The chemical elements are found in river sediments as part of their constituent minerals, as oxides, ions adsorbed on colloidal particles of clays, and organic matter, resulting from erosion, sedimentation processes, or both (Hussein & Al-Owaidi, 2021). Major and minor oxides and trace elements contents in the sediments of studied valleys are shown in Tables 3 & 4.
3.1. Geochemistry of major and minor oxides
Silica (SiO2): The overall similarity in content levels may be related to the source rocks, which include mudstone, marl, claystone, and sandstone from the Injanah Formation, limestone, evaporites, and marl from the Fat'ha Formation, and sediments from Quaternary deposits. Al-Khosar and Al-Shor valleys have the largest SiO2 content since they are the longest and pass through the Injanah and Muqdadiyah formations, which are dominated by sandstone-containing rocks. These values are lower than the reference values, as shown in Table 3.
SiO2 directly correlates with Al, Ti, Mn, and K oxides (Fig. 2). This relationship reflects the association of these elements in the form of substitution with the cation in the clay mineral crystal lattice or adsorption on the surfaces of these minerals, depending on their chemical composition and atomic structure (Bergaya, Theng & Lagaly, 2006).
Table 3
The content of major and minor oxides, carbon dioxide, organic matter, and H2O+ in valley sediment samples (wt%).
Samp. | SiO2 | TiO2 | Al2O3 | Fe2O3 | MgO | CaO | Na2O | K2O | P2O5 | SO3 | Cl | CO2 | O.M. | H20+ | Total |
R1 | 35.06 | 0.79 | 8.30 | 5.12 | 3.41 | 25.72 | 0.42 | 1.29 | 0.21 | 0.21 | 0.01 | 11.45 | 6.34 | 0.38 | 98.71 |
R2 | 33.55 | 0.71 | 7.67 | 4.86 | 3.24 | 22.47 | 0.51 | 1.20 | 0.21 | 0.58 | 0.01 | 11.46 | 3.77 | 8.97 | 99.21 |
R3 | 33.24 | 0.69 | 7.59 | 4.67 | 3.25 | 29.92 | 0.44 | 1.16 | 0.12 | 0.16 | 0.01 | 13.06 | 4.71 | 0.79 | 99.81 |
R4 | 33.66 | 0.79 | 7.99 | 5.00 | 3.45 | 26.45 | 0.53 | 1.26 | 0.16 | 0.43 | 0.03 | 11.68 | 6.19 | 0.41 | 98.02 |
R6 | 35.56 | 0.78 | 8.18 | 5.23 | 3.97 | 22.69 | 0.79 | 1.29 | 0.18 | 0.79 | 0.14 | 11.93 | 6.35 | 0.67 | 98.55 |
KH1 | 32.50 | 0.53 | 6.26 | 3.48 | 2.53 | 25.40 | 0.64 | 0.87 | 0.21 | 0.43 | 0.02 | 12.63 | 8.31 | 4.43 | 98.24 |
KH3 | 33.25 | 0.65 | 7.67 | 4.63 | 3.36 | 27.23 | 0.51 | 1.05 | 0.24 | 0.30 | 0.02 | 12.49 | 6.76 | 0.35 | 98.52 |
KH4 | 35.10 | 0.73 | 7.84 | 4.75 | 3.76 | 23.80 | 0.44 | 1.15 | 0.14 | 0.17 | 0.01 | 10.77 | 5.02 | 4.93 | 98.61 |
KHA2 | 34.57 | 0.67 | 7.59 | 4.75 | 3.06 | 23.32 | 0.49 | 1.20 | 0.23 | 0.28 | 0.01 | 9.17 | 8.04 | 5.04 | 98.42 |
KS1 | 32.89 | 0.49 | 5.82 | 2.35 | 2.13 | 24.49 | 1.06 | 1.42 | 0.11 | 0.22 | 0.02 | 15.83 | 1.50 | 11.43 | 99.76 |
KS2 | 33.17 | 0.49 | 6.39 | 2.85 | 2.67 | 25.80 | 0.82 | 1.40 | 0.13 | 0.32 | 0.02 | 15.05 | 3.28 | 7.33 | 99.72 |
KS3 | 36.80 | 0.75 | 8.18 | 4.58 | 3.86 | 22.09 | 0.69 | 1.48 | 0.16 | 0.88 | 0.02 | 14.61 | 5.37 | 0.91 | 100.38 |
KS4 | 36.62 | 0.69 | 7.54 | 4.21 | 3.49 | 23.83 | 0.79 | 1.42 | 0.24 | 1.01 | 0.02 | 13.70 | 4.95 | 0.32 | 98.83 |
KS5 | 34.60 | 0.61 | 6.59 | 3.07 | 2.89 | 24.56 | 0.96 | 1.36 | 0.16 | 0.54 | 0.03 | 15.69 | 3.06 | 5.19 | 99.32 |
KS7 | 39.52 | 0.85 | 9.61 | 5.91 | 4.29 | 17.73 | 0.54 | 1.54 | 0.20 | 0.28 | 0.01 | 11.86 | 6.08 | 1.08 | 99.49 |
KSA2 | 30.64 | 0.68 | 7.11 | 4.70 | 3.57 | 26.17 | 1.34 | 1.03 | 0.14 | 4.73 | 0.05 | 12.85 | 7.34 | 0.20 | 100.55 |
KSB3 | 36.80 | 0.79 | 8.87 | 5.43 | 4.01 | 23.15 | 0.53 | 1.41 | 0.19 | 0.47 | 0.02 | 10.87 | 6.34 | 0.87 | 99.75 |
D1 | 34.03 | 0.72 | 7.62 | 5.11 | 3.12 | 24.30 | 0.60 | 1.05 | 0.26 | 0.61 | 0.03 | 11.17 | 7.02 | 2.97 | 98.61 |
D2 | 31.94 | 0.72 | 7.68 | 5.56 | 3.24 | 19.63 | 0.97 | 1.08 | 0.44 | 2.32 | 0.05 | 8.86 | 15.75 | 0.77 | 99.01 |
D3 | 33.35 | 0.68 | 6.95 | 5.55 | 2.94 | 19.74 | 0.94 | 1.05 | 0.36 | 1.99 | 0.04 | 8.72 | 13.65 | 2.77 | 98.73 |
D4 | 34.85 | 0.66 | 6.26 | 5.35 | 2.54 | 21.71 | 0.95 | 0.95 | 0.21 | 1.62 | 0.04 | 10.20 | 8.48 | 4.77 | 98.59 |
D5 | 35.18 | 0.73 | 7.50 | 5.58 | 3.17 | 20.75 | 0.92 | 1.13 | 0.47 | 1.16 | 0.05 | 8.78 | 11.34 | 1.32 | 98.08 |
DA | 33.64 | 0.67 | 7.30 | 4.83 | 3.15 | 24.32 | 0.79 | 1.08 | 0.29 | 1.16 | 0.03 | 10.17 | 8.85 | 1.80 | 98.08 |
DB1 | 26.62 | 0.37 | 4.29 | 2.70 | 1.72 | 34.13 | 0.73 | 0.87 | 0.13 | 0.80 | 0.02 | 19.25 | 5.29 | 1.57 | 98.48 |
