The TEs concentration of olive orchard soils
The complementary statistical results of olive orchard soils are given in Table 3. The pH values were changed between 5.36-8.12 and 46% of them are in the mild alkaline class (7.4-7.9) (Table 3). The most abundant TEs were Al, followed by Fe and Mn. Another trace element was under their respective limits established by research and regulation According to the Regulation of Turkish Soil Pollution Control, Cu, Pb, and Zn concentrations of soils were below limit values, and Cr and Ni maximum concentrations were regarded as approximately 2.11 and 4.15 times higher than limit levels (SPCR, 2005). Concentrations of Cr and Ni pass over their limit levels in 8 (10.4%), and 15 (19.5%) samples, respectively. According to the soil world average levels (Kabata-Pendias, 2011), Cd, Cu, and Zn concentrations were lightly bigger, where about 1.2, 1.02, and 1.13 times bigger than their suitable average worldwide, respectively. While Co and Cr concentrations were bigger by about 3.5 times, Mn concentration by about 2 times, and Ni concentration was about 10 times bigger than the worldwide average. The Pb concentration was narrowly below its Worldwide and Europe average levels (Kabata-Pendias, 2011). Also, Ni, Co, Cu, Cr, Mn, Cd, and Zn concentrations were about 8.42, 3.8, 2.8, 2.2, 2.02, 1.5, and 1.16 times bigger than the European soils average (Kabata-Pendias, 2011) (Table 3). According to Rudnick & Gao (2004), Zn was about 1.19, Mn about 1.27, Cu about 1.71, Co and Cr about 2.3, Ni about 6.63 times bigger, and concentrations of Al, Fe, and Pb were below UCC values (Table 3).
Compared to mean TEs concentrations of agricultural soils in Harran Plain of Turkey, Fe and Al concentrations in our study were a little low than those in Harran Plain. Ni concentration was about 3.5, Co, Cr, and Pb about 2.5, Cu 1about.8, and Zn about 1.2 times higher than their respective in Harran plain (Varol et al., 2020) (Table 3). When compared with TEs concentration in Malatya province soils, while Ni concentration was about 4.4, Co about 3.2, Mn about 2.1, Cd and Pb about 1.8, Cu and Fe about 1.4, Zn about 1.2 were higher, Cr was slightly higher than their respective values (Varol et al., 2021) (Table 3). Also, according to Sungur and Isler (2021), Cd concentrations were below average in Canakkale agricultural soils (Table 3). These results related to various regions had distinct TEs concentrations in the soil the reason for the variability in both natural mineral corrosion and human activity.
Table 3 Summary statistics of TEs of olive orchard soils in Izmir province and comparison with other studies, regulation and average levels in the upper crust, Europe soils, and worldwide soils (mg/kg)
|
Al
|
Cd
|
Co
|
Cr
|
Cu
|
Fe
|
Mn
|
Ni
|
Pb
|
Zn
|
References
|
Izmir Province
|
Mean
|
22520.9659
|
0.1762
|
7.5828
|
44.9147
|
19.1078
|
15821.2499
|
352.3812
|
37.8760
|
8.8498
|
34.8845
|
This study
|
Median
|
22465.5000
|
0.1700
|
6.8300
|
33.8200
|
17.,4300
|
15874.6000
|
325.5400
|
24.8000
|
8.6100
|
32.7600
|
This study
|
Standart deviation
|
5622.62491
|
0.08738
|
4.06986
|
36.49086
|
7.97687
|
5012.75707
|
148.31770
|
39.53544
|
4.44061
|
11.79008
|
This study
|
Standart error
|
495.04452
|
0.00769
|
0.,35833
|
3.21284
|
0.70232
|
441.34865
