Accepted Manuscript Evaluations of environmental hazard parameters of natural and some artificial radionuclides in river water and sediments
Özlem Selçuk Zorer PII: DOI: Reference:
S0026-265X(18)31229-3 https://doi.org/10.1016/j.microc.2018.11.035 MICROC 3480
To appear in:
Microchemical Journal
Received date: Revised date: Accepted date:
27 September 2018 19 November 2018 19 November 2018
Please cite this article as: Özlem Selçuk Zorer , Evaluations of environmental hazard parameters of natural and some artificial radionuclides in river water and sediments. Microc (2018), https://doi.org/10.1016/j.microc.2018.11.035
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ACCEPTED MANUSCRIPT Evaluations of Environmental Hazard Parameters of Natural and Some Artificial Radionuclides in River Water and Sediments
Özlem Selçuk Zorer
Turkey
SC RI PT
Van Yuzuncu Yil University, Faculty of Science, Department of Chemistry, 65080, Van,
E-mail:
[email protected] Abstract
137
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In order to evaluate the radiological baseline in the Lake Van basin, 238U, 232Th, 226Ra, Cs and 40K activity concentrations and gross radioactivity were determined in twelve river
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water and sediment samples. To determine radionuclide activities and gross radioactivity, a gamma ray spectrometer with HPGe detector and a gross-alpha/beta-counting system low
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background multi-detector were used, respectively. Therefore, based on the measured activity concentrations, parameters of radiological hazards such as radium equivalent activity, outdoor
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absorbed dose rate, annual effective dose, and internal and external hazard indices were
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calculated. Req, Hex and Hin values in samples were generally lower than worldwide average
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values; while Dout and AED values were higher than worldwide average values in general.
Keywords: Natural radionuclides; gross radioactivity; sediment; water; hazard parameters
1. Introduction
Naturally-occurring radioisotopes in the environment are connected with 232
Th, and
40
226
Ra (238U),
K radioisotopes in rocks, sand, soils, and sediments. Artificial radionuclides in
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ACCEPTED MANUSCRIPT the environment arise from anthropogenic sources, such as weapon tests, nuclear medicine, nuclear accidents, and nuclear fuel cycles. Radioactivity in the environment and external exposure due to gamma radiation occurs at different levels in nature and it varies geographically due to geological changes in each region of the world [1]. 226Ra (238U), and
40
232
Th,
K distributions in sands are associated with radionuclide availability in bedrock,
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together with the chemical and mechanical processes through which the sands are concentrated. The specific terrestrial background radiation levels are connected with the types of rocks from which the sediments originate. Igneous rocks containing dark-coloured heavy minerals usually have higher radiation, whereas lower level radiation comes from sedimentary
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rocks. The ratio of Th to U in bedrock is considerably lower than in soils due to the accumulation and migration capabilities of Th and U.
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Radionuclides with half-lives long enough to be compared with the earth's crust are called primordial radionuclides. Radioactivity in the surface layers of the soil originates in the 238
U, 232Th, 40K and 87Rb. The anthropogenic
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decay of primordial radionuclides such as
radionuclides such as 137Cs and 90Sr are also available in considerable amounts in the soil due
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to nuclear weapon tests and nuclear accidents. The terrestrial gamma radiation levels are
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highly affected by radioisotopes that are present in soil. The purposes of the present research were to investigate the distribution of
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radionuclide activity in the Lake Van Basin and to compute radiation hazard parameters due to the presence of 238U, 232Th and 40K in samples. It is essential to establish both radiometric and radiological baseline data, which do not exist yet. Therefore, radionuclide activity and gross-α/β radioactivity concentrations were measured by using a gamma ray spectrometer with HPGe detector and gas-flow proportional counter, respectively.
2. Results and Discussion
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2.1. Radioactivity analysis
The activity concentrations of detected radionuclides, 238U, 232Th, 40K, 137Cs, and gross radioactivity in water samples for spring and summer seasons are reported in Table 1. The
238
U, 2.9-12.7 Bq/L for
232
Th, 6.4-28.18 Bq/L for
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activity concentrations in the water samples were measured at a range of 1.67-8.91 Bq/L for 40
137
K and 0.27-0.52 Bq/L for
Cs in the
spring season. In the summer season, the activity concentrations of radionuclides varied: for U between 2.09 and 7.36 Bq/L; for
12.75 and 35.95 Bq/L; and for
232
Th between 0.71 and 11.95 Bq/L; for
137
40
K between
Cs between 0.29 and 0.59 Bq/L. The mean activities of
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238
Bq/L for 40K and 0.36 Bq/L for 137Cs.
