Parameters of soil and heavy metals in reference site
In the reference site (Loc. 75°38`24.5” N — 13°44`25.4” E, altitude: 627 m asl) the soil temperature ranged between 28°C and 30°C. The pH of the reference site remained acidic to circumneutral, recorded between 5.3 and 7.2. Statistics of parameters of soil and heavy metal concentrations of reference site are presented in Table 2. The SMC and SOC of the reference site are low while, WHC was recorded up to 25%. The SMC, SOC and WHC showed a little variance over the study period. In reference site, we analyzed and recorded concentrations (ppm) of Copper (Cu), Zinc (Zn), Manganese (Mn), Iron (Fe), Chromium (Cr), Nickel (Ni), Lead (Pb) and Cadmium (Cd). The statistics of these parameter represents that all these values are normally distributed. Further, Table 2 also presents concentrations of heavy metals recorded in reference site with general heavy metal concentrations recorded for typical uncontaminated agricultural soil (Nagajyoti et al., 2010). Except the concentration of Cu, all other heavy metals recorded in the reference site fall within the upper limit of the concentrations detailed for uncontaminated soils. In the reference site, we recorded Cu at a concentration 140.33 ± 0.021 ppm which is higher than those cited by Nagajyoti et al., (2010) for uncontaminated sites.
Table 2
Descriptive statistics of parameters of soil and heavy metals in reference site. The SMC, SOC and WHC of soil are represented in percentage (%) and all heavy metals are represented as mg kg− 1 of soil.
Parameter | Min | Max | Range | Mean | SE | Variance | Skewness | Kurtosis | Reference* ppm. dry wt (range) |
SMC | 1.20 | 1.30 | 0.10 | 1.27 | 0.236 | 0.002 | -1.414 | 1.5 | — | |
SOC | 0.72 | 0.78 | 0.06 | 0.75 | 0.123 | 0.001 | 0.000 | 1.5 | — | |
WHC | 22.50 | 23.00 | 0.50 | 22.83 | 0.118 | 0.06 | -1.414 | 1.5 | — | |
Cu | 140.10 | 140.50 | 0.40 | 140.33 | 0.850 | 0.03 | -1.056 | 1.5 | 2-100 | |
Zn | 26.20 | 26.60 | 0.40 | 26.43 | 0.850 | 0.03 | -1.056 | 1.5 | 10–300 | |
Mn | 162.60 | 163.00 | 0.40 | 162.77 | 0.850 | 0.03 | 1.056 | 1.5 | 100-4,000 | |
Fe | 9600.00 | 9695.00 | 95.0 | 9650.00 | 19.472 | 1516.67 | -0.381 | 1.5 | 7,000–55,000 | |
Cr | 77.70 | 81.40 | 3.70 | 79.97 | 0.811 | 2.63 | -1.270 | 1.5 | 5-3000 | |
Ni | 30.40 | 31.70 | 1.30 | 30.93 | 0.278 | 0.31 | 1.111 | 1.5 | 10–100 | |
Pb | 16.20 | 18.30 | 2.10 | 16.93 | 0.484 | 0.94 | 1.403 | 1.5 | 2-200 | |
Cd | 0.10 | 0.20 | 0.10 | 0.13 | 0.024 | 0.002 | 1.414 | 1.5 | 0.001-0.7 | |
*Nagajyoti et al. (2010) |
Result of correlation co-efficient analysis
Table 3 details correlation coefficient between parameters of soil and heavy metal concentration in reference site. The analysis indicates the reduction in concentration of Mn, Ni, and Pb, with increase in SMC (%). In contrast, the concentration of Zn showed an increase with SMC at a significant level. The increase in SOC the concentration of Mn and Ni are reduced. The Cu concentration increased with increasing WHC while Cd concentration decreased significantly. Among the correlations of heavy metals, the increase in Cd concentration has decreased the Cu content. Increase in lead content concurrently increased the concentration of Mn and Ni and decreased Zn concentration. Increase in Fe content showed an increase in Cr content while similar increase was observed between Pb and Ni. Among the parameters of the soil, the SMC comprised maximum correlation with heavy metals. This exhibited R2 = 0.942; F = 32.667, p = 0.029. The WHC, SMC, SOC and pH of the soil did not exhibit correlation in reference site.
Table 3
Pearson correlation co-efficient between parameters of soil and heavy metals of reference site (N = 16).
