions but also to other parts of the world.

Arsenic toxicity to humans

Toxicity of As to humans depends on the number of factors like age, gender,
concentration and speciation of arsenic, duration and dose of As exposure, nutritional status
(Jovanovic & Rasic-Milutinovic, 2017). Its toxicity in humans has been linked to epigenetic
changes like DNA methylation, RNA interference and histone modification. Chronic exposure to
iAs increases the risk of diabetes mellitus, adverse pregnancy outcomes (APO) and even cancers
of the skin, lungs, and urinary bladder (Paul et al., 2007; Vahter, 2009; Wang et al., 2014,
Jovanovic & Rasic-Milutinovic, 2017). Arsenic exposure during gestation period has ill-effects
on fetus development through irreversible impairment of thioredoxin reductase,
methyltransferases and DNA repair enzymes. In fact, As is the first metalloid directly linked with
adverse pregnancy after-effects (Jovanovic & Rasic-Milutinovic, 2017; Vahter, 2009). Paul et al.
(2007) have demonstrated the close relationship of high As levels with elevated blood sugar
level, which in turn affects insulin signal transduction and insulin sensitivity. Long-term
exposure to iAs leads to arsenicosis, a term used for As related health effects including skin
problems, skin cancers, internal cancers (bladder, kidney, lung), diseases of the blood vessels of
the legs and feet (WHO, 2011), hyperkeratosis, hyperpigmentation, mee's lines and hair
hypomelanosis (Hashim et al., 2013). The exact mechanisms of As induced cancers are yet not
fully understood; however, roles of critical events like loss of p53 gene do take place (States,
Barchowsky, Cartwright, Reichard, Futscher & Lantz, 2011). In some studies, As toxicity has
been linked to effects on child intelligence (e.g., perceptual reasoning, working memory, verbal
comprehension) (Wasserman et al., 2014). Davis et al. (2017) reviewed epidemiological studies
that analyzed rice consumption and its association with As exposure. They concluded that early
life exposure or during pregnancy exposure to iAs can lead to adverse health effects throughout
life (Signes-Pastor et al., 2018). Earlier, high levels of urinary As were detected in pregnant
women in USA (Gilbert-Diamond et al., 2012) and Bangladeshis in the UK (Cascio, Raab,
Jenkins, Feldmann, Meharg, & Harris, 2011) who consumed high amounts of rice in their diet. In
the year 2001, Ahmad et al. reported that in Bangladesh, the frequency of spontaneous abortions,
stillbirths and preterm births were 2.9, 2.24 and 2.54 times higher, respectively in the group
exposed to average 240 g As L
-1
than in the group exposed to average ≤ 20 g As L
-1
in water
(Ahmad et al., 2001).
The US EPA evaluates any carcinogen on the basis of a lifetime cancer risk upper limit of
1 in 10,000 persons (US EPA, 2018). The calculated median increased lifetime cancer risk
values for As in the people of Bangladesh and West Bengal, India were found to be as high as 22
and 7.2 in 10,000 persons, respectively (Meharg et al., 2009; Meharg & Zhao, 2012). Halder et
al. (2013) conducted an assessment of As exposure risk in rural villages of West Bengal where
safe drinking water was already being supplied. It was found that with As concentration in
drinking water was <10 μg L
−1 , the total daily intake of iAs exceeded in 35% cases while it was
100% when As concentration in water was >10 μg L
-1
, considering the provisional tolerable
daily intake (PTDI) limit of 2.1 μg day−1 kg−1 body weight (b.w.) (WHO, 1993). In fact in the
year 2011, WHO withdrawn both PTDI and PTWI value of As and proposed Benchmark Dose
Lower Limit (BMDL0.5; suggesting a 0.5% increased incidence of cancer) for As. In this report,
the BMDL0.5 values for lung cancer, bladder cancer and skin lesion were set as 3 μg day−1
kg−1
bw, 5.2 μg day−1 kg−1 bw and 5.4 μg day−1 kg−1 bw respectively (WHO, 2011; JFCFA,
2011).Based on several epidemiological studies, European Food Safety Authority (EFSA) has
suggested the health risks for dietary As intakes should be assessed using margins of exposure
(MOEs), a ratio calculated by comparing the dose at which a small but measurable adverse effect
is first observed and the level of exposure to iAs (EFSA, 2009). The MOE is calculated from a
point of departure (POD, also known as a reference point) and the estimated dietary exposure in
humans. The MOE does not precisely quantify the health risk but gives an indication of the level
of deserved concern: the smaller the MOE, the higher the potential risk posed by exposure to
iAs. A benchmark dose (BMD) approach was adopted by the EFSA for deriving a suitable POD
in the observable dose-response range and the POD for iAs has been given by the EFSA from 0.3
to 8 g day-1
kg-1