DB2 | 36.52 | 0.66 | 7.27 | 6.13 | 2.93 | 23.79 | 1.00 | 1.13 | 0.55 | 1.09 | 0.06 | 8.46 | 8.25 | 0.67 | 98.52 |
DB3 | 34.35 | 0.76 | 7.85 | 5.81 | 3.54 | 24.42 | 0.64 | 1.28 | 0.30 | 0.63 | 0.02 | 10.25 | 5.82 | 3.42 | 99.09 |
DC1 | 36.56 | 0.79 | 8.56 | 5.36 | 3.51 | 20.51 | 0.61 | 1.34 | 0.31 | 0.89 | 0.03 | 8.23 | 9.00 | 2.34 | 98.04 |
DC2 | 34.37 | 0.62 | 6.90 | 4.07 | 3.15 | 24.89 | 0.62 | 1.26 | 0.24 | 0.49 | 0.02 | 10.20 | 4.24 | 7.27 | 98.33 |
SH1 | 30.20 | 0.55 | 6.56 | 4.16 | 3.12 | 22.06 | 1.13 | 1.11 | 0.52 | 1.94 | 0.12 | 9.12 | 15.40 | 2.57 | 98.56 |
SH2 | 34.39 | 0.62 | 6.61 | 4.37 | 3.23 | 24.39 | 1.17 | 1.23 | 0.29 | 2.69 | 0.07 | 9.70 | 7.69 | 2.04 | 98.49 |
SH3 | 35.71 | 0.77 | 8.09 | 4.83 | 4.53 | 23.53 | 1.46 | 1.35 | 0.21 | 2.25 | 0.18 | 8.50 | 6.86 | 0.37 | 98.64 |
SH4 | 36.52 | 0.82 | 7.87 | 4.56 | 3.76 | 23.93 | 0.67 | 1.35 | 0.18 | 0.61 | 0.03 | 9.88 | 5.67 | 2.90 | 98.75 |
SH5 | 36.94 | 0.73 | 8.42 | 4.94 | 3.87 | 25.37 | 0.76 | 1.32 | 0.19 | 0.95 | 0.03 | 9.77 | 5.09 | 0.99 | 99.37 |
SHA | 38.96 | 0.82 | 8.13 | 4.96 | 3.87 | 23.37 | 0.66 | 1.41 | 0.17 | 0.34 | 0.03 | 9.28 | 3.76 | 2.74 | 98.50 |
SH6 | 38.50 | 0.81 | 8.23 | 4.59 | 3.80 | 25.68 | 0.71 | 1.42 | 0.18 | 0.36 | 0.02 | 8.98 | 3.64 | 1.09 | 98.01 |
SH7 | 37.99 | 0.81 | 8.64 | 5.00 | 3.95 | 23.00 | 0.68 | 1.46 | 0.24 | 0.78 | 0.03 | 9.50 | 6.38 | 0.71 | 99.18 |
SD: | - | 0.81 | 11.10 | 6.51 | 2.99 | 2.83 | 2.19 | 1.51 | 0.14 | - | - | - | - | - | - |
UCC: | 66.62 | 0.64 | 15.4 | 5 04 | 2.48 | 3.59 | 3.27 | 2.8 | 0.15 | - | - | - | - | - | - |
SD: (Ohta et al., 2017) ; UCC: (Rudnick & Gao, 2013) |
Table 4
Contents of trace elements in valley sediment samples and reference values (ppm)
Samp. | V | Cr | Mn | Co | Ni | Cu | Zn | As | Rb | Zr | Pb |
R1 | 117 | 257 | 699 | 7.9 | 154 | 31 | 93 | 6.9 | 26 | 157 | 14 |
R2 | 110 | 223 | 610 | 10.7 | 146 | 35 | 111 | 6.8 | 24 | 138 | 14 |
R3 | 88 | 316 | 693 | 8.7 | 151 | 31 | 81 | 6.5 | 24 | 131 | 10 |
R4 | 115 | 281 | 751 | 7.9 | 150 | 31 | 120 | 7.9 | 26 | 164 | 12 |
R6 | 62 | 348 | 673 | 19.0 | 155 | 43 | 226 | 6.3 | 25 | 150 | 23 |
KH1 | 74 | 175 | 393 | 3.1 | 83 | 37 | 173 | 3.4 | 17 | 109 | 21 |
KH3 | 72 | 184 | 626 | 7.9 | 128 | 38 | 179 | 6.7 | 21 | 123 | 21 |
KH4 | 106 | 269 | 603 | 16.2 | 142 | 31 | 81 | 5.8 | 22 | 143 | 14 |
KHA2 | 81 | 221 | 534 | 17.1 | 135 | 30 | 116 | 5.8 | 24 | 140 | 15 |
KS1 | 54 | 304 | 570 | 3.1 | 54 | 13 | 40 | 3.8 | 33 | 118 | 8 |
KS2 | 61 | 311 | 569 | 3.1 | 76 | 16 | 54 | 3.9 | 30 | 119 | 9 |
KS3 | 100 | 314 | 635 | 7.9 | 141 | 28 | 109 | 5.5 | 29 | 156 | 11 |
KS4 | 99 | 301 | 635 | 10.2 | 119 | 37 | 181 | 3.9 | 28 | 170 | 47 |
KS5 | 61 | 479 | 564 | 3.1 | 84 | 22 | 83 | 4.0 | 28 | 130 | 17 |
KS7 | 79 | 303 | 709 | 20.4 | 174 | 46 | 122 | 7.5 | 30 | 159 | 21 |
KSA2 | 90 | 181 | 631 | 3.1 | 132 | 30 | 173 | 6.6 | 22 | 132 | 22 |
KSB3 | 98 | 187 | 601 | 7.8 | 146 | 34 | 119 | 6.9 | 27 | 144 | 14 |
D1 | 94 | 270 | 508 | 7.9 | 132 | 82 | 346 | 8.0 | 22 | 141 | 112 |
D2 | 112 | 183 | 417 | 10.1 | 135 | 135 | 790 | 10.3 | 23 | 129 | 168 |
D3 | 78 | 311 | 409 | 7.6 | 120 | 174 | 593 | 5.8 | 20 | 135 | 457 |
D4 | 105 | 333 | 441 | 13.1 | 108 | 246 | 415 | 8.6 | 18 | 130 | 339 |
D5 | 90 | 252 | 475 | 10.9 | 128 | 164 | 755 | 10.9 | 22 | 143 | 305 |
DA | 89 | 259 | 515 | 7.9 | 118 | 90 | 442 | 9.4 | 21 | 124 | 184 |
DB1 | 71 | 190 | 445 | 3.1 | 69 | 24 | 68 | 2.7 | 16 | 89 | 20 |
DB2 | 76 | 291 | 753 | 18.3 | 122 | 114 | 494 | 11.2 | 21 | 133 | 206 |
DB3 | 85 | 280 | 613 | 8.8 | 136 | 56 | 197 | 6.4 | 24 | 149 | 53 |
DC1 | 106 | 195 | 500 | 17.1 | 148 | 45 | 165 | 5.0 | 28 | 147 | 50 |
DC2 | 68 | 276 | 542 | 13.1 | 108 | 44 | 120 | 6.4 | 21 | 142 | 88 |
SH1 | 72 | 159 | 527 | 7.4 | 110 | 62 | 264 | 4.8 | 20 | 107 | 35 |
SH2 | 61 | 271 | 606 | 7.9 | 115 | 70 | 171 | 6.3 | 22 | 129 | 33 |
SH3 | 81 | 255 | 687 | 8.5 | 138 | 33 | 104 | 6.4 | 26 | 158 | 16 |
SH4 | 75 | 325 | 843 | 7.9 | 132 | 29 | 78 | 6.1 | 27 | 181 | 13 |
SH5 | 86 | 230 | 612 | 14.1 | 139 | 33 | 97 | 6.7 | 26 | 146 | 18 |
SHA | 80 | 317 | 783 | 11.5 | 146 | 31 | 80 | 6.5 | 27 | 181 | 12 |
SH6 | 86 | 328 | 870 | 8.7 | 131 | 28 | 77 | 6.5 | 27 | 185 | 22 |
SH7 | 101 | 264 | 750 | 8.5 | 142 | 38 | 142 | 5.6 | 26 | 172 | 24 |