238
U, 5.61 Bq/L for
232
Th, 21.6
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radionuclides in both seasons were found as 3.97 Bq/L for
Radionuclides in structure of soils and rocks arrive to surface waters with rain and
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snow waters via precipitation and flooding. Radionuclides mixed to groundwater by filtering from soil have contributed to the increased radioactivity concentration in water samples. Due
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to the high rainfall in the spring season, radionuclides are more likely to reach the surface
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water through filtration and leaching. It can be said that decreasing rainfall in summer season affects radionuclides and their activities reaching surface waters.
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The distribution of radionuclide activities in water samples are illustrated in Figure S1. The radionuclide activity concentration values varied according to sampling points, because the bed of each river passes through regions with different geological structure and may have different chemical and mineralogical composition. Limit values proposed by the EPA for radioactivity concentrations in groundwater are 0.2 Bq/L (5 pCi/L) for
226
Ra (with
228
Ra), 1.1 Bq/L (30 pCi/L) for
234
U (with
238
U) and 0.6
Bq/L (15 pCi/L) for gross alpha activity (without radon and uranium) [2]. According to these
3
ACCEPTED MANUSCRIPT limit values; while the uranium activities in the river water samples for both seasons are found to be high, the gross-α activity concentrations are quite low. However, the permissible limits 232
Th, 235U and 226Ra in drinking water according to the World Health Organization are
1 Bq/L while the limit for 238U and consideration, the
238
U and
137
137
Cs is 10 Bq/L [3]. When these limits are taken into
Cs activity concentrations in the water samples are below the
limit values for both seasons, while the
232
Th concentrations are above the values. At the
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for
same time, recommended values for drinking waters are 0.5 Bq/L for gross-α radioactivity and 1 Bq/L for gross-β radioactivity [3]. In all samples, gross-α/β activity concentrations measured are below the limit values.
Ra, 40K and 137Cs) and gross radioactivity in the sediment samples for spring and summer
seasons. The
226
Ra activity concentrations ranged between 23.46 and 85.29 Bq/kg and mean
concentration of
226
radioactivities of
232
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226
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Table 2 demonstrates the natural radionuclide radioactivity concentrations (232Th,
Ra was calculated as 47.48 Bq/kg. The maximum, minimum and mean
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Th were 118.07, 20.64 and 57.87 Bq/kg, respectively. The
137
Cs activity
concentrations were measured as 0.3 Bq/kg for minimum, 17.92 Bq/kg for maximum and 4.37
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Bq/kg for mean. The lowest and highest activity concentrations of
40
K were found as 400.64
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Bq/kg in S3 sample in summer and 1722.59 Bq/kg in S9 sample in spring, while the mean concentration was found as 1021.43 Bq/kg. The gross-α and gross-β activity concentrations
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ranged from 0.22-6.44 Bq/kg and 0.7-8.22 Bq/kg, respectively. Radioactive elements are concentrated mostly in the surface layers of soil as their migration downwards is limited and depends on the many chemical and physical conditions of the soil system [4, 5]. The leached radionuclides from igneous rocks, soils and agricultural areas are transported to under terrains and into rivers by rainwater and erosion. However, agricultural fertilizers products contain various trace elements such as uranium and thorium decay series members [6]. Due to temperature increase effect, chemical structure of soil and
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ACCEPTED MANUSCRIPT fertilization activities, radioactivity in sediments is expected to be partly high in summer season. Worldwide average concentrations of
226
Ra,
232
Th and
40
K in soil are 35 Bq/kg, 30
Bq/kg and 400 Bq/kg, respectively. The population-weighted average concentrations of these radionuclides are 32 Bq/kg, 45 Bq/kg and 420 Bq/kg, respectively [7]. Compared to these 226
Ra activities of samples S3, S6 and S11 were determined to be lower than the
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limits, the
permissible population-weighted average values. In terms of
232
Th activities, S2, S3, S7, S11
and S12 samples have lower concentrations than both the permissible average and populationweighted average limit values. The
40
K radioactivity of S3 sample is lower than the
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worldwide population-weighted average limit, while it almost equals to the worldwide average limit.