bw (BMDL01) (EFSA, 2009) that would result in 1 % increased risk of lung,

skin and bladder
Arsenic in rice and other crops, and animals
3.1. Arsenic in rice
Rice is a widely consumed staple food, especially in India, Bangladesh as well as other Southeast
Asian countries; the regions where As contamination is widespread and where rice cultivation is
major agricultural practice. The problem of As accumulation in rice plant is a major global
concern as rice grains, rice milk and rice bran are consumed by millions of people of different
ages (from infants to adults), groups and regions. As. The amount and forms of As in grains are
influenced by irrigation regime, geographical location and environment (Williams et al., 2006;
Rahman, Asaduzzaman, & Naidu, 2011; Awasthi et al., 2017), rice genotypes (Zavala &
Duxbury, 2008; Bhattacharya, Samal, Majumdar, & Santra, 2010), and rice grain processing
(Signes-Pastor et al., 2008). Dittmar et al. (2010) showed that the concentration of As varied
even across a single field with highest concentration recorded near the irrigation water inlet. The
variations in As exposure to humans are also caused due to differences in cooking methods
(Gray, Conklin, Todorov, & Kasko, 2016; Mwale, Rahman, & Modal, 2018), dietary habits of
people which change not only according to age, sex and region but also with the seasons. A
study by Biswas, Deb, Ghose, Santra, & Guha Mazumder, (2014) conducted in Nadia, West
Bengal, demonstrated seasonal changes in As levels in drinking water (26 g L
−1 in summer, 6
g L
−1 in winter) as well as water intake by people from summer to winter (male: 3.8 and 2.5 L
day−1 and female: 2.6 and 1.2 L day−1). Hence, any evaluation of health risk should also
include
seasonal changes in As concentrations in water and food, seasonal diet and water intake
and also
probably the seasonal (temperature dependent) changes in bio accessibility and
metabolism of As
in humans.
There are hundreds of reports on As in rice. The studies include field based evaluations as
well as market based surveys. Owing to the growing concerns about As in rice, WHO has set
a
permissible limit for iAs of 0.2 mg kg-1 for white rice and 0.4 mg kg-1
for brown rice in July
2014. The maximum limits have been prescribed by European Union (EU) for iAs i.e. 0.2 mg
kg−1 for white rice. For rice based food products for infants and young children, a limit of
0.1 mg
kg−1 has been set while for other rice-based food products the limit is 0.3 mg kg−1
. The maximum
contaminant limit for iAs is 0.15 mg kg-1
in China while it is 0.7 mg kg-1
for tAs (Qian, Chen,
Zhang, Li, Chen, & Li, 2010).
Arsenic concentrations have been found to vary in field and market based studies
(Meharg et al., 2009; Rahman et al., 2011; Williams et al., 2007; Zavala & Duxbury, 2008)
with
a maximum level of 1.835 mg kg−1 reported by Meharg & Rahman (2003). However, As
usually
remains below 1.0 mg kg−1
. The average concentration of iAs has been found be <0.1 mg kg−1 in
India, 0.13 mg kg−1 in Bangladesh, 0.14 mg kg−1 in Taiwan and China, and 0.19 mg kg−1
in
Japan (Meharg et al., 2009; Zavala, Gerads, Gurleyuk, & Duxbury, 2008; Williams, Price,
Raab, Hossain, Feldmann, & Meharg, 2005). Williams et al. (2005) found that white basmati
rice from
Indian supermarkets contains very low amount of tAs as 0.05 mg kg−1 (0.03−0.08 mg
kg−1). In
Spanish rice, tAs concentrations of 0.17 mg kg−1 (Williams et al., 2006) and 0.05−0.82 mg
kg−1
(Meharg et al., 2009) are reported. Zavala & Duxbury (2008) reported 0.156–0.19 mg kg-1
as the
highest mean As level in rice grown in USA, Italy and Spain. Rice from Bangladesh, Thailand
and Venezuela were found to have mean As level of 0.062–0.089 mg kg-1
and rice from India
and Pakistan contained significantly less mean As concentrations of around 0.051–0.053
mg kg1
.
Sun et al. (2008) reported that As concentration in rice bran samples were very high (∼1
mg kg-1
dry weight; dw) i.e. 10-20 fold higher than concentrations found in bulk grain. It is
important to note that rice bran products are sold as super food and as a supplement to
malnourished children in International aid programs. In market survey of Batista, Souza,
Souza,
& Barbosa (2011) in Brazil on different types of rice (total 44), the highest mean As level
was
found in brown rice (0.348 mg kg-1
) followed by parboiled brown rice (0.266 mg kg-1
), white
rice (0.223 mg kg1
) and parboiled white rice (0.215 mg kg-1
). An experiment with 216 rice
genotypes showed that the ranges of As contents in indica rice and japonica rice were
0.021–
0.296 mg kg−1 and 0.005–0.274 mg kg−1, respectively (Jiang, Shi, & Wu, 2012).
Nookabkaew, Rangkadilok, Mahidol, Promsuk, & Satayavivad (2013) assessed 185
samples various types of rice in Thailand and some other Asian countries and reported
range of
tAs (0.023 – 0.375 mg kg-1
) and iAs (0.0139 – 0.233 mg kg−1). Rahman, Rahman, Reichman,
Lim, & Naidu (2014) evaluated total As concentrations in Australian grown organic brown,
medium grain brown, and organic white rice and found the average levels to be 0.438,
0.287, and
0.283 mg kg−1 dw, respectively. By contrast, rice imported from Bangladesh, India,
Pakistan, and Thailand in Australia was found to contain tAs concentrations of 0.056, 0.092,
0.082 and 0.172
mg kg−1, respectively; the values being significantly lower than Australian grown rice.
Sofuoglu, Guzelkaya, Akgul, Kavcar, Kurucaovali, & Sofuoglu (2014) analyzed As
concentrations in rice samples from Turkey and found iAs to be major fraction (0.16 mg kg-
1
).
Seyfferth, McCurdy, Schafer, & Fendorf (2014) evaluated As content in rice in Cambodia,
where
As problem is expected to arise due to similar geological settings and agricultural practises
as
that of otherAs contaminated Southeast Asian countries. The rice was collected from five
provinces (Kandal, Prey Veng, Battambang, Banteay Meanchey, and Kampong Thom) in the
rice-growing regions of Cambodia. Total grain As concentrations ranged from 0.1 to 0.37
mg kg
-
1 with an average of 0.2 mg kg
−1
.
Huang, Wang, Mao, Qian, Chen, & Zhang (2015) reported that out of 1653 milled rice
samples from 11 provinces in China, 1.1% contained higher than maximum recommended
As
levels as per Chinese regulations. Syu, Huang, Jiang, Lee, & Lee (2015) investigated the
impact
of As phytotoxicity and rice genotypes on As levels and speciation in rice grains in Taiwan.
It
was found that As concentrations did not correlate to soil As levels and were either equal or
more in indica than in japonica genotypes. An important finding was that As phytotoxicity
not
only affects the grain yield but also the grain As concentrations. DMA was the major As
species
that increased with increased total As concentrations, while As(III) remained stable at
about 0.1-
0.3 mg kg
-1
.
In Europe, more than half of total production is from Italy and hence, analysis of As in
Italian rice is necessary. In Italian rice, Williams et al. (2006) reported tAs concentrations
around
0.19 – 0.22 mg kg−1 while Meharg et al. (2009) found 0.07-0.33 mg kg−1 tAs. Tenni et al.
(2017)
conducted a survey of As in Italian rice of different varieties collected from major rice
producing
areas. The average concentration of total As and iAs was 0.155 mg kg−1 and 0.102 mg
kg−1
, respectively. The concentration of iAs in total As was in range of 31 and 94%. Only DMA
was
detected as oAs species in Italian rice. The iAs concentration in some samples was higher
than
limit for baby foods (i.e. >0.100 mg kg−1) (Tenni et al., 2017). A study by Sandhi, Greger,
Landberg, Jacks, & Bhattacharya (2017) evaluated total As in local aromatic rice (kalijira)
and
high yielding rice varieties (BRRI dhan 32 and BRRI dhan 28) in Bangladesh. They found
that
As accumulation factor was lower in LAR (0.2-0.4%) than in HYV (0.9 – 1%).
3.2. Arsenic in other crops (wheat, maize, pulses)
Wheat is the second most important staple food grown worldwide with annual production
of over
600 million tonnes (Williams et al., 2006). However, due to its cultivation in aerobic
conditions
and due to less affinity for silica accumulation, relatively low concentrations of As have
been
reported in wheat (Shi et al., 2015). Very little is known about the relationship between As
transport and it’s accumulation in wheat crops, especially in different wheat cultivars.
Recently,
it was demonstrated that arsenate tolerance of 57 wheat cultivars significantly varied and
the
tolerance was attributable to As retention mostly in roots (Shi et al., 2015). In wheat, total
As
concentration ranges from 0.010 mg kg
-1
to 0.500 mg kg
-1 with mean levels of <0.100 mg kg-1
(Adomako, Williams, Deacon, & Meharg, 2011; Williams et al., 2007).
Maize (Zea mays), also known as corn, is one of the most cultivated cereal in the world.
According to the Food and Agriculture Organization of the United Nations, the global
production
of maize exceeded 883 million tons per year in 2011, a production greater than the
corresponding
production for wheat (704 million tons) and rice (723 million tons). An analysis of As in
maize
in Tanzania (Marwa, Meharg, & Rice, 2012) found As content in grain to range from 0.01 -
0.17
mg kg−1. The consumption of maize is high in some countries like Mexico (315.1 g day−1)
and in such cases, corn with high As concentrations may pose health risk to people (Rosas-
Castor,
Guzman-Mar, Hernandez-Ramirez, Garza-Gonzalez, & Hinojosa-Reyes, 2014).
Pulses (legume seeds) constitute an important dietary source of proteins for populations
in Southeast Asia and especially for those dependent on vegetarian diet. Only iAs has been
reported by Williams et al. (2006) in five different pulses. The contribution from pulses to
the
dietary intake of As is small because of the relatively low As concentration and small
quantity of
pulses being consumed worldwide (Williams et al., 2006). In Brazil, the dietary exposure of
iAs
has been evaluated to be 0.255 g kg-1
