Table 1. Recorded Concentrations of Toxic Metal in Evaluated Samples
LGA
|
Sample Identity
|
Mean concentration (mg/Kg)
|
Hg
|
Cu
|
Zn
|
Ni
|
Pb
|
Cd
|
Cr
|
Mn
|
As
|
Fe
|
V
|
Co
|
Kubau
|
kb1
|
ND
|
0.04±0.00
|
0.15±0.01
|
0.01±0.00
|
0.01±0.00
|
0.010±0.001
|
0.21±0.00
|
0.09±0.00
|
0.68±0.03
|
1.42±0.03
|
0.05±0.01
|
0.03±0.00
|
kb2
|
ND
|
0.03±0.00
|
0.21±0.00
|
-0.01±0.00
|
0.02±0.00
|
0.011±0.002
|
0.23±0.00
|
0.13±0.00
|
0.77±0.04
|
0.97±0.02
|
0.04±0.00
|
0.03±0.00
|
kb3
|
ND
|
0.03±0.00
|
0.17±0.01
|
0.01±0.00
|
0.01±0.00
|
0.010±0.001
|
0.23±0.00
|
0.11±0.00
|
0.74±0.05
|
0.82±0.04
|
0.07±0.01
|
0.02±0.00
|
Soba
|
So1
|
ND
|
0.03±0.00
|
0.29±0.01
|
ND
|
0.01±0.00
|
0.009±0.001
|
0.20±0.00
|
0.18±0.00
|
0.69±0.03
|
0.83±0.03
|
0.07±0.00
|
0.03±0.00
|
So2
|
ND
|
0.06±0.00
|
0.21±0.00
|
0.03±0.01
|
0.01±0.00
|
0.009±0.001
|
0.13±0.00
|
0.05±0.00
|
0.74±0.05
|
0.42±0.01
|
0.00±0.00
|
0.03±0.00
|
So3
|
ND
|
0.11±0.00
|
0.38±0.01
|
ND
|
0.01±0.00
|
0.009±0.001
|
0.25±0.00
|
0.90±0.00
|
0.77±0.04
|
1.70±0.04
|
0.25±0.00
|
0.03±0.00
|
Giwa
|
Gw1
|
ND
|
0.06±0.00
|
0.26±0.01
|
ND
|
0.01±0.00
|
0.010±0.001
|
0.21±0.00
|
0.16±0.00
|
0.73±0.02
|
1.26±0.03
|
0.07±0.00
|
0.030.00
|
Gw2
|
ND
|
0.09±0.00
|
0.22±0.01
|
ND
|
0.01±0.00
|
0.009±0.001
|
0.21±0.00
|
0.26±0.00
|
0.69±0.02
|
1.72±0.03
|
0.12±0.00
|
0.03±0.00
|
Gw3
|
ND
|
0.06±0.00
|
0.22±0.01
|
ND
|
0.01±0.00
|
0.009±0.001
|
0.22±0.00
|
0.19±0.00
|
0.75±0.04
|
1.08±0.01
|
0.06±0.00
|
0.03±0.00
|
Makarfi
|
Mk1
|
ND
|
0.03±0.00
|
0.14±0.00
|
0.01±0.00
|
0.04±0.00
|
0.010±0.001
|
0.25±0.00
|
0.08±0.00
|
0.77±0.02
|
0.94±0.03
|
0.03±0.00
|
0.030.00
|
Mk2
|
ND
|
0.12±0.00
|
0.26±0.00
|
0.01±0.00
|
0.02±0.00
|
0.01±0.001
|
0.17±0.00
|
0.17±0.00
|
0.72±0.04
|
0.63±0.03
|
0.04±0.00
|
0.03±0.00
|
Mk3
|
ND
|
0.13±0.00
|
0.17±0.00
|
0.02±0.00
|
0.02±0.00
|
0.003±0.001
|
0.23±0.00
|
0.13±0.00
|
0.56±0.05
|
1.01±0.00
|
0.05±0.01
|
0.01±0.00
|
Kauru
|
Ka1
|
ND
|
0.02±0.00
|
0.16±0.00
|
0.00±0.00
|
0.01±0.00
|
0.010±0.002
|
0.19±0.00
|
0.10±0.00
|
0.68±0.05
|
0.70±0.02
|
0.03±0.01
|
0.03±0.00
|
Ka2
|
ND
|
0.03±0.00
|
0.17±0.00
|
0.01±0.00
|
ND
|
0.010±0.001
|
0.17±0.00
|
0.08±0.00
|
0.71±0.06
|
0.56±0.02
|
0.04±0.00
|
ND
|
Ka3
|
ND
|
0.06±0.00
|
0.33±0.03
|
ND
|
0.02±0.00
|
0.011±0.002
|
0.20±0.00
|
0.21±0.00
|
0.71±0.05
|
1.92±0.03
|
0.07±0.01
|
0.03±0.00
|
Table 1(cont.).