|
13.05865
|
3.48090
|
0.39097
|
1.03806
|
This study
|
Minimum
|
10955.80
|
0.02
|
2.06
|
9.28
|
6.59
|
5463.83
|
133.91
|
6.50
|
1.29
|
13.42
|
This study
|
Maximum
|
37521.50
|
0.42
|
39.79
|
210.74
|
47.82
|
28834.00
|
984.11
|
311.49
|
25.41
|
79.60
|
This study
|
Soils of Worldwide
|
-
|
0.41
|
11.3
|
59.5
|
38.9
|
-
|
488
|
29
|
27
|
70
|
Kabata-Pendias (2011)
|
Soils of Europe
|
-
|
0.28
|
10.4
|
94.8
|
17,3
|
-
|
524
|
37
|
32
|
68.1
|
Kabata-Pendias (2011)
|
Maximum allowable concentration
|
|
5
|
50
|
200
|
150
|
|
|
60
|
300
|
|
Kabata-Pendias (2011)
|
Control regulation of Turkish roil
|
-
|
-
|
-
|
100
|
140
|
-
|
-
|
75
|
300
|
300
|
SPCR (2005)
|
Upper continental crust (UCC)
|
81500
|
0.09
|
17.3
|
92
|
28
|
39.200
|
774
|
47
|
17
|
67
|
Rudnick and Gao (2004)
|
Amik Plain of Turkey
|
-
|
-
|
20.4
|
-
|
-
|
-
|
-
|
274
|
5.6
|
-
|
Karanlik et al. (2011)
|
Bursa province ofTurkey
|
-
|
-
|
-
|
125
|
40
|
-
|
1667
|
158
|
81
|
477
|
Aydinalp and Marinova (2003)
|
Thrace region of Turkey
|
-
|
-
|
11
|
173
|
20
|
26900
|
600
|
50
|
33
|
45
|
Coskun et al. (2006)
|
Sinop province of Turkey
|
-
|
-
|
-
|
194.73
|
43,19
|
38849
|
-
|
85.02
|
17.01
|
65.1
|
Baltas et al. (2020)
|
Malatya province of Turkey
|
27524
|
0.244
|
12.6
|
59.9
|
36,4
|
21195
|
475
|
70.9
|
14.2
|
67
|
Varol et al. (2021)
|
Harran Plain of Turkey
|
42692
|
|
16
|
85
|
27
|
37505
|
679
|
89
|
10.6
|
68
|
Varol et al. (2020)
|
Canakkale province of Turkey
|
-
|
1.75
|
-
|
102.2
|
46,63
|
-
|
-
|
117.6
|
68.85
|
-
|
Sungur and Isler (2021)
|
Contamination indices of olive orchard soils
The calculated pollution indices (1.49 < EF < 7.18; -2.49 < Igeo < 0.16; 0.28 < Cf < 1.96) are given in Figure 2. The highest EF value was obtained by Cd (7.18). It was followed by Ni (2.94) >Cu (2.56) > Zn (1.93) > Pb (1.9) > Cr (1.79) > Mn (1.63) > Co (1.59) (Figure 2). According to Sutherland’s (2000) classification, Cd showed significantly (2-20), Ni, Cu, Zn showed moderate (2-5), and Pb, Cr, Mn, and Co showed minimal (<2) enrichment. The highest Igeo value was obtained from Cd (0.16). It was followed by Cu (-1.25) > Ni (-1.32) > Zn (-1.60) ≥ Pb (-1.72) > Mn (-1.83) > Cr (-1.92) = Co (-1.92) > Fe (-1.97) > Al (-2.49) (Figure 2). Soils were unpolluted to moderately polluted (0-1) by Cd, and unpolluted (<0) by other elements (Mazurek et al. 2017). The highest Cf values was obtained by Cd (1.96) that was followed by Ni (0.81) > Cu (0.68) > Zn (0.52) ≥ Pb (0.52) > Cr (0.49) > Mn (0.46) > Fe (0.40) > Al (0.28) (Figure 2). The soils were “moderately contaminated (1-3)” with Cd, and “low contamination (<1)” with Ni, Cu, Zn, Pb, Cr, Mn, Fe, Al. Oils, diesel oils, rotors, phosphate fertilizers, sludges, pesticides, colorings, batteries, production of semimetal, waste incineration, and manufacturing of iron and steel are all cited as possible anthropogenic sources of trace components of the environment (Lagerwerff & Specht, 1970; Sutherland 2000). In a research conducted in the olive orchards area, approximately 60% of the soils were sufficient class in terms of phosphorus (Deliboran et al., 2019). As it is known, phosphorus fertilizers have high Cd content (Assche & Clijsters, 1990). As a result of our study, it is thought that the high Cd content is due to phosphorus fertilization.