body weight per day that is about 9% of the BMDL0.5 of
3 g kg-1
body weight per day. Rice and beans, the main Brazilian staple food, were the major
factors in total As intake of 67-90% (46 -79% from rice and 11- 23% from beans). This was
the
first such report indicating beans as a potential As source and it is important as beans
constitute a
main staple food in some countries especially in Latin America and Southeastern Africa
countries (Ciminelli, Gasparon, Ng, Silva, & Caldeira, 2017). In sub-Saharan Africa, beans
supply more than 50% of the protein requirements and the consumption is up to 60 kg per
year
(164 g d-1
) (Margaret, Tenywa, Otabbong, Mubiru, & Ali, 2014). Beans contained on average
0.050 mg kg-1 As, which was less than the limit in Brazil of 0.1 mg kg-1 (ANVISA, 2013).
Rahman, Asaduzzaman, & Naidu (2013) demonstrated a range of 0.121 to 0.429 mg kg-1
dw in
pulses in a study conducted in West Bengal, India.
3.3. Arsenic in vegetables and mushrooms
Vegetables constitute another important category of human food and hence several reports
assessed As concentrations in a variety of vegetables and mushrooms. Potato (Solanum
tuberosum) is one of the largest crops of world after maize, rice and wheat (Leff,
Ramankutty, &
Foley, 2004). Arsenic speciation in potato tuber samples was determined by Williams et al.
(2006). The samples were from Bangladesh and the study reported presence of only iAs,
with no
detectable oAs species. The presence of MMA in potato tubers was reported by Signes-
Pastor et
al. (2008) from the samples collected from a village in West Bengal. The data on As in
vegetables indicated that the As-concentrations in some of the vegetable produce can be as
high
as that of rice on dry weight basis. Bhattacharya et al. (2010) reported that potatoes had
the
highest As accumulation even more than that in rice. Analysis by Rahman et al. (2013)
indicated
that total As concentrations in Malda, West Bengal showed a range of 0.000 to 1.464 mg kg-
1
dw
in food crops with the highest As concentration being in potato (0.456 mg kg-1
), followed by rice
grain (0.429 mg kg-1
). The range of total As concentration was 0.243 to 0.456 mg kg-1
dw in
tuber crops, 0.031 to 0.175 mg kg-1
dw in spices, 0.021 to 0.145 mg kg-1
in fruits and 0.032 to
0.411 mg kg-1
dw in vegetables. In Bangladesh, the range of As in vegetables has been found
to be different for different regions viz., Chandpur and Jamalpur districts (0.070–3.990 mg
kg−1) and Sathkhira, Rajshahi, and Comilla districts (<0.040–1.930 mg kg−1) (Williams et
al.,
2006). In West Bengal, India, As analysis in vegetables from Jalangi and Domkal blocks
showed mean As levels of 0.0209 mg kg−1 (<0.00004–0.138 mg kg−1) and 0.0212 mg
kg−1
(0.00004–0.212 mg kg−1), respectively (Roychowdhury, Tokunaga, & Ando, 2003). As
levels
have been found to be higher in leafy vegetables (0.041–0.464 mg kg−1) than in non-leafy
vegetables (0.011–0.145 mg kg−1) (Williams et al., 2006). In cooked vegetables, a range of
0.019–2.334 mg kg−1 has been found from Munshiganj and Monohordi of Bangladesh
(Smith,
Lee, Heitkemper, Cafferky, Haque, & Henderson, 2006). There are some aquatic
macrophytes
also, which are used for eating. Falinski, Yost, Sampaga, & Peard (2014) assessed As
contamination of edible Nasturtium officinale (watercress) and Diplazium esculentum
(warabi),
which are consumed in Hawaii from an As contaminated area (Soil As: 356 mg kg-1
). Total As in
N. officinale and D. esculentum was 0.572 mg kg-1
and 0.075 mg kg-1
, respectivelyMushrooms constitute an important food item and the consumption of edible
mushrooms
has increased considerably worldwide in recent years due to their nutritional properties
(Seyfferth, McClatchy, & Paukett (2016)). Wildly-growing mushrooms are capable of
accumulating certain elements in large amount in their fruit bodies (Wang et al., 2014).).
Zhang,
Liu, Li, Li, Wang, & Li (2015a) analyzed total As in 48 species of wild-grown edible and
medicinal mushrooms in China. The results showed highest As in Scleroderma citrinum
(1.70
mg kg-1
dw) and the lowest As in Termitomyces eurrhius (0.17 mg kg-1
dw). In an analysis
(Zhang et al. 2015a), Laccaria proxima and L. vinaceoavellanea growing naturally as well as
Laccaria mushroom samples from market were evaluated for As in Yunnan, China. The
mean
As concentrations in caps were 135, 14.1–143, 5.5 and 130–163 mg kg−1 dw for Laccaria
amethystina, L. laccata, L. proxima and L. vinaceoavellanea, respectively. In an analysis,
Seyfferth, et al. (2016) analyzed 40 mushroom samples of 12 types in US from two major
producing regions for As, Pb, and Cd. Differences were found in total As concentrations
(Cremini > Shiitake) and also in As localization (fruiting body in Cremini vs. hymenophore
in
Shiitake). However, As concentration was less than 1 mg kg
−1 dw in all mushroom samples.
Recently, As speciation analysis was performed in Elaphomyces spp. It was found that the
tAs
content ranged from 12 to 42 mg kg-1
dw in E. asperulus and from 120 to 660 mg kg-1
dw in E.
granulatus and E. muricatus. The dominant species of As were oAs namely, MMA(V) (about
30% of extractable As), trimethylarsine oxide (TMAO, about 0.3 to 28% of extractable As)
and
MMA(III) (about 0.08-0.73% of extractable As) (Braeuer, Borovicka, & Goessler, 2018). In
mushrooms, the oAs content has been found to be comparatively higher than iAs that can
be
attributed to a more efficient enzymatic transformation of As from iAs to oAs species
(Braeuer et
al., 2018). Arsenic in food of animal origin
Consumption of animal products (e.g. meat, meat products, egg, milk and dairy based
products)
has also been an important pathway of As uptake in humans. Fish and other seafood
constitute
the major source of dietary oAs in general (Taylor et al., 2017). Sigrist, Beldomenico, & Rosa
(2010) studied the effect of As concentration in drinking water on tAs levels in cow’s raw
milk.
The concentration of As in drinking water were up to 300 µg L
-1
, whereas the As concentration
in milk were below 2.2 µg L
-1
indicating the relatively low transfer of ingested As to the milk in
cow. Mean As content in meat (0.021 mg kg-1
in beef and chicken) and freshwater fish (0.233 mg
kg-1
) were also reported to be lower than the limits of 0.5 mg kg-1
for meat and 1.00 mg kg-1
for
fish established by the Brazilian legislation (ANVISA, 2013). However, total As
concentrations
in range of 0.11 - 0.93 mg kg-1
in fish from Southeastern Brazil has been reported (Meche,
Martins, Lofrano, Hardaway, Merchant, & Verdade, 2010). Marine food products have been
reported to be mainly affected by oAs species as the organisms present at the primary
trophic
level take up the iAs and transform it to oAs (methylated As species, arsenosugars,
arsenobetains, arsenolipids etc.) (Taylor et al., 2017). The low concentration of iAs in fish
(<0.015 mg kg
-1
) was found in a study on a large number of fish samples from Norwegian waters
(Julshamn et al., 2012). Wang, Sthiannopkao, Chen, Man, Du, & Xing (2013) analyzed food
samples from Kandal, Kratie and Kampong Cham in Cambodia. The maximum As
concentration
was found in fish (2.832 mg kg
-1
, ww) collected from Kandal province. Generally As
concentration in sea water is low (1-5µg/L). Wu et al. (2014) estimated total As content in
200
samples of 22 species of seafood collected from eight cities in Shandong, China. Among
three
categories of seafood i.e. fish, shrimp and bivalves, the bivalves showed the highest total As
concentrations. The mean total As concentrations ranged from 0.037 mg kg
-1 ww in fish to 3.4
mg kg-1
in bivalves. It was found that seafood consumption can pose risk for health as the tested
consumption scenarios statistically showed a cancer risk >10-4
, which is more than the accepted
level (10-6
) (US EPA, 2018). In one of the recent study it was assessed that As levels in baked,
fried, grilled and raw fishes and it was found that raw fishes contained the lower amount of
As
than that in cooked fish with frying causing the maximum increment in As concentration,
followed by grilling and baking (Ling et al., 2014). This was because, at high temperatures
of
cooking, oAs species like arsenobetaine and arsenocholine converted into TMA, TMAO and
DMA (Cheyns, Waegeneers, de Wiele, & Ruttens, 2017). Thus, oAs species with lower
toxicity
can also be a threat as they can get transformed into inorganic As species. Indeed, cooking
method and cooking temperature have profound effects on As speciation in food items (Liu,
Zheng & Chen, 2018). The calculation of cancer risk also indicated that fried fish would
pose
significant risk to health.
4. Infant cereals and other market based food products
Rice and rice-based food products constitute the major route for human exposure to As
particularly in people dependent on substantial rice-based foods and via baby food in
children
(Juskelis, Li, Nelson & Cappozzo, 2013; Tenni et al., 2017). Jackson, Taylor, Karagas,
Punshon,
& Cottingham (2012) reported presence of total As in infant formulas in Hanover
(Germany) and
New Hampshire (USA) in range of 2.2 to 12.6 μg kg−1 which was high for infants.
CarbonellBarrachina et al. (2012) analyzed Spanish gluten-free rice, cereals with gluten,
and pureed baby
foods and also pure infant rice samples from China, USA, UK and Spain. The concentration
of
iAs was found to be higher in gluten-free rice than in cereals mixtures with gluten. Cereals
prepared with mixed grains contained the lowest concentration of total (105 μg kg−1) and
iAs (63
μg kg−1). DMA was found as major oAs species, while MMA was not found. Juskelis et al.
(2013) analyzed 31 infant rice cereals from US supermarkets for As. The iAs ranged from
55.5 and 158.0 μg kg−1 while the average tAs and iAs concentrations in were 174.4 and
101.4 μg kg−1
,
respectively. Some people suffer from lactose intolerance and hence cannot consume cow
milk.