LGA
|
Sample Identity
|
Mean concentration (mg/Kg)
|
Hg
|
Cu
|
Zn
|
Ni
|
Pb
|
Cd
|
Cr
|
Mn
|
As
|
Fe
|
V
|
Co
|
|
Kudan
|
Kd1
|
ND
|
0.030.00
|
0.13±0.00
|
0.02±0.00
|
0.01±0.00
|
0.009±0.00
|
0.24±0.00
|
0.05±0.00
|
0.78±0.04
|
0.63±0.01
|
0.05±0.00
|
0.02±0.00
|
|
Kd2
|
ND
|
0.02±0.00
|
0.14±0.00
|
0.01±0.00
|
0.06±0.00
|
0.009±0.001
|
0.23±0.00
|
0.09±0.00
|
0.74±0.05
|
0.63±0.03
|
0.04±0.00
|
0.03±0.00
|
|
Kd3
|
ND
|
0.02±0.00
|
0.12±0.00
|
0.01±0.00
|
0.02±0.00
|
0.009±0.00
|
0.19±0.00
|
0.07±0.00
|
0.71±0.03
|
0.49±0.02
|
0.05±0.00
|
0.03±0.00
|
|
Ikara
|
Ik1
|
ND
|
0.16±0.00
|
0.20±0.01
|
0.02±0.00
|
0.00±0.00
|
0.007±0.00
|
0.16±0.00
|
0.12±0.00
|
0.68±0.07
|
0.76±0.02
|
0.020.00
|
0.03±0.00
|
|
Ik2
|
ND
|
0.10±0.00
|
0.17±0.00
|
0.03±0.00
|
0.01±0.00
|
0.004±0.001
|
0.15±0.00
|
0.09±0.00
|
0.72±0.04
|
0.66±0.05
|
0.02±0.00
|
0.02±0.00
|
|
Ik3
|
ND
|
0.04±0.00
|
0.22±0.01
|
ND
|
0.02±0.00
|
0.010±0.001
|
0.20±0.00
|
0.17±0.00
|
0.71±0.04
|
1.14±0.02
|
0.05±0.01
|
0.03±0.00
|
|
Kajuru
|
Kj1
|
ND
|
0.11±0.00
|
0.20±0.00
|
0.03±0.00
|
0.01±0.00
|
0.005±0.00
|
0.23±0.00
|
0.09±0.00
|
0.70±0.06
|
1.15±0.04
|
0.02±0.00
|
0.02±0.00
|
|
Kj2
|
ND
|
0.06±0.00
|
0.27±0.00
|
ND
|
0.16±0.00
|
0.011±0.001
|
0.24±0.00
|
0.13±0.00
|
0.70±0.05
|
1.13±0.04
|
0.05±0.00
|
0.03±0.00
|
|
Kj3
|
ND
|
0.15±0.00
|
0.2±0.00
|
0.01±0.00
|
ND
|
0.001±0.001
|
0.18±0.01
|
0.09±0.00
|
0.33±0.05
|
0.95±0.02
|
0.03±0.00
|
0.01±0.00
|
|
Sanga
|
Sa1
|
ND
|
0.11±0.00
|
0.15±0.00
|
0.02±0.00
|
0.00±0.00
|
0.001±0.002
|
0.17±0.00
|
0.06±0.00
|
0.45±0.05
|
0.57±0.02
|
0.04±0.00
|
0.02±0.00
|
|
Sa2
|
ND
|
0.04±0.00
|
0.20±0.00
|
0.00±0.01
|
0.02±0.00
|
0.010±0.001
|
0.24±0.00
|
0.23±0.00
|
0.75±0.06
|
1.22±0.02
|
0.11±0.00
|
0.02±0.00
|
|
Sa3
|
ND
|
0.18±0.01
|
0.17±0.00
|
0.03±0.00
|
0.00±0.00
|
0.006±0.001
|
0.18±0.00
|
0.11±0.00
|
0.71±0.07
|
0.53±0.03
|
0.02±0.00
|
0.03±0.00
|
|
Lere
|
Le1
|
ND
|
0.07±0.00
|
0.31±0.01
|
ND
|
0.01±0.00
|
0.010±0.001
|
0.21±0.00
|
0.28±0.00
|
0.71±0.05
|
0.92±0.03
|
0.09±0.00
|
0.03±0.00
|
|
Le2
|
ND
|
0.08±0.00
|
0.18±0.00
|
0.02±0.00
|
ND
|
0.009±0.001
|
0.17±0.00
|
0.10±0.00
|
0.75±0.04
|
0.73±0.02
|
ND
|
0.03±0.00
|
|
Le3
|
ND
|
0.06±0.00
|
0.24±0.00
|
0.03±0.00
|
0.03±0.00
|
0.009±0.001
|
0.14±0.00
|
0.08±0.00
|
0.72±0.07
|
0.54±0.02
|
0.01±0.01
|
0.03±0.00
|
|
Table 1 (cont.).