SD | 134 | 60 | 1046 | 15.4 | 23 | 33 | 145 | 14.0 | 52 | - | 38 |
UCC | 97 | 92 | 775 | 17.3 | 47 | 28 | 67 | 4.8 | 84 | 193 | 17 |
SD: (Ohta et al., 2017) ; UCC: (Rudnick & Gao, 2013) |
Titanium Oxide (TiO2): The content values generally increase as we move away from the beginnings of the valleys. The highest content of this oxide is located in Al-Shor Valley. Layers of exposed claystone of Injanah Formation were observed near the valley basin, which passes through mostly agricultural lands in the study area, where the soils containing clay minerals are leached towards the valley during the rainy seasons. In sediments, TiO2 is associated with Si, Al, Mn, and K oxides, which indicate the existence of different phases of clay minerals. Clay minerals increase with the claystone and marl contents of Injanah and Fat'ha formations, so TiO2 increases by substituting Al3+ for Ti4+ due to the ionic radius similarity (Almayyahi & Aljaberi, 2018); in addition, owing to its strong resistance to weathering, TiO2 is transferred as rutile and ilmenite. TiO2 is related to trace elements by substitution and adsorption on clay minerals (Dreher & Follmer, 2004).
Alumina (Al2O3): The content of this oxide converges in valley sediments in general. That is owing to the effect of erosion and weathering of soils derived from the formations of Fat'ha, Injanah, and Muqdadiyah rocks which supply the valley with clay components from several streams during the rainy seasons. Low contents appear at the beginning of the valleys due to the high content of sandy sediments, as in sample (DB1) in the Al-Danffilli valley. In contrast, the highest content values were recorded at the valleys' end due to the mud components' leaching processes, as in sample (KS7) in Al-Khosar. Figure 2 shows a direct correlation between Al, Ti, Mn, K oxides, and SiO2, which may indicate different phases of clay minerals and inverse correlations with organic matter and CaO, Table 5.
Table 3 shows that the contents of iron oxides generally are low at the beginnings of the valleys, as in the samples KS1 and KS2 in Al-Khosar valley near Al-Abbasiya village and countryside, respectively, and DB1 in Al-Danffilli valley and increase towards their ends. The highest contents was (6.13 wt%), which appeared in the sample (DB2) in Al-Danffilli Valley. It was near the livestock market and its breeding fields. In addition, slaughtering and throwing waste and blood in the valley's waters may be attributed to the increase in content, consistent with Ebong et al. (2020). Iron oxide is related to Si, Ti, Al, Mn, and P oxides due to the association of iron oxides with clay minerals during the erosion and weathering stages. Iron oxides move as colloidal particles with clay minerals, adsorbing on their surfaces (Brady and Weil, 2008) or coating their grains. Relationship of iron oxides with trace elements in three forms; substitution into the crystal lattice of Fe-oxides and hydroxides phases through coprecipitation, such as Zn and Mn (van Groeningen et al., 2020a; van Groeningen et al., 2020b); adsorption on grain surface of iron oxides through adsorption and surface complexation, such as phosphorous, copper, arsenic, and lead (Polowczyk et al., 2018), and adsorption on clay minerals that transported associated with iron oxides as colloides such as vanadium and nickel (Fadillah et al., 2020).
Magnesia (MgO): Mg is essential to several mineral groups, such as silicates and carbonates; (clay minerals; chlorite, palygorskite, and sepiolite) and (dolomite) respectively. Therefore, it is found in higher proportions in clay rocks such as shale and marl than in other clastic and carbonate rocks (Salminen et al., 2005). The average concentration of magnesium oxide in the valley sediments was 3.34 wt%, which exceeds the reference values. Table 3 indicates that the highest concentrations are in Al-Shor Valley because it passes through agricultural lands. Their soils are derived from the Injanah and Muqdadiyah formations, which are rich in clay minerals. Its content is also increasing at the end parts of the Al-Khosar Valley, which may be attributed to the high proportion of clay minerals such as chlorite and palygorskite (Pozo and Calvo, 2018).