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The locations of S4, S5, S8, S9 and S10 samples have volcanic rock structure. S4 and S5 samples were collected from rivers on the skirts of Mount Nemrut Volcano, while S8, S9
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and S10 samples were from rivers flowing in beds composed of volcanic rocks produced by Mount Süphan Volcano and the volcanic Tendürek Mountain. Since uranium and thorium can
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be concentrated in rocks by igneous and sedimentary processes [8], it is an expected result
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that natural radionuclide concentrations are high in these samples taken from rivers flowing in volcanic terrain. Based on the high natural radionuclide concentrations in these samples, the
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gross-α/β activities are also relatively high. In addition, the measurements showed that the higher than the other radionuclides. The
40
40
K activities in all samples were
K activity concentration is higher than the
concentration of 226Ra and 232Th, which is normally expected for soil. The excess of 40K in the study regions may be due to over-fertilization and geological differences. The relationships between radionuclides in sediments are illustrated in Figure S2. As seen in the figure, moderate positive correlations were observed between 226Ra and 232Th (Fig.
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ACCEPTED MANUSCRIPT S2b) (R2=0.62) and between 226Ra and 40K (Fig. S2c) (R2=0.54), a weak positive correlation was observed between 226Ra and 137Cs (Fig. S2a) (R2=0.05), and strong positive correlation was observed between 232Th and 40K (Fig. S2d) (R2=0.90). In the literature, positive correlations between 232Th and 226Ra, while
232
Th and
40
232
Th and 40K,
226
Ra and 40K have been shown [9-11],
K have a weak positive correlation [12] and
Ra and 137Cs have a weak
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negative correlation [13].
226
The correlation of gross-α and gross-β in sediment samples is illustrated in Figure S3. The gross-β activity concentrations are higher than gross-α concentrations, but there is a positive correlation between both activity concentrations.
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The comparison of radionuclide activity concentrations in river water and sediment samples with reported values in other locations around the world are presented in Table 3. In
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the present study, the mean radioactivity values of
226
Ra,
232
Th and
are almost in accord with the other average values. The mean
40
238
K in sediment samples
U,
232
Th,
40
K and
137
Cs
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radioactivities in water samples are quite close to the radionuclide activities in many parts of
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the world.
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2.2. Radiation Hazard Parameters
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Radium equivalent activity (Raeq), outdoor absorbed gamma dose rate (Dout) and annual effective dose (AED), and external and internal hazard indices (Hex, Hin) calculated based on radionuclide activities in sediment samples are presented in Table 4. The values of Raeq for the sediment samples ranged from 92.8 to 386.8 Bq/kg in spring and from 91.3 to 321.0 Bq/kg in summer. The average Raeq value reported is 370 Bq/kg [7]. Except for S9 sample in spring, Raeq values in all sediment samples were determined to be within world standards.
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ACCEPTED MANUSCRIPT The outdoor absorbed gamma dose rate (Dout) values were calculated in the range of 40.75-167.87 nGy/h for spring season and 40.15-139.55 nGy/h for summer season. The worldwide average and the population-weighted average values of Dout reported are 57 nGy/h and 59 nGy/h, respectively [7]. Except for three samples (S2, S3, and S7) in spring season and three samples (S3, S7 and S11) in summer season, Dout was found to be higher than the
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recommended world average values in all other samples.
The calculated annual effective dose (AED) ranged from 49.96 to 205.88 μSv/y with the mean value of 110.25 μSv/y for spring and ranged from 49.24 to 171.14 μSv/y with the mean value of 114.93 μSv/y for summer. As in the case of Dout values, all AED values are
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higher than the world average value of 70 μSv/y [1], except for three samples in both seasons. The minimum and maximum external hazard index (Hex) calculated depending upon
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radionuclide activities in sediment samples were 0.25 and 1.05 for spring season and 0.25 and 0.87 for summer season. The internal hazard index (Hin) ranged from 0.31 to 1.28 for spring
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and 0.31 to 1.06 for summer. While the internal and external hazard indices should not exceed 1, the Hex value in S9 sample for only the spring season and Hin values in S8, S9 and S10
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samples for both spring and summer seasons were higher than 1. When the internal hazard
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index is considered as the hazard for the respiratory organs due to radon and short-lived isotopes, there may be a health hazard in stations with Hin values greater than 1.
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Figure S4 shows the comparison of all radiation hazard parameters with the world averages. According to the figure, outdoor absorbed gamma dose rate (Dout) and annual effective dose (AED) values in sediment samples are higher than worldwide averages except for six samples.
3. Conclusions
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ACCEPTED MANUSCRIPT The river sediment and water samples, collected from 12 points in both spring and summer seasons, were analysed for natural and anthropogenic radionuclides and gross radioactivity using HPGe detector and gas-flow proportional counter. In river water samples, the mean radioactivity concentrations of
238
U, 232Th, 40K and 137Cs in both seasons were 3.97
Bq/L, 5.61 Bq/L, 21.6 Bq/L, and 0.36 Bq/L, respectively. In river sediment samples, while S3
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sample had the lowest value for radionuclide activity concentrations, S8, S9 and S10 samples, especially, had the highest average values. As these samples were collected from rivers flowing in a volcanic field and the concentrations of radioactive elements in the volcanic rocks was higher, the radionuclide activities of these samples and their corresponding gross
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radioactivity were found to be higher. All of the results show that radioactivity concentrations were influenced by the geological structure and distribution.