LGA
|
Sample Identity
|
Mean concentration (mg/Kg)
|
Hg
|
Cu
|
Zn
|
Ni
|
Pb
|
Cd
|
Cr
|
Mn
|
As
|
Fe
|
V
|
Co
|
Chikun
|
Ch1
|
ND
|
0.04±0.00
|
0.26±0.00
|
0.00±0.00
|
0.01±0.00
|
0.010±0.001
|
0.23±0.00
|
0.20±0.00
|
0.78±0.03
|
1.06±0.05
|
0.07±0.01
|
0.03±0.00
|
Ch2
|
ND
|
0.04±0.00
|
0.17±0.00
|
0.00±0.00
|
0.02±0.00
|
0.010±0.00
|
0.22±0.00
|
0.15±0.00
|
0.72±0.02
|
0.91±0.04
|
0.06±0.00
|
0.03±0.00
|
Ch3
|
ND
|
0.05±0.00
|
0.15±0.00
|
0.00±0.00
|
0.01±0.00
|
0.011±0.001
|
0.23±0.00
|
0.13±0.00
|
0.75±0.04
|
1.57±0.06
|
0.05±0.00
|
0.03±0.00
|
Kachia
|
Kc1
|
ND
|
0.05±0.00
|
0.17±0.00
|
0.03±0.00
|
0.01±0.00
|
0.009±0.001
|
0.20±0.00
|
0.10±0.00
|
0.72±0.06
|
0.79±0.03
|
0.02±0.00
|
0.03±0.00
|
Kc2
|
ND
|
0.05±0.00
|
0.16±0.00
|
0.02±0.00
|
0.00±0.00
|
0.010±0.001
|
0.13±0.00
|
0.06±0.00
|
0.73±0.03
|
0.34±0.02
|
0.01±0.00
|
0.03±0.00
|
Kc3
|
ND
|
0.05±0.00
|
0.16±0.00
|
0.02±0.00
|
0.03±0.00
|
0.008±0.00
|
0.13±0.00
|
0.07±0.00
|
0.68±0.04
|
0.77±0.02
|
0.01±0.01
|
0.03±0.00
|
Sabon Gari
|
Sb1
|
ND
|
0.11±0.00
|
0.19±0.00
|
-0.020.00
|
0.01±0.00
|
0.009±0.001
|
0.22±0.00
|
0.21±0.00
|
0.73±0.05
|
3.66±0.02
|
0.11±0.00
|
0.02±0.00
|
Sb2
|
ND
|
0.09±0.00
|
0.24±0.00
|
-0.02±0.00
|
0.02±0.00
|
0.0080.001
|
0.23±0.01
|
0.280.00
|
0.71±0.03
|
2.47±0.07
|
0.08±0.01
|
0.03±0.00
|
Sb3
|
ND
|
0.06±0.00
|
0.210.00
|
-0.01±0.00
|
0.02±0.00
|
0.010±0.001
|
0.24±0.00
|
0.19±0.00
|
0.74±0.06
|
1.80±0.03
|
0.09±0.00
|
0.02±0.00
|
Key: ND= Not Detected,kb1 = Pambegua, kb2 = Anchau, kb3 = Zuntu, So1 = Damari, So2 = Maigana, So3 = Tashan Ice, Gw1 = Yakawada, Gw2 = Kaya, Gw3 = Gangara, Mk1 = Meyere, Mk2 = Makarfi Town, Mk3 = Gubuci, Ka1 = Chawai Kafin-Fadama, Ka2 = Anguwan-juri, Ka3 = Fadamam Badarin kasa, Kd1 = Hunkuyi, Kd2 = Zabi, Kd3 = Kudan Town, Ik1 = Sabon Gari, Ik2 = Saya Saya, Ik3 = Jamfalan, Kj1 = Kasuwan Magani, Kj2 = Maraba, Kj3 = Kufana, Sa1 = Gwantu, Sa2 = Fadan Karshi, Sa3 = Aboro, Le1 = YarKasuwa, Le2 = Lahadi, Le3= Mariri, Ch1 = Kujama, Ch2 = Mahuta, Ch3 = Maraban-Rido, Kc1 = Gummel, Kc2 = Katari, Kc3= Kurmin Musa, Sb1 = Likoro, Sb2 = Saka-Dadi, Sb3 = Jama’a, OR = Oriba, KI = King, TO = Tomato, MR = Mr. Rice, AM = Amaria.
Table 2. Regulatory Limits for Toxic Metal Concentration in Grains and Cereals
Elements
|
Toxicological guidance value (mg/kg)
|
WHO/FAO
|
NAFDAC
|
Hg
|
0.004
|
NA
|
Cu
|
0.073
|
0.04
|
Zn
|
0.1
|
0.05
|
Ni
|
0.067
|
0.027
|
Pb
|
0.0003
|
0.002
|
Cd
|
0.0001
|
0.0002
|
Cr
|
0.0023
|
0.002
|
Mn
|
500
|
NA
|
As
|
0.35
|
NA
|
Fe
|
48.00
|
NA
|
V
|
NA
|
NA
|
Co
|
50
|
NA
|
Key: NA= Not Available;
Table 3. Carcinogenic Grading of Investigated Metals
Element
|
Cancer Classification by IARC/EPA
|
ORfD
(mg/(kg/day)
|
OCSF
(mg/(kg/day)
|
Minimal Risk Level (MRL) Oral (mg/m3,day)
|
Cd
|
B1
|
1.00E-3
|
3.80E-2
|
0.0001
|
As
|
A
|
3.00E-4
|
1.50E+00
|
0.0003
|
Pb
|
B2
|
4.00E-03
|
8.50E-03
|
-
|
Mn
|
B2
|
2.00E-02
|
|
-
|
Co
|
-
|
-
|
-
|
-
|
Hg
|
D
|
1.00E-4
|
0
|
0.0002
|
Cr
|
A(Cr VI), D(Cr III)
|
1.50E-1
|
5.00E-01
|
0.005
|
Fe
|
|
|
|
-
|
Cu
|
D
|
4.00E-2
|
|
0.01
|
Ni
|
B2
|
2.00E-2
|
1.70E+1
|
-
|
V
|
|
|
|
-
|
Zn
|
|
3.00E-1
|
|
-
|
*MRL: estimates of the daily human exposure to a hazardous substance that is likely to be without an appreciable risk of adverse non-cancer health effects over specified routes and durations of exposure.
*Cancer classification: A-Human carcinogen, B1- probable human carcinogen, B2- probable human, C- possible human carcinogen, D-not classifiable as to human carcinogenicity [27].