Calcium oxide (CaO): The lowest contents generally appear in the valleys where the percentage of SiO2 increases, as in Al-Khosar, Al-Shor, and Al-Danffilli valleys. The lowest rate of oxide was 17.73 wt% in the sample (KS7), which is located near the estuary in the Al-Khosar valley, where the sedimentation of the floodplain of the Tigris River, while the highest percentage was 34.13 wt% in the sample (DB1), as it contains the lowest rate of silica among all samples. Table 5. displays a positive correlation between calcium oxide and carbon dioxide (r = 0.59), which may be attributed to calcium carbonate CaCO3. In contrast, the inverse relationship between calcium oxide and magnesium oxide (r=-0.40) and between magnesium oxide and carbon dioxide (r=-0.43) may indicate the absence of dolomite mineral or its presence in a small proportion.
Sodium oxide (Na2O): The content of Na2O in the sediments of the valleys was low and below the reference values. The presence of Na2O is attributed to the evaporite rocks and the urban subtractions. Sodium oxide concentrations are low at the beginning of the valley and increase towards the estuary, as in the valleys of Al-Rashediya and Al-Danffilli. On the other hand, in Al-Kharrazi, Al-Khosar, and Al-Shor valleys, sodium oxide concentrations are high at the beginning of the valley and decrease in their estuaries, possibly because it dissolves during the leaching process. Table 5 shows that Na2O is related to chlorine (r = 0.69), meaning it exists as secondary halite.
Potassium oxide (K2O): The oxide content is close to their reference value in sediments, and their values are the lowest in the beginnings of the valleys and increase downstream. The increase may be due to the rise of clay minerals and k-feldspar in addition to its accumulation in plants and decay in the valley sediments (Ragel et al. 2019). Table 5 shows a positive correlation between K2O and SiO2, Al2O3, TiO2, and MgO. This association reflects its presence in clay minerals and k-feldspar owing to the erosion and transport of source rocks from the Fat'ha, Injanah, and Muqdadiyah formations.
Sulphur oxide (SO3): The high SO3 content appears in the samples representing the beginnings of the valleys, as in Al-Khosar and Al-Shor valleys. The samples reflected the presence of gypsum and carbonate rock fragments in the transported soil resulting from the weathering of Fat'ha Formation rocks, especially in the samples KSA1 and SH1 ~ SH3 in Al-Khosar and Al-Shor valleys, respectively. It was also observed that there were high concentrations of sulfur oxide in the industrial region that Al-Danffilli Valley flows through, it may result from human activities (especially industrial ones), represented by samples D2 ~ D5 (Table 3).
Phosphorus oxide (P2O5): Oxide content is high in Al-Danffilli Valley in samples collected from industrial zones D1, D4, and DA, which is likely to be the source of P due to local factories manufacturing detergents and washing powders (including polyphosphate), as well as wastewater. In contrast, the high content of P2O5 in Table 3 reflects the samples that represent areas of agricultural activity and livestock fields adjacent to the valleys of Al-Shor, Al-Danffilli, Al-Khosar, and Al-Rashediya due to the use of fertilizers, agricultural pesticides, and fodders (Dias et al., 2019). Table 5 shows the significant relationship between P and O.M., which is attributed to the fact that O.M. contributes to the increase and fixation P in the soil and that humic substances increase the biological role of P in plants (Yang et al., 2019). P is also associated with trace elements adsorbed on O.M. matter, the existence of these elements in slight concentrations in fertilizers, or both (da Silva et al., 2017).
Organic matter (O.M.): Several sources of organic matter in the sediments may be natural from the soil or anthropogenic from sewage water, fertilizers, and wastes. O.M. with H.M.s forms complex compounds through adsorption and other mechanisms (Reyes & Crisosto, 2016). content of O.M. varies according to nutrients and the type of subtractions. It appears from Table 3 that the content of O.M. are generally low in the beginnings of valleys because they are far from sources of pollution, while samples with high contents reflect areas of agricultural activity such as livestock breeding and throwing dead animals. Table 5 displays the association of O.M. with Na2O, P2O5, and SO3 that may be attributed to human activities; industrial, agricultural, and domestic (Michael-Kordatou et al., 2015).
3.2. Geochemistry of trace elements
Vanadium (V): The presence of V is usually associated with sedimentary rocks. Clay minerals and hydrated iron-manganese oxides reflect the presence of V due to substitution and adsorption during morphological processes (O'loughlin et al., 2021; Zhu et al., 2018). Table 4 shows that vanadium concentrations in sediments are less than the reference value. Its concentration varies in samples depending on the content of clay minerals, iron oxides, and organic matter, as indicated by the direct correlation between V and Al2O3 (r = 0.46), TiO2 (0.53), and Fe2O3 (0.53). (Table 5 and Fig. 3a). V content is significantly increased in samples collected from industrial sites due to the presence of automotive oil change and wash stations (Ikhajiagbe et al., 2014), which dumped their wastes into valleys, as demonstrated by samples KH4 from Al-Kharrazi Valley, KS3 and KSB3 from Al-Khosar Valley, and D2 and DA from Al-Danffilli Valley.
Table 5
Correlation among major and minor oxides, CO2, O.M., and trace elements of valley sediments, n = 36.