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However, depending upon the measured activity concentrations, radium equivalent activity (Req), outdoor absorbed dose rate (Dout), annual effective dose (AED), and external
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and internal hazard indices (Hex, Hin) were calculated and the health risks were evaluated. When the calculated hazard parameter values are compared to the world averages, it can be
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said that the radioactivities in samples S8, S9 and S10 could constitute a radiation risk for the
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local population.
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Acknowledgements: The author thanks to the University of Van Yuzuncu Yil Scientific Research Projects Support Unit for their financial support (Project No. 2009-FED-B011).
References
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ACCEPTED MANUSCRIPT Table 1. The radionuclide and gross-α/β activity concentrations of water samples in spring and summer (Bq/L) Spring 238
U
137
Cs
232
Th
Summer 40
K
Gross-α
Gross-β
238
137
U
232
Cs
40
Th
K
Gross-α
Gross-β
15.04
0.01
0.66
0.71
21.95
BDL
BDL
2.59
12.79
BDL
BDL
T P
W1
4.42
BDL
12.7
22.13
0.01
BDL
3.33
BDL
W2
4.25
0.30
6.20
10.37
BDL
BDL
2.09
0.59
W3
7.45
BDL
2.90
28.18
BDL
BDL
3.57
BDL
W4
8.91
0.52
9.27
25.41
BDL
0.96
2.89
BDL
11.95
14.00
BDL
0.16
W5
4.27
BDL
3.52
26.27
BDL
0.25
3.43
BDL
6.02
19.88
BDL
0.12
W6
1.75
0.31
4.28
32.50
0.01
0.14
2.41
0.29
3.21
22.64
BDL
0.37
W7
3.43
BDL
6.96
20.74
BDL
BDL
6.29
21.43
0.11
BDL
W8
1.67
BDL
7.49
22.99
0.01
M
2.38
0.33
4.20
BDL
5.84
21.61
BDL
0.15
W9
2.84
BDL
5.80
6.40
0.02
BDL
6.10
BDL
5.98
31.29
BDL
0.50
W10
2.27
BDL
3.59
10.56
BDL
0.82
4.77
0.23
5.14
23.96
BDL
0.72
W11
4.11
BDL
4.73
22.99
BDL
0.61
7.36
BDL
6.87
22.13
BDL
0.04
W12
3.35
0.27
5.08
27.14
BDL
BDL
4.01
BDL
4.91
35.95
0.03
BDL
Min.
1.67
0.27
2.90
6.40
0.01
0.14
2.09
0.29
0.71
12.79
0.01
0.04
Max.
8.91
0.52
12.7
28.18
0.02
0.96
7.36
0.59
11.95
35.95
0.11
0.72
Mean
4.06
0.35
6.04
21.31
0.01
0.56
3.88
0.37
5.18
21.89
0.05
0.34
PT
E C
C A
D E
0.78
2.63
C S U
I R
N A
BDL: Below detection limit
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ACCEPTED MANUSCRIPT Table 2. The radionuclide and gross-α/β activity concentrations of sediment samples in spring and summer (Bq/kg) Spring 226
137
226
137
232
S1
42.79
7.10
57.79
5.44
38.32
10.29
64.09
S2
32.68
1.52
0.81
2.55
68.06
2.01
S3
23.58
420.11
0.22
2.64
24.33
5.35
S4
54.25
1042.27
3.70
5.90
60.71
3.33
71.21
1186.62
3.73
6.35
31.14
2.57
48.76
1206.84
1.77
4.16
S7
33.06
1.24
24.76
449.12
0.67
2.02
S8
66.17
1.33
94.45
1645.03
3.82
S9
85.29
6.01
118.07
1722.59
S10
64.52
8.26
82.48
1690.92
S11
26.38
3.09
36.69
S12
45.08
2.90
31.31
Min.
23.58
1.24
Max.