Indices of ecological risk
The highest Er values was obtained by Cd (58.83), Cd was followed Ni (4.03) > Cu (3.41) > Pb (2.60) > Cr (0.98) > Zn (0.52) (Figure 2). According to Hakanson (1980), the olive orchard soils have “a moderate potential ecological risk (40-80)” caused by Cd. Similarly, Vural et al. (2021) suggested that Cd has the biggest Er level in Malatya province of Turkey, and Hu et al. (2020) that in the agricultural fields of Handan (China). In the other study, Cd, Ni, and As were the highest Er level in India’s agricultural soils (Kumar et al., 2019). RI is generally found in four grades: low hazard (RI ≤ 150), middle hazard (150 < RI ≤ 300), major hazard (300 < RI ≤ 600), and upper hazard (RI > 600) (Mazurek et al., 2017; Pan et al., 2016). RI values ranged from 12.01 to 158.34, and RI levels of the vast majority of all samples were low risk (Figure 2). Only 1.5% of soils were at moderate risk with a few differences>150, because of this, soils had low ecological risk same (Figure 2) as the Harran Plain soils (Vural et al., 2020). High RI levels of soils are seldom recorded in the literature. For example, agricultural soils have a high ecological hazard in India (RI ¼ 544) because of the using agricultural practice like as chemical fertilizers or pesticides (Kumar et al., 2019), Similarly, agricultural soils have very high RI levels near a smelter in China (Wu et al., 2019).
Analysis of multivariate statistics
Pearson correlation matrix was used to determine relationships between TEs (Table 4). The highest correlation was determined between Ni and Cr (r=0.951) and between Ni and Co (r=0.813) (Table 4). Finding strong correlations between heavy metals may indicate that the elements are of the same origin or interdependent (Yi et al., 2011). The strong correlation between Cr and Ni shows that these two heavy metals originate from similar sources and were of a lithogenic origin (Taspinar et al., 2021). This highest correlation followed by Cr and Co (r=0.743), Zn and Cd (r=0.680), Mn and Al (r=0.668), Co and Fe (r=0.655), Zn and Fe (r=0.637), Cd and Fe (r=0.561), Fe and Al (r=0.543), Cu and Fe (r=0.506) (Table 4). In addition, positive correlation was found between Cd and Al (r=0.448), Co and Cd (r=0.419), Cr and Al (r=0.240), Cr and Fe (r=0.338), Cr and Cd (r=0.299), Cu and Al (r=0.266), Cu and Cd (r=0.283), Cu and Co (r=0.237) (Table 4).