| SiO2 | TiO2 | Al2O3 | Fe2O3 | MgO | CaO | Na2O | K2O | P2O5 | SO3 | Cl | CO2 | OM |
SiO2 | 1.0** | | | | | | | | | | | | |
TiO2 | 0.8** | 1.0** | | | | | | | | | | | |
Al2O3 | 0.8** | 0.9** | 1.0** | | | | | | | | | | |
Fe2O3 | 0.5** | 0.8** | 0.7** | 1.0** | | | | | | | | | |
MgO | 0.7** | 0.9** | 0.9** | 0.6** | 1.0** | | | | | | | | |
CaO | -0.5** | -0.5** | -0.5** | -0.5** | -0.4* | 1.0** | | | | | | | |
Na2O | -0.2 | -0.3 | -0.4* | -0.1 | -0.1 | -0.1 | 1.0** | | | | | | |
K2O | 0.7** | 0.5** | 0.6** | 0.0 | 0.6** | -0.3 | -0.1 | 1.0** | | | | | |
P2O5 | -0.1 | 0.0 | 0.0 | 0.5 | -0.1 | -0.5** | 0.3 | -0.3 | 1.0** | | | | |
SO3 | -0.3 | -0.1 | -0.2 | 0.2 | 0.1 | -0.2 | 0.8** | -0.3 | 0.3 | 1.0** | | | |
Cl | -0.1 | 0.0 | 0.0 | 0.1 | 0.3 | -0.2 | 0.7** | 0.0 | 0.3 | 0.5** | 1.0** | | |
CO2 | -0.5** | -0.6** | -0.5** | -0.7** | -0.4** | 0.6** | 0.0 | 0.0 | -0.6** | -0.1 | -0.3 | 1.0** | |
OM | -0.3 | 0.0 | 0.0 | 0.4* | -0.1 | -0.4* | 0.3 | -0.5** | 0.8** | 0.5** | 0.4* | -0.5** | 1.0** |
V | 0.2 | 0.5** | 0.5** | 0.5** | 0.3 | -0.2 | -0.4* | 0.0 | 0.1 | 0.0 | -0.3 | -0.3 | 0.1 |
Cr | 0.4* | 0.2 | 0.0 | -0.1 | 0.1 | -0.1 | 0.0 | 0.4** | -0.3 | -0.3 | 0.0 | 0.1 | -0.4* |
Mn | 0.6** | 0.6** | 0.5** | 0.2 | 0.6** | 0.1 | -0.2 | 0.6** | -0.3 | -0.2 | 0.0 | -0.1 | -0.5** |
Co | 0.5** | 0.5** | 0.5** | 0.6** | 0.4* | -0.5** | -0.3 | 0.2 | 0.3 | -0.2 | 0.1 | -0.5** | 0.1 |
Ni | 0.6** | 0.9** | 0.9** | 0.8** | 0.8** | -0.4* | -0.4* | 0.3 | 0.1 | 0.0 | 0.1 | -0.5** | 0.1 |
Cu | -0.1 | 0.0 | -0.2 | 0.5** | -0.2 | -0.4** | 0.3 | -0.5** | 0.6** | 0.3* | 0.1 | -0.5** | 0.6** |
Zn | -0.1 | 0.0 | -0.1 | 0.5** | -0.2 | -0.5** | 0.3 | -0.5** | 0.8** | 0.4* | 0.2 | -0.4** | 0.8** |
As | 0.2 | 0.4** | 0.4* | 0.7** | 0.2 | -0.4* | 0.1 | -0.2 | 0.5** | 0.2 | 0.1 | -0.6** | 0.4* |
Rb | 0.6** | 0.4* | 0.5** | -0.1 | 0.4* | -0.3 | -0.1 | 0.9** | -0.4* | -0.3 | -0.1 | 0.1 | -0.5** |
Zr | 0.8** | 0.9** | 0.8** | 0.4** | 0.8** | -0.3 | -0.2 | 0.7** | -0.2 | -0.2 | 0.0 | -0.4* | -0.3 |
Pb | -0.1 | 0.0 | -0.2 | 0.4* | -0.3 | -0.4* | 0.3 | -0.4** | 0.6** | 0.3 | 0.1 | -0.4* | 0.6** |
V | Cr | Mn | Co | Ni | Cu | Zn | As | Rb | Zr | Pb |
1.0** | | | | | | | | | | |
-0.3 | 1.0** | | | | | | | | | |
0.0 | 0.3 | 1.0** | | | | | | | | |
0.2 | 0.0 | 0.2 | 1.0** | | | | | | | |
0.6** | -0.1 | 0.5** | 0.6** | 1.0** | | | | | | |
0.2 | 0.0 | -0.5** | 0.2 | 0.0 | 1.0** | | | | | |
0.2 | -0.1 | -0.5** | 0.1 | 0.0 | 0.8** | 1.0** | | | | |
0.4* | -0.1 | 0.1 | 0.4* | 0.5** | 0.6** | 0.7** | 1.0** | | | |
0.0 | 0.4* | 0.5** | 0.1 | 0.2 | -0.5** | -0.4** | -0.2 | 1.0** | | |
0.4* | 0.4* | 0.7** | 0.3* | 0.6** | -0.2 | -0.2 | 0.2 | 0.5** | 1.0** | |
0.1 | 0.1 | -0.5** | 0.1 | -0.1 | 0.9** | 0.8** | 0.5** | -0.4** | -0.2 | 1.0** |
** Significant at P value = 0.01 |
* Significant at P value = 0.05 |
Chromium (Cr): Cr is present in sedimentary rocks as primary clastic phases, such as chromite, magnetite, and ilmenite. The geochemical behaviour of trivalent chromium (Cr3+) is similar to that of (Fe3+) and (Al3+), which leads to its widespread dispersal in iron oxides and clay minerals by substitution or adsorption (Liu et al. 2017). Organic matter also plays a role in activating the reduction of Cr6+ to Cr3+, which is present in the above mineral phases (Kabata-Pendias 2011). Chromium concentrations in these sediments are higher than the reference value. Its concentrations vary in the valleys but generally increase towards the estuary, according to the sediment content of iron oxides and clay minerals. Various human sources contribute to the distribution of chromium in the sediments, especially near industrial areas, where it is used in plumbing and dyeing workshops, dyes, photography, polishing, some detergents, and the manufacture of household appliances(Tumolo et al. 2020).
Manganese (Mn): Mn content in sedimentary rocks depends on the source rocks' geochemistry and the redox potential in the sedimentary environment (Goldberg and Humayun, 2016). Fe is usually associated with Mn due to similar geochemical behavior (Hylander et al., 2000). Table 4 indicates the concentrations of Mn in the sediments below the reference value. It rises towards the mouths of the valleys with an increase in the proportion of clay minerals (Fig. 3) and iron oxides by adsorption and substitution. Therefore, it is noted in Table 5 that there are (moderate-strong) correlations between Mn and SiO2, TiO2, Al2O3, Fe2O3, MgO, and K2O, in addition to V, Ni, Rb, and Zr.
Nickle (Ni): Ni is present with clay minerals and iron oxides in sedimentary rocks due to the substitution and adsorption of Mg and Fe2+, or both (Bide et al., 2008). Table 4 indicates that the Ni concentrations are higher than the reference value. And this is due to the clay minerals proportion in the valley sediments. The concentrations are low in the beginnings of the valleys and increase towards their mouths due to the leaching processes of the fine particles of the clay. Table 5 and Fig. 3c show the strong correlation between Ni and oxides of Al, Ti, Fe, and Mg and its association with trace elements; V, Mn, Co, Ga, As, Sr. These relations demonstrate the variety of natural and human influences on the distribution of elements in the valley sediments.