3.1 Non Cancer Risk Index
Table 4. Estimated Daily Intake of Metals (EDIM)
Metals
|
Kb1
|
kb2
|
kb3
|
So1
|
So2
|
So3
|
Gw1
|
Gw2
|
Gw3
|
Ni
|
0.000085
|
-8.5E-05
|
0.000085
|
0
|
0.000255
|
0
|
0
|
0
|
0
|
Pb
|
0.000085
|
0.00017
|
0.000085
|
0.000085
|
0.000085
|
0.000085
|
0.000085
|
0.000085
|
0.000085
|
Cd
|
0.000085
|
9.35E-05
|
0.000085
|
7.65E-05
|
7.65E-05
|
7.65E-05
|
0.000085
|
7.65E-05
|
7.65E-05
|
Cr
|
0.001785
|
0.001955
|
0.001955
|
0.0017
|
0.001105
|
0.002125
|
0.001785
|
0.001785
|
0.00187
|
Mn
|
0.000765
|
0.001105
|
0.000935
|
0.00153
|
0.000425
|
0.00765
|
0.00136
|
0.00221
|
0.001615
|
As
|
0.00578
|
0.006545
|
0.00629
|
0.005865
|
0.00629
|
0.006545
|
0.006205
|
0.005865
|
0.006375
|
Co
|
0.000255
|
0.000255
|
0.00017
|
0.000255
|
0.000255
|
0.000255
|
0.000255
|
0.000255
|
0.000255
|
|
Mk1
|
Mk2
|
Mk3
|
Ka1
|
Ka2
|
Ka3
|
Kd1
|
Kd2
|
Kd3
|
Ni
|
0.000085
|
0.000085
|
0.00017
|
0
|
0.000085
|
0
|
0.00017
|
0.000085
|
0.000085
|
Pb
|
0.00034
|
0.00017
|
0.00017
|
0.000085
|
0
|
0.00017
|
0.000085
|
0.00051
|
0.00017
|
Cd
|
0.000085
|
0.000085
|
2.55E-05
|
0.00085
|
0.000085
|
9.35E-05
|
7.65E-05
|
7.65E-05
|
7.65E-05
|
Cr
|
0.002125
|
0.001445
|
0.001955
|
0.001615
|
0.001445
|
0.0017
|
0.00204
|
0.001955
|
0.001615
|
Mn
|
0.00068
|
0.001445
|
0.001105
|
0.00085
|
0.00068
|
0.001785
|
0.000425
|
0.000765
|
0.000595
|
As
|
0.006545
|
0.00612
|
0.00476
|
0.00578
|
0.006035
|
0.006035
|
0.00663
|
0.00629
|
0.006035
|
Co
|
0.000255
|
0.000255
|
0.000085
|
0.000255
|
0
|
0.000255
|
0.00017
|
0.000255
|
0.000255
|
|
Ik1
|
Ik2
|
Ik3
|
Kj1
|
Kj2
|
Kj3
|
Sa1
|
Sa2
|
Sa3
|
Ni
|
0.00017
|
0.000255
|
-8.5E-05
|
0.000255
|
0
|
0.000085
|
0.00017
|
0
|
0.000255
|
Pb
|
0
|
0.000085
|
0.00017
|
0.000085
|
0.00136
|
0
|
0
|
0.00017
|
0
|
Cd
|
0.0000595
|
0.000034
|
0.000085
|
4.25E-05
|
9.35E-05
|
8.5E-06
|
8.5E-06
|
0.000085
|
0.000051
|
Cr
|
0.00136
|
0.001275
|
0.0017
|
0.001955
|
0.00204
|
0.00153
|
0.001445
|
0.00204
|
0.00153
|
Mn
|
0.00102
|
0.000765
|
0.001445
|
0.000765
|
0.001105
|
0.000765
|
0.00051
|
0.001955
|
0.000935
|
As
|
0.00578
|
0.00612
|
0.006035
|
0.00595
|
0.00595
|
0.002805
|
0.003825
|
0.006375
|
0.006035
|
Co
|
0.000255
|
0.00017
|
0.000255
|
0.00017
|
0.000255
|
0.000085
|
0.00017
|
0.00017
|
0.000255
|
Metals
|
Kb1
|
kb2
|
kb3
|
So1
|
So2
|
So3
|
Gw1
|
Gw2
|
Gw3
|
Ni
|
0.000085
|
-8.5E-05
|
0.000085
|
0
|
0.000255
|
0
|
0
|
0
|
0
|
Pb
|
0.000085
|
0.00017
|
0.000085
|
0.000085
|
0.000085
|
0.000085
|
0.000085
|
0.000085
|
0.000085
|
Cd
|
0.000085
|
9.35E-05
|
0.000085
|
7.65E-05
|
7.65E-05
|
7.65E-05
|
0.000085
|
7.65E-05
|
7.65E-05
|
Cr
|
0.001785
|
0.001955
|
0.001955
|
0.0017
|
0.001105
|
0.002125
|
0.001785
|
0.001785
|
0.00187
|
Mn
|
0.000765
|
0.001105
|
0.000935
|
0.00153
|
0.000425
|
0.00765
|
0.00136
|
0.00221
|
0.001615
|
As
|
0.00578
|
0.006545
|
0.00629
|
0.005865
|
0.00629
|
0.006545
|
0.006205
|
0.005865
|
0.006375
|
Co
|
0.000255
|
0.000255
|
0.00017
|
0.000255
|
0.000255
|
0.000255
|
0.000255
|
0.000255
|
0.000255
|
3.2 Cancer Risk Index
Table 5. Incremental lifetime cancer risk in adult from consumption of rice (CR)
Metals
|
Kb1
|
kb2
|
kb3
|
So1
|
So2
|
So3
|
Gw1
|
Gw2
|
Gw3
|
|
Ni
|
0.001445
|
-0.00145
|
0.001445
|
0
|
0.004335
|
0
|
0
|
0
|
0
|
|
Pb
|
7.225E-07
|
1.45E-06
|
7.23E-07
|
7.23E-07
|
7.23E-07
|
7.23E-07
|
7.23E-07
|
7.23E-07
|
7.23E-07
|
|
Cd
|
0.00000323
|
3.55E-06
|
3.23E-06
|
2.91E-06
|
2.91E-06
|
2.91E-06
|