Therefore, rice, almond and soya bean milk are used due to their low allergenic activities
(Guillod-Magnin, Brüschweiler, Aubert, & Haldimann, 2018). Shannon & Rodriquez (2014)
tested rice milk for As concentration that ranged 2.7 to 17.9 μg L
−1. The study by Meharg et al.
(2008) reported total mean As level to be 22 μg L
−1 (range 10.2–33.322 μg L
−1). Sofuoglu et al.
(2014) analyzed As concentrations in rice and bulgur (an ancient food prepared from
wheat that
is still popular in Turkey and other eastern Mediterranean, Middle East, and eastern
European
countries). They found iAs to be major fraction in both; however rice had higher average
concentrations (0.16 mg kg-1
) than bulgur. The people who participated in the study also
consumed rice more than bulgur and hence carcinogenic risks were evaluated to be higher
with
rice consumption than with bulgur (Sofuoglu et al., 2014). In a case study in Chile, it was
found
that those who were exposed to high As during pregnancy or as children had higher
frequency of
bladder and lung cancers as adults (Steinmaus et al., 2014). In Italy, cereals and cereal
products
(rice, bread, and pasta etc.) contribute predominantly to iAs exposure to people (Cubadda,
D’Amato, Aureli, Raggi, & Mantovani, 2016). In a recent survey of Spanish and Serbian
market,
90 baby food samples were collected and analyzed for 10 heavy metals. It was found that
porridge made by vegetables and fish for infants is of specific concern as this had high level
of
metals including As and Pb (Skrbic, Zivancev, Jovanovic, & Farre, 2017). One porridge
sample
could cause daily intake of 13.45 g As kg bw−1 day−1 (4.5-times more than safe limit of
As 3 g
kg bw−1 day−1 established by EFSA, 2009. Hence, not only rice, food products prepared
from
fish and vegetables etc. may also contain high As levels.
Following recommendations, up to 6 months, infants should drink only the breast milk;
however, this practice is true only for about 35% of the world’s infants (WHO, 2013). In
During-2012, only 25% of infants were breastfed for the first 6 months in the European
region,
which is very low and means that 75% of infants relied on baby food products (WHO, 2013;
Bagsi Bosi, Eriksen, Sobko, Wijnhoven & Breda, 2015). Hence, infant foods and baby
porridges
(made of vegetables, fruits, rice, meat) are important for nutritional requirement of infants
(Ikem,
Nwankwoala, Odueyungbo, Nyavor, & Egiebor, 2002) and are crucial products to monitor
for
toxic elements, which may come from contaminated raw food or any other means. The
problem
is further exacerbated by the fact that infants and young children are at greater risk by
these
elements as they consume more food than adult people on body weight basis (Iwegbue,
Nwozo,
Overah, & Nwajei, 2010). Children below 3 years of age have been reported to suffer dietary
As
exposure as much as 3-fold more than that of adults (EFSA, 2014). Differences have been
found
to exist in rice consumption pattern and thus in urinary As levels in children (6-17 years of
age)
of different ethnic groups like Asian, Mexican and Black (Lai, Cottingham, Steinmaus,
Karagas,
& Miller, 2015). Karagas, Punshon, Sayarath, Jackson, Folt, & Cottingham (2016) analyzed
urine samples of infants of 12 months of age for As. The mean total As concentration was
9.53
g L-1
in the infants who ate infant rice cereal, compared with 4.97 g L-1
in those who ate rice
snacks and 2.85 g L-1
in those who did not eat any rice or rice products. Nachman, Ginsberg,
Miller, Murray, Nigra, & Pendergrast (2017) suggests following specific recommendations
for
different food items specially the prioritized foods, known for As contamination, and
monitoring
that set limit are met. Further, they stress that awareness among public should be a primary
strategy and they should also be given information about alternative safe foods and also
about quantity of food.
Rice processing and their effect on As contents
ratio of rice to water used for cooking of rice, water used for washing rice and the cooking
duration have been shown to significantly influence the As content and its bioaccessibility
in
cooked rice (Mwale et al., 2018; Althobiti, Sadiq, & Beauchemin, 2018). There are studies
which
show significant decrease of As in brown and polished rice when several washing steps are
performed. A large water to rice ratio for cooking and then removing extra water has been
found
to yield significant reductions in As (Sengupta et al., 2006; Rasheed, Kay, Slack, & Gong,
2018).
Sengupta et al. 2006 found up to 57% reduction in As with washing the rice until the water
runs
clear, cooking in a 6:1 water-to-rice ratio and draining the excess water (Sengupta et al.
2006).
This seems to vary because the water used for washing may also have different amounts of
As
(Rahman, Hasegawa, Rahman, Rahman, & Miah, 2006). However, it is also reported that
using
As contaminated water may lead to increase in As in rice due to absorption during rice
preparation (Rahman et al. 2006; Signes-Pastor et al., 2008; Liu et al., 2018). By contrast,
no
significant change was observed in mean As concentration in 14 raw Aman rice samples
before
(0.153 mg kg−1) and after (0.139 mg kg−1) cooking (Rahman et al., 2011). Other workers
(Smith
et al., 2006) also report that most of the As is retained in cooked rice. Naito, Matsumoto,
Shindoh, & Nishimura (2015) observed that washing was the major factor responsible for
reduced As in cooked rice rather than cooking procedure as when low water to rice ratio
(1.4–
2.0:1) was used for cooking, no As reduction was noticed. Carey, Jiujin, Farias, & Meharg
(2015) developed a specially designed cooker with percolating technology that removed up
to
85% of As during cooking. Brown rice contains vitamins and minerals which are lost during
polishing when the bran layer and germ are removed. To compensate for this loss, polished
white
and parboiled rice in the United States are fortified with a water soluble coating of iron
(Fe),
niacin, riboflavin, folic acid and thiamin. Hence, the cooking for such rice is prescribed to be
without any washing step and cooking in minimum water. Gray et al. (2016) also found that
if excess water is used for cooking rice, iAs is reduced by 40% from long grain polished,
60% from
parboiled and 50% from brown rice; however, this also leads to loss in Fe (90%) and
vitamins
(folate, thiamin and niacin; up to 80%). Total As, iAs, iron (Fe), vitamins, cadmium (Cd) and
manganese (Mn) all leached more from parboiled rice than from long grain polished rice.
On the
positive side of the extensive researches and policy changes conducted, a marked change in
composition and types of infant and children food products (rice proportion, mixing of
different
grains: rice and maize, rice with gluten free grans, muselis etc.) has been observed in food
samples collected from Ireland (Carey, Donaldson, Signes-Pastor, & Meharg, 2018).
The use of arsenic contaminated groundwater for irrigation of agricultural fields facilitates
the entry of arsenic in the food chain through consumption of contaminated food products
affecting a large number of people mainly in the South Asia and other parts of the world [3].
The long term use of arsenic contaminated groundwater for irrigation of agricultural soils
may lead to excessive accumulation of arsenic in the soil which, in turn, may exert land
degradation in terms of loss of yield i.e. decline in crop production and disease like
‘straighthead disease’ with empty panicle in rice [4]. It is highly warranted to initiate
monitoring and assessment programmes for arsenic contamination into irrigation
groundwater sources, agricultural fields being irrigated using those sources and the crops
grown in those fields. These programmes will explore the threat of arsenic contamination
in the newer areas still unexplored for the purpose. Because, data of spiked soil and
hydroponics experiments cannot be extrapolated as truly representative of the field
condition of arsenic contamination of soil and crops [5]. An understanding of soil arsenic
content and other soil properties (physico-chemical and biochemical) in relation to its
uptake and toxicity to crops is therefore urgently needed under field conditions. A good
correlation between arsenic uptake in plants/crops and total arsenic content in soils is not
always found. It is revealed that soil total arsenic content is not likely a good predictor of
arsenic uptake and toxicity under different soil types and micro-climatic conditions. It is the
bioavailable fraction of total arsenic in specific soil condition, which is potentially causing a
threat to the crops/plants. The arsenic-induced phytotoxicity is likely to be observed at 20
mg As kg-1 soil [6]. In case of paddy crop cultivation
with reference to soil arsenic pollution, representative data of arsenic toxicity are required
under non-flooded and flooded soil conditions to ascertain role of arsenic in limiting paddy
growth and yield under field conditions. It is necessary to sufficiently understand and
quantify the factors determining soil arsenic accumulation, its bioavailability and toxicity to
crops in the fields. Identification of geographic areas either presently contaminated with
arsenic or susceptible to its contamination, is an important step for risk assessment and
developing remediation strategies. The mapping of arsenic content which is being
transported from soil or irrigation water to edible plant parts, is important for protecting
against human arsenic exposure through arsenic contamination of the food chain.
Assessment of soil arsenic bioavailability may greatly support the scope of remediation
required at contaminated sites. It is concluded that future R&D is to be focused on
speciation, transformation and bioavailability of arsenic in soil and associated soil
properties to reveal tangible latent hazards of soil arsenic contamination to agriculture and
related food chain links.