Cobalt (Co): Co is similar to Ni in its distribution in sedimentary rocks, concentrated in fine grains representing clays and iron oxides (Salminen et al., 2005). Table 4 shows that the cobalt concentration varies according to the clay minerals and iron oxides proportion. The strong correlation is supported by Co and SiO2, TiO2, Al2O3, Fe2O3, and MgO (Fig. 3d) and Ni and As elements.
Copper (Cu): Cu is present in sediments as substitution, adsorption on Fe and Mn oxides, clay minerals, or both (van Everbroeck et al., 2020)d (Ugwu & Igbokwe, 2019). Cu content is generally higher than the reference value. Cu concentrations are close in almost all sediments but increase significantly in the Al-Danffilli Valley, especially in the industrial part (Table 4). Table 5 supports the association of Cu with Fe and O.M., which reflects the state of adsorption of Cu on them, in addition to its association with As and Pb elements by the exact mechanism.
Zinc (Zn): Zn is found in sedimentary rocks within iron oxides and clay minerals, in addition to its presence in small and varying proportions in sandstone and shale (Berger et al. 2017). Zn concentrations in the valley sediments vary according to the proportion of iron oxides and clay minerals (Table 5).
Arsenic (As): content varies in valleys and is lower than river sediments' reference value. The highest content was in Al-Danffilli Valley, especially the two samples (D2 and D5) that pass through the industrial area. In addition to (DB2) passes near the fields of livestock breeding and slaughterhouses (Ebong et al., 2020). Table 5 demonstrates a direct correlation between As, and oxides of (Ti, P, Fe), and O.M.. The reason is attributed to the adsorption on iron hydroxides (goethite), organic matter, or both (Deng et al., 2019).
Lead (Pb): The content of Pb are within relative levels in the valleys of Al-Rashediya, Al-Kharrazi, Al-Khosar, and Al-Shor, close to the reference value and sometimes lower than it. At the same time, it was very high in Al-Danffilli Valley, especially in the industrial area (Table 4). Table 5 shows the association of lead with iron and phosphorous oxides and organic matter.
3.3. Factor analysis:
The results of the factor analysis Table 6 showed the presence of four main components representing 80.86% of the total variances, as follows: the first component was 33.83%; the second component was 29.75%; the third component was 11.82% and the fourth component was 5.46%.
The first principal component: This component shows the relationship between Ti, Al, Fe and Mg oxides and Ni (Table 6). This association may reflect varied phases of clay minerals resulting from weathering and transport factors of the source rocks from Muqdadiyah, Injanah, and Fat'ha formations. The valleys are long, with a wide basin and a large catchment area. Therefore, rain and surface water, the topography, and the predominant soil cover control the phases of the clay minerals and the geochemical distribution of the elements in the sediments.
Table 6
The main compound principles control the elemental distribution in the sediments of the main valleys.
| Components | | | | | |
| PC1 | PC2 | PC3 | PC4 | | Eigenvalue | Total variance (%) | Cumulative of variance (%) |
SiO2 | 0.654 | -0.079 | -0.169 | 0.662 | PC1 | 7.104 | 33.829 | 33.829 |
TiO2 | 0.931 | 0.001 | -0.011 | 0.221 | PC2 | 6.248 | 29.754 | 63.584 |
Al2O3 | 0.916 | -0.089 | -0.092 | 0.273 | PC3 | 2.482 | 11.817 | 75.401 |
Fe2O3 | 0.825 | 0.511 | 0.036 | -0.03 | PC4 | 1.147 | 5.461 | 80.862 |
MgO | 0.860 | -0.260 | 0.240 | 0.242 | | | | |
Cao | -0.360 | -0.516 | -0.154 | -0.62 | | | | |
Na2O | -0.326 | 0.147 | 0.858 | 0.137 | | | | |
K2O | 0.357 | -0.489 | -0.074 | 0.721 | | | | |
P2O5 | 0.090 | 0.760 | 0.268 | 0.039 | | | | |
SO3 | -0.056 | 0.236 | 0.768 | -0.23 | | | | |
Cl | 0.093 | 0.053 | 0.889 | 0.032 | | | | |
CO2 | -0.579 | -0.531 | -0.196 | -0.23 | | | | |
O.M. | 0.054 | 0.727 | 0.404 | -0.17 | | | | |
Mn | 0.574 | -0.555 | 0.009 | 0.161 | | | | |
Co | 0.614 | 0.289 | -0.142 | 0.238 | | | | |
Ni | 0.966 | 0.009 | -0.033 | -0.06 | | | | |
Cu | -0.029 | 0.914 | 0.127 | 0.006 | | | | |
Zn | 0.026 | 0.921 | 0.174 | -0.08 | | | | |
As | 0.529 | 0.628 | 0.026 | -0.14 | | | | |
Br | 0.168 | 0.278 | 0.823 | 0.007 | | | | |
Pb | -0.101 | 0.898 | 0.059 | 0.045 | | | | |
PC values ≥ 0.5 | |
The second principal component: Table 6 and Fig. 4 show a correlation between the O.M. and Cu, Zn, Pb, and P. The presence of O.M. is attributed to the wastewater in the industrial area, domestic wastes and wastewater, and various agricultural activities. In comparison, the source of H.M.s is due to multiple industrial, agricultural, and anthropogenic activities.
The third principal component: Tables 5 and 6 demonstrate a correlation between Na2O, Cl, SO3, and bromine Br, which represent the phases of secondary minerals (e.g., gypsum and halite) resulting from the weathering of Fat'ha Formation evaporite rocks and the gypsum rock fragment of in the soil.
The fourth principal component: This compound shows the association between SiO2 and K2O. It is believed that this relationship reflects the presence of K-feldspar, one of the common minerals of sandy rocks for the formations of Injanah and Muqdadiyah, and is characterized by its relative resistance to weathering processes.
According to the capacity of the watershed areas for the valleys of the study area, it's found that the influence of the erosion and weathering factor of the exposed rocks and the soil derived from them is the most controlling factor in the distribution of elements in the sediments, This also clearly shows the association of the first, third, and fourth factors with the quality of the influential rocks. The first factor is attributed to the effect of soil weathering, mainly derived from the Fat'ha, Injanah, and Muqdadiyah rocks. In contrast, the third factor reflects the impact of the secondary minerals in the soil. The fourth factor is the effect of the sandstones of the Injanah and Muqdadiyah formations. In contrast, the second factor was occupied by the impact of anthropogenic activities due to the largely residential area capacity and the industrial and agricultural wastes.