Table 4 Pearson correlation analysis of TEs
|
Al
|
Fe
|
Cd
|
Co
|
Cr
|
Cu
|
Mn
|
Ni
|
Pb
|
Zn
|
Al
|
1
|
|
|
|
|
|
|
|
|
|
Fe
|
0,543**
|
1
|
|
|
|
|
|
|
|
|
Cd
|
0,448**
|
0,561**
|
1
|
|
|
|
|
|
|
|
Co
|
0,468
|
0,655**
|
0,419**
|
1
|
|
|
|
|
|
|
Cr
|
0,240**
|
0,338**
|
0,299**
|
0.743**
|
1
|
|
|
|
|
|
Cu
|
0,266**
|
0,506**
|
0,283**
|
0.237**
|
0.119
|
1
|
|
|
|
|
Mn
|
0,668**
|
0,459**
|
0,405**
|
0.490**
|
0.256**
|
0.274**
|
1
|
|
|
|
Ni
|
0,222*
|
0,312**
|
0,282**
|
0.813**
|
0.951**
|
0.069
|
0.266**
|
1
|
|
|
Pb
|
0,405**
|
0,17
|
0,268**
|
-0.067
|
-0.207*
|
0.038
|
0.395**
|
-0.170
|
1
|
|
Zn
|
0,484**
|
0,637**
|
0,680**
|
0,312**
|
0.126
|
0.491**
|
0.445**
|
0.134
|
0.474**
|
1
|
Three significant components with eigenvalues >1 were identified according to the analysis of the principal component (PCA). The first component of PCA was representing 44% of the total variance. PC1 had big positive loading (≥0.7) in terms of Co, Fe, Al, Cd, Zn, and Mn (Table 5). The median concentration of these elements and Ni did not above the UCC levels (Table 3). Also, Co, Fe, Al, and Mn were connected (Table 5), and these TEs were influenced by sources of natural (lithogenic). These elements have low EF, Igeo, and Cf, and this supported this finding (Figure 2). It is accepted that the heavy metals present in PC1 consist of the decomposition of the bedrock material of lithogenic origin (Batlas et al., 2020; Chandrasekaran et al., 2015; Taspinar et al. 2021). The Cd median concentrations are above the UCC levels (Table 3), and the mean concentration of Ni is above the world soil average level (Table 3). Cd and Ni were greater than other TEs in terms of the EF, Igeo, and Cf levels (Fig. 2). Also, Cd has positively correlated with Al, Fe, Mn, and Zn which are the majority of abundant elements in the Earth’s crust (Table 4). These results related to Cd and Ni were natural origins and anthropogenic sources for example agricultural practices. It is known that phosphate fertilizers are an important source of Cd and Ni (Rutigliano et al., 2019). As a result, the first component was particularly related to lithogenic origin although agricultural practices contributed completely to Cd and Ni.
The second component represented 22% of the total variance, Pb and Zn had great positive loaded these components, while the third component represented 11% of the total variance and Pb had a high positive loaded. Pb has a positive correlation with Al, Cd, and Mn, and Zn with Fe, Cd, Cu, Al, and Pb. Also, the median concentration of these elements did not exceed the UCC and the world soil average levels (Table 3), and generally, their EF, Igeo, and Cf levels were low (Fig 2). Because of these results, Pb and Zn came from natural sources, and the second component was mostly associated with lithogenic sources. Also, it is known that the main reasons for the increase of Pb, Zn, Al, Cd, Mn, Cu, and Ni in the soils were the livestock manure and phosphorus fertilizers that are frequently used in agricultural production as anthropogenic (Baltas et al., 2020; Marrugo-Negrete et al., 2017). According to Cevik et al. (2009) and Kumar et al. (2019), the leading cause of cadmium in agriculturally produced soil is the use of fertilizers and pesticides in agriculture.