Reference:
2. Singh AK (2006) Chemistry of arsenic in groundwater of Ganges-Brahmaputra river
basin. Current Science 91: 599-606.
3. Brammer H, Ravenscroft P (2009) Arsenic in groundwater: a threat to sustainable
agriculture in South and South-east Asia. Environ Int 35: 647-654.
4. Rahman MA, Hasegawa H, Rahman MM, Miah M, Tasmin A (2008) Straighthead disease of
rice (Oryza sativa L.) induced by arsenic toxicity. Environ Exp Bot 62: 54-59.
5. Heikens A, Panaullah GM, Meharg AA (2007) Arsenic behaviour from groundwater and
soil to crops: impacts on agriculture and food safety. Rev Environ Contam Toxicol 189: 43-
87.
6. Huq SMI, Rahman A, Sultana N, Naidu R (2003) Extent and severity of arsenic
contamination in soils of Bangladesh. In: Feroze AM, Ashraf AM, Adeel Z (eds) Fate of
Arsenic in the Environment. ITN Centre, Bangladesh.
Soil Arsenic Pollution: A Threat to Crops Pankaj Kumar Srivastava*, Manvi Singh, Nandita
Singh and Rudra Deo Tripathi Department of Environmental Science, CSIR-National
Botanical Research Institute, Rana Pratap Marg, Lucknow 226001, India