3.4. Contamination criteria
3.4.1. Geoaccumulation Index (Igeo)
Table 7 shows the values of Igeo for some H.M.s in the valley sediments. Generally, the lower values were in the samples at the beginnings of the valleys or their tributaries because they were not significantly exposed to the effects of pollution because they are relatively far from the industrial, agricultural, and residential pollution sites.
The Igeo values of Cr ranged from 0.24 to 1.83; for Ni, they went from − 0.92 to 0.77, which fall within the category of uncontaminated to moderately contaminated for all valleys. The highest Igeo values for Cr and Ni in Al-Khosar Valley were 1.83 and 0.77, respectively. The reason is attributed to the fact that the drainage basin of Al-Khosar Valley is wide, so the amount of mud sediments that pass through it to the Tigris River is large, and most of the components of these sediments are clay minerals. Cr and Ni are associated with clay minerals, usually in the substitution and adsorption formulas. The Igeo values for Cu ranged between − 2.41 to 0.05 in Al-Rashediya, Al-Kharrazi, Al-Khosar, and Al-Shor valleys, so it was classified under the uncontaminated category. While its values in Al-Danffilli Valley ranged between − 1.48 to 1.86, it fell within the uncontaminated to moderately contaminated category. The Igeo values for Zn in all valleys except Al-Danffilli Valley were − 1.83 to 0.89, and therefore they are classified as uncontaminated to moderately contaminated. As for the Danffilli Valley, the Igeo values ranged from − 1.06 to 2.47, meaning it falls within the two categories of uncontaminated to moderately contaminated and moderately to strongly contaminated. The highest pollution values appear in the industrial area adjacent to the Al-Danffilli Valley. While the highest Igeo values for Cu, Zn and Pb were found in Al-Danffilli Valley at 1.86, 2.47, and 3.93, respectively, which represents an industrial and service activity crowded on its banks with vehicle maintenance workshops, batteries and dyeing workshops. The elements are concentrated in the waste that is thrown into the valley. The Igeo values of Pb ranged from − 1.54 to 0.36 in Al-Rashediya and Al-Kharrazi valleys within the category of uncontaminated. In Al-Khosar Valley, the values were between − 1.96 to 0.44 within the uncontaminated category, except for the sample KS4 (Igeo = 0.64) within the category uncontaminated to moderately contaminated. Al-Shor Valley's values ranged from − 1.31 to 0.33 within the category (uncontaminated) except SH1 and SH2, which fall into the category uncontaminated to moderately contaminated due to the industrial activity of tin smithing and vehicle repair workshops.
On the other hand, the Igeo values for Pb in Danffilli Valley ranged from − 0.59 to 3.93. The low values indicate a low concentration of Pb in the tributaries feeding Al-Danffilli Valley and generally fall within the categories of uncontaminated to moderately contaminated. In contrast, the high Igeo values of Pb that fall within the category of strongly contaminated reflect the high sediment content due to the Pb contamination of the main valley during Passing through the industrial area.
The Igeo for As ranged between − 2.84 and 0.80, meaning they are uncontaminated. Despite that, the highest values were in Al-Danffilli Valley, especially in the industrial area.