Parameter | SMC | SOC | WHC | Cu | Zn | Mn | Fe | Cr | Ni | Pb | Cd |
SMC | - | | | | | | | | | | |
SOC | 0.866 | - | | | | | | | | | |
WHC | -0.500 | -0.866 | - | | | | | | | | |
Cu | -0.277 | -0.721 | 0.971* | - | | | | | | | |
Zn | 0.971* | 0.721 | -0.277 | -0.038 | - | | | | | | |
Mn | -0.971* | -0.961* | 0.693 | 0.500 | -0.885 | - | | | | | |
Fe | -0.817 | -0.419 | -0.091 | -0.327 | -0.932 | 0.655 | - | | | | |
Cr | -0.625 | -0.151 | -0.363 | -0.577 | -0.794 | -0.419 | 0.961* | - | | | |
Ni | -0.975* | -0.955* | 0.679 | 0.482 | -0.894 | 1.000** | 0.670 | 0.438 | - | | |
Pb | -0.999** | -0.886 | 0.536 | 0.318 | -0.960* | 0.980* | 0.792 | 0.592 | 0.984* | - | |
Cd | 0.500 | 0.866 | -1.000** | -0.971* | 0.277 | -0.693 | 0.091 | 0.363 | -0.679 | -0.536 | - |
*Significant at 0.05 level (2 tailed)
**Significant at 0.01 level (2 tailed)
Parameters of soil and Heavy metals in contaminated sites
In contaminated sites (15 sites located 75°38`00.4” — 75° 38`29.8” N and 13° 43`20.0” — 13° 49`0.3” E; altitude: range 624 — 637 m. asl) the soil temperature ranged between 25°C and 35° C. Circumneutral pH ranged between 5.6 and 7 was recorded. Table 4 details the statistics of parameters of soil and heavy metals. The SMC and organic carbon content remained low; while WHC ranged between 21 and 49%. The values of heavy metal concentration of different contaminated sites over the study period showed a considerably low variance and data are normally distributed. Except concentration of Cu and Cd, the values of all other parameters were found within the range detailed for typical uncontaminated soils (Nagajyoti et al., 2010). The Cu and Cd concentration was found to be high.
Table 4
Descriptive statistics of parameters of soil and heavy metals in contaminated sites. The SMC, SOC and WHC of soil are represented in percentage (%) and all heavy metals are in mg kg− 1.
Parameter | Min | Max | Range | Mean | SE | Variance | Skewness | Kurtosis |
SMC | 1.67 | 12.43 | 10.76 | 5.98 | 0.827 | 10.267 | 0.711 | -0.346 |
SOC | 0.36 | 1.10 | 0.74 | 0.70 | 0.702 | 0.74 | 0.256 | -1.1557 |
WHC | 21.67 | 48.13 | 26.46 | 33.15 | 2.173 | 70.837 | 0.999 | -0.097 |
Cu | 126.63 | 202.10 | 75.47 | 162.49 | 5.798 | 504.286 | -0.151 | -0.504 |
Zn | 27.40 | 43.70 | 16.30 | 34.76 | 1.429 | 30.620 | 0.475 | -1.265 |
Mn | 92.20 | 943.33 | 851.13 | 368.25 | 66.838 | 67009.817 | 1.205 | 0.238 |
Fe | 10946.6 | 33336.67 | 22390.00 | 21253.89 | 1693.542 | 43021273.920 | 0.155 | -0.649 |
Cr | 22.50 | 255.83 | 233.33 | 147.50 | 18.597 | 5187.474 | -0.147 | -0.708 |
Ni | 17.60 | 177.87 | 160.27 | 86.21 | 12.630 | 2392.581 | 0.473 | -0.416 |
Pb | 11.27 | 83.03 | 71.76 | 30.35 | 4.991 | 373.658 | 1.605 | 2.920 |
Cd | 0.40 | 6.03 | 5.63 | 1.10 | 0.358 | 1.921 | 3.660 | 13.816 |
Result of correlation co-efficient analysis
Table 5 represents correlation co-efficient analysis between parameters of soil and heavy metals. The SMC showed a strong correlation with Zn, Fe, Cr, Ni, and Cd. The concentration of Zn, Fe, Cr, Ni and Cd have showed an increase with the increase in concentration of SMC. Whereas, the concentration of Fe, Cr, Ni and Cd decreased with increase in SOC content. Similarly, with the increase in WHC of the soil the Cu concentration decreased and Pd and Cd concentration increased. Among the heavy metals the Cd concentration has increased with an increase in Fe, Cr, Ni, and Pb. While, Pb showed only positive correlation with Mn; as Pb increased the concentration of Mn increased. Ni content showed a strong positive correlation with Cu, Zn, Fe, and Cr. An increase in Ni content increased the concentration of these metals.