3. Arsenic in rice and other crops, and animals

3.1. Arsenic in rice
Rice is a widely consumed staple food, especially in India, Bangladesh as well as other
Southeast
Asian countries; the regions where As contamination is widespread and where rice
cultivation is
major agricultural practice. The problem of As accumulation in rice plant is a major global
concern as rice grains, rice milk and rice bran are consumed by millions of people of
different
ages (from infants to adults), groups and regions. As. The amount and forms of As in grains
are
influenced by irrigation regime, geographical location and environment (Williams et al.,
2006;
Rahman, Asaduzzaman, & Naidu, 2011; Awasthi et al., 2017), rice genotypes (Zavala &
Duxbury, 2008; Bhattacharya, Samal, Majumdar, & Santra, 2010), and rice grain processing
(Signes-Pastor et al., 2008). Dittmar et al. (2010) showed that the concentration of As
varied
even across a single field with highest concentration recorded near the irrigation water
inlet. The

variations in As exposure to humans are also caused due to differences in cooking methods
(Gray, Conklin, Todorov, & Kasko, 2016; Mwale, Rahman, & Modal, 2018), dietary habits of
people which change not only according to age, sex and region but also with the seasons. A
study by Biswas, Deb, Ghose, Santra, & Guha Mazumder, (2014) conducted in Nadia, West
Bengal, demonstrated seasonal changes in As levels in drinking water (26 g L−1 in
summer, 6
g L−1 in winter) as well as water intake by people from summer to winter (male: 3.8 and
2.5 L
day−1 and female: 2.6 and 1.2 L day−1). Hence, any evaluation of health risk should also
include
seasonal changes in As concentrations in water and food, seasonal diet and water intake
and also
probably the seasonal (temperature dependent) changes in bio accessibility and
metabolism of As
in humans.
There are hundreds of reports on As in rice. The studies include field based evaluations as
well as market based surveys. Owing to the growing concerns about As in rice, WHO has set
a
permissible limit for iAs of 0.2 mg kg-1 for white rice and 0.4 mg kg-1 for brown rice in July
2014. The maximum limits have been prescribed by European Union (EU) for iAs i.e. 0.2 mg
kg−1 for white rice. For rice based food products for infants and young children, a limit of
0.1 mg
kg−1 has been set while for other rice-based food products the limit is 0.3 mg kg−1. The
maximum
contaminant limit for iAs is 0.15 mg kg-1 in China while it is 0.7 mg kg-1 for tAs (Qian,
Chen,
Zhang, Li, Chen, & Li, 2010).
Arsenic concentrations have been found to vary in field and market based studies
(Meharg et al., 2009; Rahman et al., 2011; Williams et al., 2007; Zavala & Duxbury, 2008)
with
a maximum level of 1.835 mg kg−1 reported by Meharg & Rahman (2003). However, As
usually
remains below 1.0 mg kg−1. The average concentration of iAs has been found be <0.1 mg
kg−1 in
India, 0.13 mg kg−1 in Bangladesh, 0.14 mg kg−1 in Taiwan and China, and 0.19 mg kg−1
in
Japan (Meharg et al., 2009; Zavala, Gerads, Gurleyuk, & Duxbury, 2008; Williams, Price,
Raab, Hossain, Feldmann, & Meharg, 2005). Williams et al. (2005) found that white basmati
rice from
Indian supermarkets contains very low amount of tAs as 0.05 mg kg−1 (0.03−0.08 mg
kg−1). In
Spanish rice, tAs concentrations of 0.17 mg kg−1 (Williams et al., 2006) and 0.05−0.82 mg
kg−1
(Meharg et al., 2009) are reported. Zavala & Duxbury (2008) reported 0.156–0.19 mg kg-1
as the
highest mean As level in rice grown in USA, Italy and Spain. Rice from Bangladesh, Thailand
and Venezuela were found to have mean As level of 0.062–0.089 mg kg-1 and rice from
India
and Pakistan contained significantly less mean As concentrations of around 0.051–0.053
mg kg
1.
Sun et al. (2008) reported that As concentration in rice bran samples were very high (∼1
mg kg-1 dry weight; dw) i.e. 10-20 fold higher than concentrations found in bulk grain. It is
important to note that rice bran products are sold as super food and as a supplement to
malnourished children in International aid programs. In market survey of Batista, Souza,
Souza,
& Barbosa (2011) in Brazil on different types of rice (total 44), the highest mean As level
was
found in brown rice (0.348 mg kg-1) followed by parboiled brown rice (0.266 mg kg-1),
white
rice (0.223 mg kg-1) and parboiled white rice (0.215 mg kg-1). An experiment with 216
rice
genotypes showed that the ranges of As contents in indica rice and japonica rice were
0.021–
0.296 mg kg−1 and 0.005–0.274 mg kg−1, respectively (Jiang, Shi, & Wu, 2012).
Nookabkaew, Rangkadilok, Mahidol, Promsuk, & Satayavivad (2013) assessed 185
samples various types of rice in Thailand and some other Asian countries and reported
range of
tAs (0.023 – 0.375 mg kg-1) and iAs (0.0139 – 0.233 mg kg−1). Rahman, Rahman,
Reichman,
Lim, & Naidu (2014) evaluated total As concentrations in Australian grown organic brown,
medium grain brown, and organic white rice and found the average levels to be 0.438,
0.287, and
0.283 mg kg−1 dw, respectively. By contrast, rice imported from Bangladesh, India,
Pakistan, and

10

Thailand in Australia was found to contain tAs concentrations of 0.056, 0.092, 0.082 and
0.172
mg kg−1, respectively; the values being significantly lower than Australian grown rice.
Sofuoglu, Guzelkaya, Akgul, Kavcar, Kurucaovali, & Sofuoglu (2014) analyzed As
concentrations in rice samples from Turkey and found iAs to be major fraction (0.16 mg kg-
1).
Seyfferth, McCurdy, Schafer, & Fendorf (2014) evaluated As content in rice in Cambodia,
where
As problem is expected to arise due to similar geological settings and agricultural practises
as
that of otherAs contaminated Southeast Asian countries. The rice was collected from five
provinces (Kandal, Prey Veng, Battambang, Banteay Meanchey, and Kampong Thom) in the
rice-growing regions of Cambodia. Total grain As concentrations ranged from 0.1 to 0.37
mg kg
1 with an average of 0.2 mg kg−1.
Huang, Wang, Mao, Qian, Chen, & Zhang (2015) reported that out of 1653 milled rice
samples from 11 provinces in China, 1.1% contained higher than maximum recommended
As
levels as per Chinese regulations. Syu, Huang, Jiang, Lee, & Lee (2015) investigated the
impact
of As phytotoxicity and rice genotypes on As levels and speciation in rice grains in Taiwan.
It
was found that As concentrations did not correlate to soil As levels and were either equal or
more in indica than in japonica genotypes. An important finding was that As phytotoxicity
not
only affects the grain yield but also the grain As concentrations. DMA was the major As
species
that increased with increased total As concentrations, while As(III) remained stable at
about 0.1
0.3 mg kg-1.
In Europe, more than half of total production is from Italy and hence, analysis of As in
Italian rice is necessary. In Italian rice, Williams et al. (2006) reported tAs concentrations
around
0.19 – 0.22 mg kg−1 while Meharg et al. (2009) found 0.07-0.33 mg kg−1 tAs. Tenni et al.
(2017)
conducted a survey of As in Italian rice of different varieties collected from major rice
producing
areas. The average concentration of total As and iAs was 0.155 mg kg−1 and 0.102 mg
kg−1,