3.23E-06
|
2.91E-06
|
2.91E-06
|
|
Cr
|
0.0008925
|
0.000978
|
0.000978
|
0.00085
|
0.000553
|
0.001063
|
0.000893
|
0.000893
|
0.000935
|
|
As
|
0.00867
|
0.009818
|
0.009435
|
0.008798
|
0.009435
|
0.009818
|
0.009308
|
0.008798
|
0.009563
|
|
Metals
|
Mk1
|
Mk2
|
Mk3
|
Ka1
|
Ka2
|
Ka3
|
Kd1
|
Kd2
|
Kd3
|
|
Ni
|
0.001445
|
0.001445
|
0.00289
|
0
|
0.001445
|
0
|
0.00289
|
0.001445
|
0.001445
|
|
Pb
|
0.00000289
|
1.45E-06
|
1.45E-06
|
7.23E-07
|
0
|
1.45E-06
|
7.23E-07
|
4.34E-06
|
1.45E-06
|
|
Cd
|
0.00000323
|
3.23E-06
|
9.69E-07
|
3.23E-05
|
3.23E-06
|
3.55E-06
|
2.91E-06
|
2.91E-06
|
2.91E-06
|
|
Cr
|
0.0010625
|
0.000723
|
0.000978
|
0.000808
|
0.000723
|
0.00085
|
0.00102
|
0.000978
|
0.000808
|
|
As
|
0.0098175
|
0.00918
|
0.00714
|
0.00867
|
0.009053
|
0.009053
|
0.009945
|
0.009435
|
0.009053
|
|
Metals
|
Ik1
|
Ik2
|
Ik3
|
Kj1
|
Kj2
|
Kj3
|
Sa1
|
Sa2
|
Sa3
|
|
Ni
|
0.00289
|
0.004335
|
-0.00145
|
0.004335
|
0
|
0.001445
|
0.00289
|
0
|
0.004335
|
|
Pb
|
0E+00
|
7.23E-07
|
1.45E-06
|
7.23E-07
|
1.16E-05
|
0
|
0
|
1.45E-06
|
0
|
|
Cd
|
0.000002261
|
1.29E-06
|
3.23E-06
|
1.62E-06
|
3.55E-06
|
3.23E-07
|
3.23E-07
|
3.23E-06
|
1.94E-06
|
|
Cr
|
0.00068
|
0.000638
|
0.00085
|
0.000978
|
0.00102
|
0.000765
|
0.000723
|
0.00102
|
0.000765
|
|
Metals
|
Le1
|
Le2
|
Le3
|
Ch1
|
Ch2
|
Ch3
|
Kc1
|
Kc2
|
Kc3
|
Ni
|
0
|
0.00289
|
0.004335
|
0
|
0
|
0
|
0.004335
|
0.00289
|
0.00289
|
Pb
|
7.225E-07
|
0
|
2.17E-06
|
7.23E-07
|
1.45E-06
|
7.23E-07
|
7.23E-07
|
0
|
2.17E-06
|
Cd
|
0.00000323
|
2.91E-06
|
2.91E-06
|
3.23E-06
|
3.23E-06
|
3.55E-06
|
2.91E-06
|
3.23E-06
|
2.58E-06
|
Cr
|
0.0008925
|
0.000723
|
0.000595
|
0.000978
|
0.000935
|
0.000978
|
0.00085
|
0.000553
|
0.000553
|
As
|
0.0090525
|
0.009563
|
0.00918
|
0.009945
|
0.00918
|
0.009563
|
0.00918
|
0.009308
|
0.00867
|
Metals
|
Sb1
|
Sb2
|
Sb3
|
MR
|
OR
|
AM
|
TO
|
KG
|
|
Ni
|
-0.00289
|
-0.00289
|
-0.00145
|
0.00289
|
0.00289
|
0.00289
|
0.004335
|
0.004335
|
|
Pb
|
7.225E-07
|
1.45E-06
|
1.45E-06
|
0
|
2.89E-06
|
7.23E-07
|
0
|
7.23E-07
|
|
Cd
|
0.000002907
|
2.58E-06
|
3.23E-06
|
1.29E-06
|
1.29E-06
|
9.69E-07
|
6.46E-07
|
1.94E-06
|
|
Cr
|
0.000935
|
0.000978
|
0.00102
|
0.000893
|
0.000978
|
0.000638
|
0.000723
|
0.000765
|
|
As
|
0.0093075
|
0.009053
|
0.009435
|
0.008288
|
0.00918
|
0.00714
|
0.006248
|
0.009053
|
|
Table 6. Cumulative Cancer Risk for Individual Local Governments (∑CRt)
Kubau LGA
|
Soba LGA
|
Giwa LGA
|
Kb1
|
kb2
|
kb3
|
So1
|
So2
|
So3
|
Gw1
|
Gw2
|
Gw3
|
1.10E-02
|
9.35E-03
|
1.19E-02
|
9.65E-03
|
1.43E-02
|
1.09E-02
|
1.02E-02
|
9.69E-03
|
1.05E-02
|
Makarfi LGA
|
Kauru LGA
|
Kudan LGA
|
Mk1
|
Mk2
|
Mk3
|
Ka1
|
Ka2
|
Ka3
|
Kd1
|
Kd2
|
Kd3
|
0.012331
|
0.011353
|
0.01101
|
0.009511
|
0.011224
|
0.009908
|
0.013859
|
0.011865
|
0.01131
|
Ikara LGA
|
Kajuru
|
Sanga LGA
|
Ik1
|
Ik2
|
Ik3
|
Kj1
|
Kj2
|
Kj3
|
Sa1
|
Sa2
|
Sa3
|
1.22E-02
|
1.42E-02
|
8.46E-03
|
1.42E-02
|
9.96E-03
|
6.42E-03
|
9.35E-03
|
1.06E-02
|
1.42E-02
|
Lere LGA
|
Chikun LGA
|
Kachia LGA
|
Le1
|
Le2
|
Le3
|
Ch1
|
Ch2
|
Ch3
|
Kc1
|
Kc2
|
Kc3
|
9.95E-03
|
1.32E-02
|
1.41E-02
|
1.09E-02
|
1.01E-02
|
1.05E-02
|
1.44E-02
|
1.28E-02
|
1.21E-02
|
Sabon Gari LGA
|
Samaru Market
|
Sb1
|
Sb2
|
Sb3
|
MR
|
OR
|
AM
|
TO
|
KG
|
|
7.36E-03
|
7.15E-03
|
9.01E-03
|
1.21E-02
|
1.31E-02
|
1.07E-02
|
1.13E-02
|
1.42E-02
|
|
3.3 Toxic Metals Analysis