Table 5
Pearson correlation co-efficient between parameters of soil and heavy metals of contaminated sites (N = 60).
Parameter | SMC | SOC | WHC | Cu | Zn | Mn | Fe | Cr | Ni | Pb | Cd |
SMC | - | | | | | | | | | | |
SOC | -207 | - | | | | | | | | | |
WHC | 0.213 | 0.032 | - | | | | | | | | |
Cu | 0.237 | 0.164 | -0.343** | - | | | | | | | |
Zn | 0.552** | 0.128 | -0.022 | 0.636** | - | | | | | | |
Mn | -0.038 | 0.009 | 0.039 | 0.248 | 0.292* | - | | | | | |
Fe | 0.399** | -0.259* | -0.016 | 0.233 | 0.697** | 0.257* | - | | | | |
Cr | 0.342** | -0.557** | -0.008 | -0.50 | 0.343** | 0.055 | 0.839** | - | | | |
Ni | 0.421** | -0.309* | -0.126 | 0.384** | 0.699** | 0.160 | 0.927** | 0.824** | - | | |
Pb | 0.118 | 0.103 | 0.358** | -0.162 | 0.244 | 0.328* | 0.191 | 0.082 | -0.019 | - | |
Cd | 0.582** | -0.306* | 0.554** | -0.127 | 0.248 | 0.144 | 0.401** | 0.463** | 0.295* | 0.686** | - |
*Significant at 0.05 level (2 tailed) |
**Significant at 0.01 level (2 tailed) |
Increase in Cr concentration showed an increase in Zn and Fe concentration. Whereas increase in Fe concentration showed an increase in Zn and Mn concentration but Zn has showed a significant positive correlation with Cu. The correlation analysis between concentration of heavy metal and quantity of synthetic fertilizer or pesticide applied did not yield significant result except the association between synthetic fertilizer and cadmium (r = 0.594, p = 0.019). Further, pH of the soil did not show any correlation with other parameters of soil or heavy metal concentration.
Heavy metal concentration in contaminated sites
All heavy metals recorded have showed a clear increase in their concentration in the contaminated sites (Fig. 2). The magnitude of increase differs among different heavy metals. Table 6 represents the result of ANOVA and parameter of soil and heavy metals between the reference and contaminated sites. On an average, the SMC and WHC of contaminated rice paddy soil showed 4.7 and 1.5 times increase in their concentrations compared to reference site and found to be statistically significant (p < 0.05). However, SOC content slightly decreased in contaminated sites (0.9% of reference site) and differences with reference site is insignificant. All heavy metals have showed clear increase in their concentration in contaminated sites; represented 1.2, 1.3, 2.3, 2.2, 1.8, 2.8, 1.8 and 8.5 times increase for Cu, Zn, Mn, Fe, Cr, Ni, Pb and Cd respectively compared to their concentration in reference site. Among these Zn, Fe, and Ni, showed highly significant statistical difference (p < 0.01) between
Table 6
ANOVA and parameters of the soil and heavy metals showing the statistical difference between reference and contaminated sites.
Parameter | Total sum of squares | df | Mean square | F | p |
WHC | 1327.8229 | 18 | 335.9433 | 5.76 | 0.028126 |
SMC | 213.9422 | 18 | 70.1939 | 8.3 | 0.010372 |
SOC | 1.044495 | 18 | 0.007895 | 0.13 | 0.722873 |
Cu | 8609.9858 | 18 | 1549.8938 | 3.73 | 0.070291 |
Zn | 647.8236 | 18 | 219.0527 | 8.69 | 0.009000 |
Mn | 1071472.8484 | 18 | 13333.3231 | 2.42 | 0.138214 |
Fe | 1027513644.41 | 18 | 425211259.542 | 12 | 0.002966 |
Cr | 87032.9038 | 18 | 14400.3815 | 3.37 | 0.083949 |
Ni | 43146.2713 | 18 | 9649.2113 | 4.9 | 0.040817 |
Pb | 5802.3432 | 18 | 568.33 | 1.85 | 0.191548 |
Cd | 29.865607 | 18 | 2.9631 | 1.87 | 0.189284 |
reference and contaminated sites. Although, Cu and Cr were represented 1.2 and 1.8 times higher concentration, the differences are marginally significant (p < 1). Which could be due to high variance of data. Mn, Cr, Pb and Cd though represented at higher concentration did not show statistical significance. Among these, the values of Mn, Cr, and Pb also had high variance in their data. Therefore, it is apparent that Cu, Zn, Mn, Fe, Cr, Ni, and Pb have showed a strong buildup in their concentration in contaminated sites.