Table 5 Component matrix of TEs
Factor
|
PC1
|
PC2
|
PC3
|
Al
|
0.722
|
0.300
|
0.285
|
Fe
|
0.806
|
0.080
|
-0.368
|
Cd
|
0.715
|
0.226
|
-0.073
|
Co
|
0.818
|
-0.447
|
0.060
|
Cr
|
0.624
|
-0.703
|
0.114
|
Cu
|
0.485
|
0.237
|
-0.656
|
Mn
|
0.704
|
0.249
|
0.338
|
Ni
|
0.626
|
-0.713
|
0.174
|
Pb
|
0.245
|
0.691
|
0.510
|
Zn
|
0.710
|
0.490
|
-0.184
|
Eigenvalues
|
4.428
|
2.185
|
1.106
|
of variance
|
44.0
|
22.0
|
11.0
|
Cumulative
|
44.0
|
66.0
|
77.0
|
Indices of health risk assessment
The HQ, HI and THI leves for adults and children were below 1, considering that all TEs in soil via ingestion, skin contact, inhalation paths had no major non-carcinogenic risks (Table 6). Similar results were forwarded from the other researchs (Praveena et al., 2018; Varol et al., 2020; Varol et. al., 2021). For example, according to Taspinar et al. (2021), the THI values were below 1 for adults and children in peach orchards soils of Bilecik province. According to Jiang et al. (2017), in Jiangsu Province soils of China, for adults and children the THI values were 3.62 and 6.21, respectively. As a result of this study, for adult and children, the highest HQ values was obtained from Co, Cr and Mn via ingestion, dermal contact and inhalation, respectively (Table 6). For children, HQingestion levels declined in the order of Co (8.08E-02) > Fe (7.22E-02) > Al (7.20E-02) > Cr (4.78E-02) > Mn (4.69E-02) > Pb (2.02E-02) > Ni ( 6.05E-03) > Cu (1.53E-03) > Cd (5.75E-04) > Zn (3.72E-04), HQdermal levels followed the order of Cr (1.82E-02) > Mn (1.11E-02) > Ni (1.44E-03) > Co (7.67E-04) > Fe (6.86E-04) > Al (6.83E-04) > Cd (2.18E-04) > Pb (1.92E-04) > Cu (1.45E-05) > Zn (3.53E-06), and HQinhalation levels were found in the region of Mn (4.97E-03) > Al (3.18E-03) > Co (8.91E-04) > Cr (3.17E-04) > Ni (2.97E-04) > Cd (1.27E-05) (Table 6). For adult, HQingestion values reduced in the region of Co (6.92E-03) > Fe (6.19E-039 > Al (6.17E-03) > Mn (4.02E-03) > Cr (4.10E-03) > Pb (1.73E-03) > Ni (5.19E-04) > Cu (1.31E-04) > Cd (4.93E-05) > Zn (3.19E-05), HQdermal values were followed the region of Cr (9.11E-04) > Mn (5.59E-04) > Ni (7.21E-05) > Co (3.85E-05) > Fe+Al (3.44E-05) > Cd (1.10E-05) > Pb (9.62E-06) > Cu (7.27E-07) > Zn (1.77E-07), and HQinhalation values were discovered in the region of Mn (4.97E-03) > Al (3.18E-03) > Co (8.91E-04) > Cr (3.17E-04) > Ni (2.97E-04) > Cd (1.27E-05) (Table 6).
Table 6 Non-carcinogenic and carcinogenic risks for residential receivers
|
Noncarcinogenic risks for adult
|
Noncarcinogenic risks for child
|
Carcinogenic risks
|
|
HQ
ingestion
|
HQ
dermal
|
HQ inhalation
|
HI
|
HQ
ingestion
|
HQ
dermal
|
HQ inhalation
|
HI
|
CR
ingestion
|
CR
dermal
|
CR
inhalation
|
TCR
|
Al
|
6,17E-03
|
3,43E-05
|
3,18E-03
|
9,38E-03
|
7,20E-02
|
6,83E-04
|
3,18E-03
|
7,58E-02
|
-
|
-
|
-
|
-
|
Fe
|
6,19E-03
|
3,44E-05
|
-
|
6,23E-03
|
7,22E-02
|
6,86E-04
|
-
|
7,29E-02
|
-
|
-
|
-
|
-
|
Cd
|
4,93E-05
|
1,10E-05
|
1,27E-05
|
7,30E-05
|
5,75E-04
|
2,18E-04
|
1,27E-05
|
8,06E-04
|
-
|
-
|
6,01E-11
|
6,01E-11
|
Co
|
6,92E-03
|
3,85E-05
|
8,91E-04
|
7,85E-03
|
8,08E-02
|
7,67E-04