In Table 1 are presented results for toxic metals (Hg, Cu, Zn, Ni, Pb, Cd, Mn, As, Fe, V and Co) evaluated in 43 samples from 13 local governments in Kaduna State, while Table 2 presents regulatory limits (WHO/FAO and NAFDAC) for metals in grains and cereals.
Hg was not detected in any of the samples studied. The level of Cu in the rice samples was found to range between 0.02 - 0.18 mg/kg. Highest concentration of Cu (0.18 mg/kg) was observed in sample Sa3 from Sanga LGA, this was above the FAO/WHO and NAFDAC tolerable limits of 0.073 and 0.04 mg/kg. The lowest value (0.02 mg/kg) from Kudan (Kd2 and Kd3) and Kauru (Ka1) local government areas were below the regulatory limits. Copper, an essential element is usually incorporated into a number of metallo-enzymes. Exposure to excessive levels of copper can result in a number of adverse health effects including liver and kidney damage, anemia, immunotoxicity, and developmental toxicity [29].
Zinc (Zn) was found to be highest (0.38 mg/kg) in sample So3 (Soba LGA).This value was found to exceed the PTDI-WHO/FAO and NAFDAC permissible limits of 0.1 and 0.05 mg/kg. Clinical studies revealed up to 600 mg of zinc sulfate (equivalent to 200 mg elemental zinc) has been administered daily in divided doses for a period of several months, without any reported adverse effects, including effects on blood counts and serum biochemistry. There is a wide margin between nutritionally required amounts of zinc and toxic levels [28].
In the present study, the highest concentration reported for nickel (Ni) is 0.03 mg/kg, this value is below the threshold limit (0.067 mg/kg) by given WHO/FAO but just above that of NAFDAC (0.027 mg/kg), as evaluated in samples Le3 (Lere LGA), Kc1 (Kachia LGA), Ik2 (Ikara LGA), and also the imported rice TO and KG. . Samples Kb2, Ik3, and Sb3 did not record any concentration for Ni. Ni’s lithogenic availability is in abundance on earth. Studies have shown that it is an essential trace element for animals. However, the essentiality of nickel in humans has not been established [29]. Exposure to excess levels of nickel may cause neurotoxicity, hepatotoxicity, nephrotoxicity, gene toxicity, reproductive toxicity, and increased risk of cancer [30].
The comparative study of the distribution of Pb in all rice samples revealed the maximum level to be 0.16 mg/kg; this value is well beyond the stipulated limits of 0.0003 mg/kg and 0.002 mg/kg (WHO/FAO and NAFDAC). Lead is a non-essential element; excess exposure can result in neurological problems, hematological effects, renal failure, hypertension and cancer [31].
All values recorded for Cd in this study were above the WHO/FAO and NAFDAC regulatory limits of 0.0001and 0.0002 mg/kg. Cd is highly toxic to humans and excessive exposure to Cd is associated with renal, pulmonary, hepatic, skeletal, reproductive effects and cancer [32; 33]. The contamination of rice with Cd and its toxicity in large populations has been documented in countries which includes China and Thailand [34].
Chromium concentration ranged between 0.13 – 0.25 mg/kg, and was most available in samples collected from Soba and Makarfi (So3 and Mk1), the lowest value was determined in Soba (So2), as well as Kc2 and Kc3 from Kachia LGA. Generally, Cr ion quantified were beyond the permissible levels (0.0023 and 0.002 mg/kg) prescribed by WHO/FAO and NAFDAC. Kalkisim [35] reported that concentration of 0.03 –14μgg–1 Cr in the dry matter of plants is normal value, Cr levels tabulated in this study was above this consideration.