The correlation analysis reveals a maximum significant association of heavy metals (Zn, Fe, Cr, Ni and Cd) with SMC. This followed by organic carbon content of soil (with Fe, Cr, Ni and Cd) and WHC of the soil (with Cu, Pb and Cd). The Principal Component Analysis (PCA) was performed following standard procedure to illustrate the relationship of these three parameters with heavy metal concentration. The Table 7 details the component of PCA and eigen values while, Fig. 3 illustrates Principal Component Analysis (PCA) of parameters of soil and heavy metals. These three parameters together contribute 78% of the total association. Overall, the Zn, Fe, Mn, Cr, Ni and Cd correlated with PC1. Similarly, Cu, Zn, Pb and Cd with PC2 and Zn, Mn, and Pb exhibited correlation on PC3. The test revealed a significant (p = 0.001) value for Bartlett test of sphericity with a KMO = 0.484 and ꭓ2 = 128.946, df 55. Among these three parameters, the WHC revealed maximum correlation (40.259% variance) followed by SMC (20.854% variance) and SOC (16.832% variance) indicates their influence for the buildup of heavy metal in the contaminated sites. The data on parameters of the soil and heavy metal with quantity of synthetic fertilizers or pesticides did not yield significant result (KMO sampling adequacy = 0.317). Thus, data on the synthetic fertilizer or pesticide were not considered to process PCA.
Table 7
Total variance explained and component matrix for the parameters of soil and heavy metals in Rice paddy field soil
Component | Initial Eigenvalues | Extraction Sums of Squared Loadings | Rotation Sums of Squared Loadings |
Total | % of Variance | Cumulative % | Total | % of Variance | Cumulative % | Total |
1 | 4.428 | 40.259 | 40.259 | 4.428 | 40.259 | 40.259 | 3.306 |
2 | 2.294 | 20.854 | 61.112 | 2.294 | 20.854 | 61.112 | 2.509 |
3 | 1.851 | 16.832 | 77.944 | 1.851 | 16.832 | 77.944 | 3.442 |
4 | 0.877 | 7.974 | 85.917 | | | | |
5 | 0.605 | 5.498 | 91.415 | | | | |
6 | 0.385 | 3.501 | 94.916 | | | | |
7 | 0.326 | 2.966 | 97.883 | | | | |
8 | 0.160 | 1.458 | 99.341 | | | | |
9 | 0.048 | 0.438 | 99.779 | | | | |
10 | 0.016 | 0.148 | 99.926 | | | | |
11 | 0.008 | 0.074 | 100.000 | | | | |
Parameter/ Elements | | Component Matrix ∗ | | | Pattern matrix ∗ ● | | Structure Matrix ∗● | |
| PC1 | PC2 | PC3 | | | PC1 | PC2 | PC3 | | PC1 | PC2 | PC3 | |
WHC | | | -0.668 | 0.431 | | | | -0.795 | | | | -0.771 | | |
SMC | | 0.654 | | | | | 0.482 | | | | 0.543 | -0.453 | | |
SOC | | 0.507 | | 0.655 | | | | | 0.913 | | | | 0.852 | |
Cu | | | 0.779 | | | | 0.800 | | | | 0.726 | | | |
Zn | | 0.650 | 0.520 | 0.493 | | | 0.961 | | | | 0.948 | | | |
Fe | | 0.897 | | | | | 0.671 | | -0.503 | | 0.768 | | -0.640 | |
Mn | | 0.666 | | -0.424 | | | | | -0.838 | | | | -0.850 | |
Cr | | 0.872 | | | | | | | -0.841 | | 0.456 | | -0.899 | |
Ni | | 0.862 | | | | | 0.736 | | -0.498 | | 0.820 | | -0.613 | |
Pb | | | -0.464 | 0.624 | | | | -0.829 | | | | -0.802 | | |
Cd | | 0.661 | -0.580 | | | | | -0.829 | | | | -0.891 | -0.472 | |
| Kaiser-Meyer-Olkin Measure of Sampling Adequacy. | 0.484 |
Bartlett's Test of Sphericity | | Approx. Chi-Square | 128.946 |
| df | 55 |
| Sig. | .001 |
∗ Extraction method: Principal Component Analysis |
● Rotation method: Oblimin with Kaiser Normalization