11

respectively. The concentration of iAs in total As was in range of 31 and 94%. Only DMA was
detected as oAs species in Italian rice. The iAs concentration in some samples was higher
than
limit for baby foods (i.e. >0.100 mg kg−1) (Tenni et al., 2017). A study by Sandhi, Greger,
Landberg, Jacks, & Bhattacharya (2017) evaluated total As in local aromatic rice (kalijira)
and
high yielding rice varieties (BRRI dhan 32 and BRRI dhan 28) in Bangladesh. They found
that
As accumulation factor was lower in LAR (0.2-0.4%) than in HYV (0.9 – 1%).

3.2. Arsenic in other crops (wheat, maize, pulses)

Wheat is the second most important staple food grown worldwide with annual production
of over
600 million tonnes (Williams et al., 2006). However, due to its cultivation in aerobic
conditions
and due to less affinity for silica accumulation, relatively low concentrations of As have
been
reported in wheat (Shi et al., 2015). Very little is known about the relationship between As
transport and it’s accumulation in wheat crops, especially in different wheat cultivars.
Recently,
it was demonstrated that arsenate tolerance of 57 wheat cultivars significantly varied and
the
tolerance was attributable to As retention mostly in roots (Shi et al., 2015). In wheat, total
As
concentration ranges from 0.010 mg kg-1 to 0.500 mg kg-1 with mean levels of <0.100 mg
kg-1
(Adomako, Williams, Deacon, & Meharg, 2011; Williams et al., 2007).
Maize (Zea mays), also known as corn, is one of the most cultivated cereal in the world.
According to the Food and Agriculture Organization of the United Nations, the global
production
of maize exceeded 883 million tons per year in 2011, a production greater than the
corresponding
production for wheat (704 million tons) and rice (723 million tons). An analysis of As in
maize
in Tanzania (Marwa, Meharg, & Rice, 2012) found As content in grain to range from 0.01 -
0.17
mg kg−1. The consumption of maize is high in some countries like Mexico (315.1 g day−1)
and in

12

such cases, corn with high As concentrations may pose health risk to people (Rosas-Castor,
Guzman-Mar, Hernandez-Ramirez, Garza-Gonzalez, & Hinojosa-Reyes, 2014).
Pulses (legume seeds) constitute an important dietary source of proteins for populations
in Southeast Asia and especially for those dependent on vegetarian diet. Only iAs has been
reported by Williams et al. (2006) in five different pulses. The contribution from pulses to
the
dietary intake of As is small because of the relatively low As concentration and small
quantity of
pulses being consumed worldwide (Williams et al., 2006). In Brazil, the dietary exposure of
iAs
has been evaluated to be 0.255 g kg-1 body weight per day that is about 9% of the
BMDL0.5 of
3 g kg-1 body weight per day. Rice and beans, the main Brazilian staple food, were the
major
factors in total As intake of 67-90% (46 -79% from rice and 11- 23% from beans). This was
the
first such report indicating beans as a potential As source and it is important as beans
constitute a
main staple food in some countries especially in Latin America and Southeastern Africa
countries (Ciminelli, Gasparon, Ng, Silva, & Caldeira, 2017). In sub-Saharan Africa, beans
supply more than 50% of the protein requirements and the consumption is up to 60 kg per
year
(164 g d-1) (Margaret, Tenywa, Otabbong, Mubiru, & Ali, 2014). Beans contained on
average
0.050 mg kg-1 As, which was less than the limit in Brazil of 0.1 mg kg-1 (ANVISA, 2013).
Rahman, Asaduzzaman, & Naidu (2013) demonstrated a range of 0.121 to 0.429 mg kg-1
dw in
pulses in a study conducted in West Bengal, India.
3.3. Arsenic in vegetables and mushrooms
Vegetables constitute another important category of human food and hence several reports
assessed As concentrations in a variety of vegetables and mushrooms. Potato (Solanum
tuberosum) is one of the largest crops of world after maize, rice and wheat (Leff,
Ramankutty, &
Foley, 2004). Arsenic speciation in potato tuber samples was determined by Williams et al.

13

(2006). The samples were from Bangladesh and the study reported presence of only iAs,
with no
detectable oAs species. The presence of MMA in potato tubers was reported by Signes-
Pastor et
al. (2008) from the samples collected from a village in West Bengal. The data on As in
vegetables indicated that the As-concentrations in some of the vegetable produce can be as
high
as that of rice on dry weight basis. Bhattacharya et al. (2010) reported that potatoes had
the
highest As accumulation even more than that in rice. Analysis by Rahman et al. (2013)
indicated
that total As concentrations in Malda, West Bengal showed a range of 0.000 to 1.464 mg kg-
1 dw
in food crops with the highest As concentration being in potato (0.456 mg kg-1), followed
by rice
grain (0.429 mg kg-1). The range of total As concentration was 0.243 to 0.456 mg kg-1 dw
in
tuber crops, 0.031 to 0.175 mg kg-1 dw in spices, 0.021 to 0.145 mg kg-1 in fruits and 0.032
to
0.411 mg kg-1 dw in vegetables. In Bangladesh, the range of As in vegetables has been
found
to be different for different regions viz., Chandpur and Jamalpur districts (0.070–3.990 mg
kg−1) and Sathkhira, Rajshahi, and Comilla districts (<0.040–1.930 mg kg−1) (Williams
et al.,
2006). In West Bengal, India, As analysis in vegetables from Jalangi and Domkal blocks
showed mean As levels of 0.0209 mg kg−1 (<0.00004–0.138 mg kg−1) and 0.0212 mg
kg−1
(0.00004–0.212 mg kg−1), respectively (Roychowdhury, Tokunaga, & Ando, 2003). As
levels
have been found to be higher in leafy vegetables (0.041–0.464 mg kg−1) than in non-leafy
vegetables (0.011–0.145 mg kg−1) (Williams et al., 2006). In cooked vegetables, a range of
0.019–2.334 mg kg−1 has been found from Munshiganj and Monohordi of Bangladesh
(Smith,
Lee, Heitkemper, Cafferky, Haque, & Henderson, 2006). There are some aquatic
macrophytes
also, which are used for eating. Falinski, Yost, Sampaga, & Peard (2014) assessed As
contamination of edible Nasturtium officinale (watercress) and Diplazium esculentum
(warabi),
which are consumed in Hawaii from an As contaminated area (Soil As: 356 mg kg-1). Total
As in
N. officinale and D. esculentum was 0.572 mg kg-1 and 0.075 mg kg-1, respectively.