Result from this study show Manganese concentrations in all samples to be inferior to the WHO/FAO threshold (500 mg/kg). Although low levels of manganese intake are necessary for human health, exposure to high manganese levels may be toxic and can result in adverse neurological effects in humans [36].
Arsenic investigated was beyond the stipulated limit. The highest concentration (0.78 mg/kg) was reported for samples Kd1 and Ch1. Chronic exposure to As has encoreged skin, vascular, nervous system disorders and cancer [37]. WHO/FAO threshold for Arsenic in cereals and grains is 0.35 mg/kg, this value is only lower than result tabulated for Kj3 (0.33 mg/kg) from Kajuru LGA.
Levels of Fe in present study fall below the WHO/FAO regulatory limit. Iron is an abundant element on earth and a biologically essential component of every organism [38]. However, high iron intake may lead to increased risk of chronic diseases [39].
WHO/FAO and NAFDAC regulatory limits for Vanadium was not available to the researcher.
The highest concentration of Co was not more than the set limit of 50.00 mg/kg by WHO/FAO in all samples, no limit was set by NAFDAC. Cobalt is an important trace element in human diet, a component of vitamin B12. However, high oral doses of Co have resulted in adverse effects in humans including hematological, neurological, immunological, reproductive, cardiovascular, and endocrine responses [40].
3.4 Result for Statistical Test
Statistical evidence suggests that at confidence level of P < 0.05, there exist no statistical difference in concentrations of Cu, Zn, Ni, Pb, Cd, Cr, Mn, As, V and Cu amongst samples collected from farmers but there was difference in concentration of Fe. Concentration of metals in the foreign rice sample revealed there was also no significance difference (P < 0.05) in the availability of Cr, Pb, Cu, Ni, Cd, Co, V and Mn; while Zn, Fe and As, show significant difference. Similarly, metals in all samples studied showed no statistically significant difference in their concentrations except for Fe at P < 0.05.
Pearson Correlation was applied to validate the existence of correlation in concentration of determined heavy metals within the studied samples. A total of 1,936 correlations was matched in which 1806 (93 %) of documented samples gave a significant correlation at 0.001 level for a two tailed test, while 42 (2.2 %) correlations was significant at 0.05 level (two tailed). Eighty eight (4.5 %) pairing does not show any form of significant correlation.
3.5 Human Health Risk Assessment
To estimate health risks, information regarding some toxicological characteristics of the investigated elements were considered and referred to as shown in table 3. Health risk assessment indices were applied to evaluate the risk of exposure on consumption of contaminated foods via toxic metals (tables 4-6). It involves the use of mathematical models in evaluating risks of exposure to toxic metals at various concentrations, duly referenced by established standard values [41]. In this study, the safety of dietary intake of rice contaminated by toxic metals was estimated based on the intake of a 50 kg body weight Nigerian.
3.5.1 Estimated daily intake of metals (EDIM)
The result of the EDIM was computed and presented in Table 4. The highest EDIM value for Ni is 0.000255 mg/kg, this was recorded in samples Sa3, Kj1, So2, Ik2, Kc1, Le3, TO and KG, respectively. Values documented were below the mean daily intake of 0.0028 mg/50-60 kg day-1 bw [42].
Computed EDIM for Pb ranged between 0.00 mg/kg to 0.00034 mg/kg in samples Mk1 and OR; these values are below the WHO/FAO (2010) daily intake limit of 0.0005 mg/50-60 kg day-1 bw. Pb is one of the metals the human body does not need and its presence can cause severe health challenges, particularly for infants, children and pregnant women [43]. The toxic effects of lead and its compounds have been investigated for many years within several systems, contradiction beclouds data regarding to its mutagenic, clastogenic and carcinogenic properties. The International Agency for Research on Cancer classified lead as possible human carcinogen (group 2B) and its inorganic compounds as probable human carcinogens (group 2A). though there exist paucity of knowledge on the biochemical and molecular mechanisms of action of lead; still, some studies revealed existence of indirect mechanisms of genotoxicity such as inhibition of DNA repair or production of free radicals [31].The least EDIM for cadmium (Cd) was obtained in samples Kj3 and Sa1 (0.0000085 mg/kg), while the most (0.0000935 mg/kg) was obtained in samples Kj2, Kb2 and Ch3. This research reported figures below the provisional tolerable intake for Cd, stipulated as 0.001 mg/kg [44]. Cd has been classified as a B1 carcinogen, even as the present study sugest consumption of this element to be within safe-limits, the possibility of bioaccumulation, and amplification of its concentration overtime cannot be overruled [27]
The EDIM for Cr uptake calculated for this study spanned between 0.001105 mg/kg to 0.002125 mg/kg for adults. The lowest values were reported for samples So2, Kc2, and Kc3; following EFSA, 2014 valuation, these values were below the recommended amount(0.3 mg/50-60 kg day-1 bw), similarly in comparison to limit set by Expert Group on Vitamins and Mineral (EVM) safe upper level of trivalent chromium intake (0.15 mg/kg). Cr, especially in its hexavalent state is a pulmonary carcinogen and it is widely distributed, this can result eventually to DNA deletions and other genome rearrangements [45].