85.29
Mean
44.93
Ra
Cs
232
Summer 40
Th
K
Gross-α
Gross-β
1170.35
2.34
20.64
456.46
4.20
25.75
34.02
3.28
S5
54.41
S6
Gross-β
1189.60
2.06
5.59
27.82
575.09
0.97
2.45
25.29
400.64
0.62
0.70
4.32
84.77
1467.80
4.37
5.03
64.46
0.73
88.74
1501.98
3.61
4.12
28.52
2.11
46.26
1005.65
2.01
4.23
38.38
1.86
27.90
478.83
0.83
1.47
6.06
72.22
0.30
93.19
1500.77
4.26
4.75
2.33
8.22
64.46
17.92
103.49
1371.29
6.44
6.51
1.56
7.76
65.54
10.96
96.23
1457.86
4.50
5.27
715.51
0.91
4.06
23.46
2.19
36.41
515.99
0.60
3.35
1.23
3.97
51.75
1.93
28.49
650.91
2.29
2.60
20.64
420.11
0.22
2.02
23.46
0.30
25.29
400.64
0.60
0.70
8.26
C A
691.97
118.07
1722.59
3.82
8.22
72.22
17.92
103.49
1501.98
6.44
6.51
3.74
55.51
1033.15
1.92
4.93
50.02
4.99
60.22
1009.70
2.71
3.84
PT
E C
Th
K
T P
I R
C S U
N A
M
Cs
40
Gross-α
D E
Ra
13
ACCEPTED MANUSCRIPT Table 3. Comparison of activity concentrations of radionuclides in river water and sediments with different areas of the world Sediment/Soil (Bq/kg) 137Cs
232Th
40K
Reference
Turkey
-
-
27
524
[14]
Italy
25.1
-
28.1
809.8
[15]
Nigeria
47.89
-
55.37
1023
[16]
China
33.1
-
21.8
Spain
-
1.6
-
Argentina
27-69
-
3-41
Present Study
47.48
4.37
RI
PT
226Ra
[17]
328
[18]
531-873
[19]
NU
SC
833.3
57.87
1021.4
MA
Water (Bq/L)
137Cs
232Th
40K
Reference
Spain
-
<0.35
-
328
[18]
Hungary
2.51
-
1.71
41.43
[20]
Malaysia
-
-
0.37
4.82
[21]
-
-
4.93
80.09
[22]
0.32
-
0.40
4.09
[23]
3.97
0.36
5.61
21.6
PT E
AC
Present Study
CE
Iran Ghana
D
238U
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ACCEPTED MANUSCRIPT Table 4. The radiation hazard parameters of the sediment samples Spring
Summer
Req (Bq/kg)
Dout (nGy/h)
AED (μSv/y)
Hex
Hin
Req (Bq/kg)
Dout (nGy/h)
S1
215.6
96.23
118.02
0.58
0.70
221.6
98.98
S2
97.3
42.72
52.39
0.26
0.35
152.1
65.57
S3
92.8
40.74
49.96
0.25
0.31
91.3
S4
191.9
85.15
104.43
0.52
0.61
S5
247.6
108.3
132.82
0.67
0.82
S6
193.8
87.5
107.31
0.52
S7
103.1
44.78
54.92
0.28
S8
327.9
143.71
176.25
S9
386.8
167.87
205.88
S10
312.7
139.23
S11
133.9
59.47
S12
143.1
63.06
Hex
Hin
121.39
0.60
0.70
80.42
0.41
0.59
40.15
49.24
0.25
0.31
129.55
158.88
0.80
0.96
307.0
134.13
164.5
0.83
1.00
0.61
172.1
77.0
94.43
0.47
0.54
0.37
115.2
49.88
61.17
0.31
0.42
0.89
1.06
321.0
139.55
171.14
0.87
1.06
1.05
1.28
318.0
139.06
170.54
0.86
1.03
170.75
0.84
1.02
315.4
138.14
169.42
0.85
1.03
72.93
0.36
0.43
115.3
50.07
61.41
0.31
0.38
77.34
0.39
0.51
142.6
62.43
76.56
0.39
0.53
D E
T P E
C C
A
AED (μSv/y)
SC
A M
U N 294.9
I R
T P
15
ACCEPTED MANUSCRIPT Figure Captions
AC
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PT
ED
MA
NU
SC RI PT
Figure 1. Approximated location of sampling sites
16
Fig.1
AC
CE
PT
ED
MA
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SC RI PT
ACCEPTED MANUSCRIPT
17
ACCEPTED MANUSCRIPT Highlights
AC
CE
PT
ED
MA
NU
SC RI PT
1. This research is first detailed database for this area and will be radiological baseline. 2. The radiological baseline in the Lake Van basin was investigated. 3. Radiation hazard parameters (Req, Dout, AED, Hin, Hex) were calculated. 4. Gamma-ray spectrometer with HPGe detector and gross-α/β-counting system were used. 5. In some samples, Req, Hex and Hin values were higher than worldwide average values.
18