Table 7
Geoaccumulation index (Igeo) of heavy metals
Samp. | Cr | Ni | Cu | Zn | Pb | As | Samp. | Cr | Ni | Cu | Zn | Pb | As |
R1 | 0.93 | 0.59 | -1.10 | -0.62 | -1.14 | -1.50 | D1 | 1.00 | 0.37 | 0.28 | 1.28 | 1.90 | -1.29 |
R2 | 0.72 | 0.52 | -0.94 | -0.36 | -1.09 | -1.52 | D2 | 0.43 | 0.40 | 1.00 | 2.47 | 2.48 | -0.92 |
R3 | 1.23 | 0.57 | -1.10 | -0.82 | -1.54 | -1.58 | D3 | 1.20 | 0.23 | 1.36 | 2.06 | 3.93 | -1.74 |
R4 | 1.06 | 0.55 | -1.15 | -0.25 | -1.32 | -1.31 | D4 | 1.30 | 0.09 | 1.86 | 1.54 | 3.50 | -1.19 |
R6 | 1.37 | 0.61 | -0.66 | 0.67 | -0.36 | -1.63 | D5 | 0.90 | 0.32 | 1.28 | 2.41 | 3.35 | -0.84 |
KH1 | 0.37 | -0.30 | -0.86 | 0.28 | -0.55 | -2.52 | DA | 0.94 | 0.21 | 0.41 | 1.63 | 2.62 | -1.05 |
KH3 | 0.45 | 0.33 | -0.81 | 0.33 | -0.48 | -1.53 | DB1 | 0.50 | -0.56 | -1.48 | -1.06 | -0.59 | -2.84 |
KH4 | 1.00 | 0.48 | -1.15 | -0.82 | -1.06 | -1.76 | DB2 | 1.11 | 0.26 | 0.76 | 1.79 | 2.78 | -0.80 |
KHA2 | 0.71 | 0.40 | -1.15 | -0.30 | -1.03 | -1.74 | DB3 | 1.05 | 0.42 | -0.27 | 0.47 | 0.82 | -1.62 |
KS1 | 1.17 | -0.92 | -2.41 | -1.83 | -1.96 | -2.36 | DC1 | 0.53 | 0.53 | -0.59 | 0.21 | 0.74 | -1.96 |
KS2 | 1.20 | -0.43 | -2.04 | -1.41 | -1.77 | -2.31 | DC2 | 1.03 | 0.09 | -0.63 | -0.25 | 1.56 | -1.60 |
KS3 | 1.22 | 0.47 | -1.27 | -0.38 | -1.43 | -1.84 | SH1 | 0.24 | 0.10 | -0.12 | 0.89 | 0.21 | -2.03 |
KS4 | 1.15 | 0.23 | -0.86 | 0.34 | 0.64 | -2.34 | SH2 | 1.01 | 0.17 | 0.05 | 0.26 | 0.14 | -1.63 |
KS5 | 1.83 | -0.28 | -1.61 | -0.77 | -0.82 | -2.28 | SH3 | 0.92 | 0.43 | -1.02 | -0.45 | -0.94 | -1.62 |
KS7 | 1.17 | 0.77 | -0.55 | -0.22 | -0.54 | -1.38 | SH4 | 1.27 | 0.37 | -1.20 | -0.87 | -1.18 | -1.67 |
KSA2 | 0.43 | 0.37 | -1.17 | 0.28 | -0.44 | -1.57 | SH5 | 0.77 | 0.45 | -1.05 | -0.56 | -0.77 | -1.53 |
KSB3 | 0.47 | 0.52 | -0.99 | -0.26 | -1.13 | -1.50 | SHA | 1.23 | 0.51 | -1.12 | -0.84 | -1.31 | -1.58 |
| | | | | | | SH6 | 1.28 | 0.36 | -1.26 | -0.89 | -0.43 | -1.58 |
| | | | | | | SH7 | 0.97 | 0.48 | -0.82 | 0.00 | -0.31 | -1.80 |
3.4.2. Enrichment factor (E.F.)
Table 8 shows the enrichment factor values for H.M.s in the valley sediments. The Cr enrichment factor values of 3.63 to 12.50 indicate they are within the moderate enrichment to significant enrichment categories. The higher values in the samples of some sites are usually associated with agricultural activity and the impact of the erosion activities of the soils adjacent to the valleys and their erosion towards the valleys during the rainy periods of the year. The E.F. values of Ni ranged from 1.95 to 4.19 and reflected that they fall within the moderate enrichment category, representing Ni's association with the clay minerals that make up the clay fraction of the sediment. The E.F. of Cu ranged from 0.69 to 12.36; the values were less than 2 in all valley's samples within the deficiency to minimal enrichment category, except for Al-Danffilli Valley, which ranges from approximately 2 to 12.36 and classified within the moderate enrichment category. The low content of Cu in the valley's samples is associated with the clay fraction as adsorption on the surfaces of clay minerals. At the same time, the high values in Al-Danffilli Valley are the result of industrial activities in the region, especially those related to plumbing, denting, repairing electric generators and painting car workshops. The E.F. values of Zn 1.08 to 16.19 and Pb 1.25 to 62.16 for all valleys except Al-Danffilli Valley fall within deficiency to minimal enrichment and moderate enrichment. Al-Danffilli Valley lies between moderate enrichment and extremely high enrichment due to industrial activities. E.F. values for As were 0.60 to 1.79 in all valleys falling within the deficiency to minimal enrichment category, which gives a negative indication of contamination with this element.
Table 8
Enrichment Factor (E.F.) of heavy metals
Samp. | Cr | Ni | Cu | Zn | Pb | As | Samp. | Cr | Ni | Cu | Zn | Pb | As |
R1 | 5.33 | 3.89 | 1.19 | 1.76 | 1.55 | 0.97 | D1 | 6.08 | 3.62 | 3.40 | 7.14 | 13.92 | 1.21 |
R2 | 4.99 | 4.00 | 1.44 | 2.28 | 1.74 | 1.03 | D2 | 4.08 | 3.68 | 5.53 | 16.19 | 20.66 | 1.56 |
R3 | 7.15 | 4.19 | 1.30 | 1.67 | 1.28 | 1.00 | D3 | 7.69 | 3.61 | 7.88 | 13.44 | 62.16 | 0.98 |
R4 | 6.04 | 3.93 | 1.20 | 2.36 | 1.42 | 1.15 | D4 | 9.15 | 3.63 | 12.36 | 10.44 | 51.20 | 1.59 |
R6 | 7.31 | 3.99 | 1.65 | 4.36 | 2.69 | 0.89 | D5 | 5.77 | 3.58 | 6.89 | 15.86 | 38.46 | 1.69 |
KH1 | 4.80 | 2.79 | 1.88 | 4.34 | 3.10 | 0.63 | DA | 6.10 | 3.40 | 3.88 | 9.53 | 23.82 | 1.50 |
KH3 | 4.12 | 3.51 | 1.58 | 3.67 | 2.64 | 1.02 | DB1 | 7.63 | 3.40 | 1.78 | 2.50 | 4.38 | 0.74 |
KH4 | 5.90 | 3.81 | 1.23 | 1.62 | 1.73 | 0.85 | DB2 | 6.87 | 3.52 | 4.94 | 10.70 | 26.71 | 1.79 |
KHA2 | 5.00 | 3.72 | 1.26 | 2.40 | 1.82 | 0.89 | DB3 | 6.12 | 3.64 | 2.24 | 3.95 | 6.38 | 0.94 |
KS1 | 8.98 | 1.95 | 0.69 | 1.08 | 1.25 | 0.76 | DC1 | 3.91 | 3.62 | 1.65 | 3.04 | 5.51 | 0.68 |
KS2 | 8.35 | 2.49 | 0.81 | 1.32 | 1.30 | 0.72 | DC2 | 6.87 | 3.29 | 1.99 | 2.74 | 12.08 | 1.09 |
KS3 | 6.60 | 3.63 | 1.08 | 2.11 | 1.29 | 0.78 | SH1 | 4.17 | 3.51 | 2.98 | 6.33 | 5.00 | 0.85 |
KS4 | 6.85 | 3.32 | 1.55 | 3.77 | 5.85 | 0.60 | SH2 | 7.05 | 3.65 | 3.33 | 4.07 | 4.74 | 1.11 |
KS5 | 12.50 | 2.67 | 1.05 | 1.99 | 2.44 | 0.71 | SH3 | 5.41 | 3.57 | 1.30 | 2.03 | 1.82 | 0.91 |
KS7 | 5.42 | 3.80 | 1.52 | 2.01 | 2.03 | 0.91 | SH4 SH4 | 7.08 | 3.51 | 1.17 | 1.56 | 1.59 | 0.91 |
KSA2 | 4.38 | 3.90 | 1.33 | 3.82 | 2.93 | 1.08 | SH5 | 4.70 | 3.47 | 1.22 | 1.81 | 1.98 | 0.93 |
KSB3 | 3.63 | 3.46 | 1.21 | 2.12 | 1.46 | 0.90 | SH6 | 6.70 | 3.76 | 1.20 | 1.54 | 1.40 | 0.93 |
| | | | | | | SH7 | 6.86 | 3.33 | 1.08 | 1.47 | 2.56 | 0.92 |
| | | | | | | SH8 | 5.24 | 3.45 | 1.40 | 2.59 | 2.64 | 0.75 |