|
8,91E-04
|
8,24E-02
|
-
|
-
|
1,27E-08
|
1,27E-08
|
Cra
|
4,10E-03
|
9,11E-04
|
3,17E-04
|
5,33E-03
|
4,78E-02
|
1,82E-02
|
3,17E-04
|
6,63E-02
|
7,29E-06
|
3,52E-06
|
7,00E-07
|
1,15E-05
|
Cu
|
1,31E-04
|
7,27E-07
|
-
|
1,32E-04
|
1,53E-03
|
1,45E-05
|
-
|
1,54E-03
|
-
|
-
|
-
|
-
|
Mn
|
4,02E-03
|
5,59E-04
|
4,97E-03
|
9,55E-03
|
4,69E-02
|
1,11E-02
|
4,97E-03
|
6,30E-02
|
-
|
-
|
-
|
-
|
Ni
|
5,19E-04
|
7,21E-05
|
2,97E-04
|
8,88E-04
|
6,05E-03
|
1,44E-03
|
2,97E-04
|
7,79E-03
|
-
|
-
|
-
|
-
|
Pb
|
1,73E-03
|
9,62E-06
|
-
|
1,74E-03
|
2,02E-02
|
1,92E-04
|
-
|
2,04E-02
|
-
|
-
|
-
|
-
|
Zn
|
3,19E-05
|
1,77E-07
|
-
|
3,20E-05
|
3,72E-04
|
3,53E-06
|
-
|
3,75E-04
|
-
|
-
|
-
|
-
|
|
CHQ
|
CHQ
|
CHQ
|
THI
|
CHQ
|
CHQ
|
CHQ
|
THI
|
CCR
|
CCR
|
CCR
|
CTCR
|
|
2,99E-02
|
1,67E-03
|
9,66E-03
|
4,12E-02
|
3,49E-01
|
3,33E-02
|
9,66E-03
|
3,91E-01
|
7,29E-06
|
3,52E-06
|
7,13E-07
|
1,15E-05
|
HQ: hazard quotient; CHQ: cumulative HQ; HI: hazard index; THI: total HI; CR: carcinogenic risk; CCR: cumulative CR; TCR: total CR; CTCR: cumulative TCR. a b aCr(VI).
For adults, in terms of CHQ levels three exposure pathways have followed the region of CHQingestion > CHQinhalation > CHQdermal, for children, CHQ levels have followed the region of CHQingestion > CHQdermal > CHQinhalation (Table 6). For children THI level found was 8.6 times greater than adults (Table 6). This result is an indication of our study that children are further sensitive to the negative health impacts of TEs in the olive orchard soils. Many studies reported high THI values for children (Baltas et al. 2020; Jia et al., 2018; Pan et al., 2016; Rinklebe et al., 2019; Wu et al. 2018). For adults, HI values decreased in the region of Mn > Al > Co > Cr > Pb > Ni > Cu > Cd > Zn, for children followed Co > Al > Fe > Cr > Mn > Pb > Ni > Cu > Cd > Zn (Table 6). For adults and children, cumulative HQ levels of all TEs via ingestion accounted for 72,5% and 89% of THI, respectively.
The CR levels of Cd, Co, and Cr via three pathways, and TCR levels were within 1x10-4 and 1x10-6 as USEPA’s acceptable risk range (Table 6), thus suggesting that carcinogenic risks were not expected for residential receivers. In Turkey, similar results were found in other research areas, for example in Sinop province (Baltas et al. 2020), Harran Plain (Vural et al., 2020), and Malatya province (Vural et al., 2021). According to Wu et al. (2018), at the same time, great carcinogenic risks were fixed in the soils of the Qinghai-Tibet Plateau. In our research, TCR levels decreased in the region of Cr (1.15E-05) > Co (1.27E-08) > Cd (6.01E-11) (Table 6). The cumulative carcinogenic risk (CCR) levels in terms of all exposure pathways followed the region of CCRingestion > CCRdermal > CCRinhalation, and the CCRingestion level was 2.1 and 10.2 times bigger than CCRdermal or CCRinhalation levels, respectively (Table 6). The level of CCRingestion is estimated at 63.4% of the CTCR levels. Also, Cr was the major participant of the CTCR via ingestion, and dermal contact with the biggest contributions of 63.4% and 30.6%, respectively (Table 6).