14
Mushrooms constitute an important food item and the consumption of edible mushrooms
has increased considerably worldwide in recent years due to their nutritional properties
(Seyfferth, McClatchy, & Paukett (2016)). Wildly-growing mushrooms are capable of
accumulating certain elements in large amount in their fruit bodies (Wang et al., 2014).).
Zhang,
Liu, Li, Li, Wang, & Li (2015a) analyzed total As in 48 species of wild-grown edible and
medicinal mushrooms in China. The results showed highest As in Scleroderma citrinum
(1.70
mg kg-1 dw) and the lowest As in Termitomyces eurrhius (0.17 mg kg-1 dw). In an analysis
(Zhang et al. 2015a), Laccaria proxima and L. vinaceoavellanea growing naturally as well as
Laccaria mushroom samples from market were evaluated for As in Yunnan, China. The
mean
As concentrations in caps were 135, 14.1–143, 5.5 and 130–163 mg kg−1 dw for Laccaria
amethystina, L. laccata, L. proxima and L. vinaceoavellanea, respectively. In an analysis,
Seyfferth, et al. (2016) analyzed 40 mushroom samples of 12 types in US from two major
producing regions for As, Pb, and Cd. Differences were found in total As concentrations
(Cremini > Shiitake) and also in As localization (fruiting body in Cremini vs. hymenophore
in
Shiitake). However, As concentration was less than 1 mg kg−1 dw in all mushroom
samples.
Recently, As speciation analysis was performed in Elaphomyces spp. It was found that the
tAs
content ranged from 12 to 42 mg kg-1 dw in E. asperulus and from 120 to 660 mg kg-1 dw
in E.
granulatus and E. muricatus. The dominant species of As were oAs namely, MMA(V) (about
30% of extractable As), trimethylarsine oxide (TMAO, about 0.3 to 28% of extractable As)
and
MMA(III) (about 0.08-0.73% of extractable As) (Braeuer, Borovicka, & Goessler, 2018). In
mushrooms, the oAs content has been found to be comparatively higher than iAs that can
be
attributed to a more efficient enzymatic transformation of As from iAs to oAs species
(Braeuer et
al., 2018).
4. Infant cereals and other market based food products
Rice and rice-based food products constitute the major route for human exposure to As
particularly in people dependent on substantial rice-based foods and via baby food in
children
(Juskelis, Li, Nelson & Cappozzo, 2013; Tenni et al., 2017). Jackson, Taylor, Karagas,
Punshon,
& Cottingham (2012) reported presence of total As in infant formulas in Hanover
(Germany) and
New Hampshire (USA) in range of 2.2 to 12.6 μg kg−1 which was high for infants. Carbonell
Barrachina et al. (2012) analyzed Spanish gluten-free rice, cereals with gluten, and pureed
baby
foods and also pure infant rice samples from China, USA, UK and Spain. The concentration
of
iAs was found to be higher in gluten-free rice than in cereals mixtures with gluten. Cereals
prepared with mixed grains contained the lowest concentration of total (105 μg kg−1) and
iAs (63
μg kg−1). DMA was found as major oAs species, while MMA was not found. Juskelis et al.
(2013) analyzed 31 infant rice cereals from US supermarkets for As. The iAs ranged from
55.5

17

and 158.0 μg kg−1 while the average tAs and iAs concentrations in were 174.4 and 101.4
μg kg−1,
respectively. Some people suffer from lactose intolerance and hence cannot consume cow
milk.
Therefore, rice, almond and soya bean milk are used due to their low allergenic activities
(Guillod-Magnin, Brüschweiler, Aubert, & Haldimann, 2018). Shannon & Rodriquez (2014)
tested rice milk for As concentration that ranged 2.7 to 17.9 μg L−1. The study by Meharg
et al.
(2008) reported total mean As level to be 22 μg L−1 (range 10.2–33.322 μg L−1). Sofuoglu
et al.
(2014) analyzed As concentrations in rice and bulgur (an ancient food prepared from
wheat that
is still popular in Turkey and other eastern Mediterranean, Middle East, and eastern
European
countries). They found iAs to be major fraction in both; however rice had higher average
concentrations (0.16 mg kg-1) than bulgur. The people who participated in the study also
consumed rice more than bulgur and hence carcinogenic risks were evaluated to be higher
with
rice consumption than with bulgur (Sofuoglu et al., 2014). In a case study in Chile, it was
found
that those who were exposed to high As during pregnancy or as children had higher
frequency of
bladder and lung cancers as adults (Steinmaus et al., 2014). In Italy, cereals and cereal
products
(rice, bread, and pasta etc.) contribute predominantly to iAs exposure to people (Cubadda,
D’Amato, Aureli, Raggi, & Mantovani, 2016). In a recent survey of Spanish and Serbian
market,
90 baby food samples were collected and analyzed for 10 heavy metals. It was found that
porridge made by vegetables and fish for infants is of specific concern as this had high level
of
metals including As and Pb (Skrbic, Zivancev, Jovanovic, & Farre, 2017). One porridge
sample
could cause daily intake of 13.45 g As kg bw−1 day−1 (4.5-times more than safe limit of
As 3 g
kg bw−1 day−1 established by EFSA, 2009. Hence, not only rice, food products prepared
from
fish and vegetables etc. may also contain high As levels.
Following recommendations, up to 6 months, infants should drink only the breast milk;
however, this practice is true only for about 35% of the world’s infants (WHO, 2013). In
During
18

2006-2012, only 25% of infants were breastfed for the first 6 months in the European
region,
which is very low and means that 75% of infants relied on baby food products (WHO, 2013;
Bagsi Bosi, Eriksen, Sobko, Wijnhoven & Breda, 2015). Hence, infant foods and baby
porridges
(made of vegetables, fruits, rice, meat) are important for nutritional requirement of infants
(Ikem,
Nwankwoala, Odueyungbo, Nyavor, & Egiebor, 2002) and are crucial products to monitor
for
toxic elements, which may come from contaminated raw food or any other means. The
problem
is further exacerbated by the fact that infants and young children are at greater risk by
these
elements as they consume more food than adult people on body weight basis (Iwegbue,
Nwozo,
Overah, & Nwajei, 2010). Children below 3 years of age have been reported to suffer dietary
As
exposure as much as 3-fold more than that of adults (EFSA, 2014). Differences have been
found
to exist in rice consumption pattern and thus in urinary As levels in children (6-17 years of
age)
of different ethnic groups like Asian, Mexican and Black (Lai, Cottingham, Steinmaus,
Karagas,
& Miller, 2015). Karagas, Punshon, Sayarath, Jackson, Folt, & Cottingham (2016) analyzed
urine samples of infants of 12 months of age for As. The mean total As concentration was
9.53
g L-1 in the infants who ate infant rice cereal, compared with 4.97 g L-1 in those who
ate rice
snacks and 2.85 g L-1 in those who did not eat any rice or rice products. Nachman,
Ginsberg,
Miller, Murray, Nigra, & Pendergrast (2017) suggests following specific recommendations
for
different food items specially the prioritized foods, known for As contamination, and
monitoring
that set limit are met. Further, they stress that awareness among public should be a primary
strategy and they should also be given information about alternative safe foods and also
about
quantity of food.