Daily intake for Mn in investigated samples was recorded highest and least for samples To and So3 (0.00034, 0.00765 mg/kg). These values are within safe ingestion (daily) limit as presented in the EC (2006) document. Epidemiological studies have reported 4.6 mg/day and 4.3 mg/day, with no toxic effect recorded. ESADDI-US National Resource Food Council and Nutrition Board set Mn intake at 2-5 mg/day for adults. Average values for this study were below the limits set by the above bodies. Women absorb a greater percentage of Mn than men, and absorption is correlated with Fe intake. Absorption of Manganese (Mn) is boosted in women with low Fe stores. Mn, even though an essential nutrient shows toxicity at elevated concentrations of exposure. Although human deficiency is rare, lack of Mn in animals may result to defect in the skeletal system, as well as impair lipid absorption. Skin rash and abnormalities have been reported as indications in purified Mn-deficient diet. Its toxicity may resort to Parkinson’s-like neuromuscular condition, tremor and facial muscular disorders. A few research findings posited that trace levels of Mn is linked to unusual comportment [46-48].
Arsenic (As) is a toxic element that have relatively high risk of transfer from paddy soils to rice grains, its accumulation in rice grains is important for food safety and human health [49]. Dietary intake for As was evaluated for all samples; computed results were compared to the provisional tolerable daily intake (PTDI) for inorganic As (0.00214 mg/body weight/day) and the Codex Alimentarius Commission (2014), (0.2 mg/kg for inorganic arsenic in rice). The present study evaluated EDIM for As in the range 0.002805 mg/kg (Kj3) to 0.00663 mg/kg in samples Kd1 and Ch1, which measures below the daily limit. Cancer Classification by IARC/EPA implicated arsenic as a class A carcinogen [27]. Inorganic As is considered to be more toxic to humans than pentavalent methylated As species [50]; Because of their lower acute toxicity to humans, the organic forms of arsenic are not targeted for regulation [51].
The EDIM for Co is in the range of 0.001122–0.002527 mg/kg. The permissible daily tolerable intake is 0.023 mg/50-60 kg day-1bw [52]. Values recorded were below the required daily intake. Consumption of Co from samples in present study is within safe levels.
3.5.2 Non-carcinogenic risk assessment
Non-carcinogenic hazards (hazard quotient (HQ) and target hazard quotient (THQ) as health risks resulting from oral exposure to toxic metals were estimated in all samples, result gave values < 1for Ni, Pb, Cd, Cr, Mn and Co; values for As where far >1 (in the range 9.35-21.817) were recorded in all samples, even though. THQ values do not offer a quantitative evaluation of the possibility of an exposed population facing a reverse health effects but rather functions as a suggestion of the risk level due to metal exposure [43; 53].
3.5.2.1 carcinogenic risk (CR)
USEPA in 2011 proposed an acceptable risk in the range of 1.0 x 10-6 to 1.0 x 10-4 over a lifetime of 70 years. When CR exceeds 1×10-4 – 1×10-6 further chemical‐specific assessment is required; however, when CR fall below the range, no action is required from a human health perspective. The potential carcinogen exposure over a lifetime was calculated for Ni, Pb, Cd, Cr and A are presented in Tables 6a and 6b. for samples from Kubau LGA, there exist cancer risk due to Ni, Cr and As (sample Kb1), Cr and As (Kb2), Ni, Cr, and As for Kb3. Samples from Soba LGA reported values beyond the risk threshold for Cr and As in So1, Ni, Cr and As in So2, then Cr and As in So3. Qw1, Qw2 and Qw3 reported similar values for Cr and As. Values beyond the Risk limit were also reported for Ni, Cr and As for samples from Makarfi LGA. Ka1 reported for Cr and As, Ka2 for Ni, Cr and AS, Ka3 for Cr and As. Kudan recorded excessive values for Ni, Cr and As in all samples. Ni documented above limit values for samples Ik1, Ik2, Kj1, Kj3, Sa1, Sa3, Le2, Le3, Kc1, Kc2, Kc3, MR, OR, AM, TO and KG. Cancer risk due to Cr and As was recorded in samples Ik1, Ik2, Ik3, Kj1, Kj2,Kj3, Sa1, Sa2, Sa3, Le1, Le2, Le3, Ch1, Ch2, Ch3, Kc1, Kc2, Kc3, Sb1, Sb2, Sb3, MR, OR, AM, TO and KG. samples Kb2, Mk1, Mk2, Mk3, Ka3, Kd2, Kd3, Ik3, Kj2,Sa2, Le3, Ch2, Kc3, Sb2, Sb3, and OR all fell within the lower limit for cancer risk. Samples not listed are within safe limits for individual metals present with their sample matrix. When multiple carcinogenic elements are present or evaluated in a sample, the cancer risks from all carcinogen are summed up (assuming additive effects).
Table 6 presents result for the summation of carcinogenic risks posed by the elements tabulated in 6, values recorded for samples in all local governments exceeded the acceptable lower and upper limit of carcinogenic risk. CRt for this work ranged from 6.42 x 10-3 to 1.44 x 10-2, the lowest CRt was determined at Kajuru (Kj3) LGA, while the highest was recorded at Kachia LGA (Kc1). The implication of this result is that amongst consumers of rice from these study sites, indicate there exist cancer risk at a lower limit of 64 chance in 1000 lifetime exposure and an upper limit of 14 chance in 100 lifetime exposure for any combination of two or more of Ni, Pb, Cd, Cr and As available for consumption; this is particularly worrisome especially as Pb has no safe level in blood [53].
Statistical analysis at 95 % significant level show that there exist no difference in cancer risk arising from consumption of rice from sampled area.