3.1 Heavy metal content in soil
The analysis results of heavy metal element content in soil samples are shown in Table 3. The range of Cu content in soil is between 24.10-682.00mg kg− 1, with a mean value of 124.00mg kg− 1 and a large variation range. The range of Ni content is between 21.65-916.10mg kg− 1, with a mean value of 136.8mg kg− 1. The mean content of the two elements exceeds the soil background values of Jinchang City (GB62/T 4524 − 2022), which is 3.32 and 4.47 times the background value, respectively, indicating that the soil at the sampling points in the study area has been contaminated with heavy metals Cu and Ni, and the degree of pollution is relatively high. Moreover, the average value of Cu has exceeded the risk screening values for soil contamination of agricultural land (GB15618-2018), with 73.33% of the data exceeding the soil background values of Jinchang City and 26.67% exceeding the Risk screening values for soil contamination of agricultural land. The Ni content at 53.33% of the sampling points exceeds the soil background values of Jinchang City, and the Ni content at 20% of the sampling points exceeds the Risk screening values for soil contamination of agricultural land. This indicates that there is a risk of soil pollution in agricultural land in these areas.
Table 3
Descriptive statistics of soil properties and heavy metal concentrations in agricultural soils and related soil quality standards (mg kg–1)
Statistical values | Cu | Ni | Ph | EC(µScm− 1) | OM(g kg− 1) | DOC(mg l− 1) | CEC(cmol+ kg− 1) |
Minimum | 24.1 | 21.65 | 7.92 | 143 | 14.26 | 20.78 | 0.12 |
Maximum | 682.0 | 916.1 | 8.23 | 324 | 38.87 | 58.65 | 8.97 |
Mean | 124.0 | 136.8 | 8.14 | 186.23 | 28.11 | 37.39 | 3.82 |
Standard deviation | 173.36 | 224.21 | | | | | |
Coefficient of variation (%) | 139.81 | 163.95 | | | | | |
Over standard rate(%) | 26.67 | 20 | | | | | |
Risk screening values for soil contamination of agricultural land | 100 | 190 | | | | | |
Soil background values of jinchang city | 37.3 | 30.6 | | | | | |
The coefficient of variation (CV) of heavy metal pollution is a statistic that measures the uniformity and variability of heavy metal elements in the study area[31]. The larger the CV value of pollutants, the greater the impact of human activities[32]. The CV values of Cu and Ni are 139.81% and 163.95%, respectively, indicating strong variability, indicating that the spatial distribution of Cu and Ni is uneven, and the content of heavy metals in soil is not only affected by geological background, but also by human activities[37]. Large spatial differences indicate that industrial activities may be a potential source of heavy metal pollution[34].
3.2 Assessment of soil heavy metal pollution
The spatial distribution of heavy metals can be used to evaluate the possible sources of soil heavy metal pollution. The distribution of heavy metals in the soil is shown in Fig. 3, where different concentrations of different heavy metals are displayed in different colors, with green indicating low concentrations and red indicating high concentrations. The distribution of Cu and Ni in the soil is similar, with high concentration areas concentrated near sampling points 1, 2, and 3, and the concentration of heavy metals in the soil decreasing as the distance from the sampling points increases. This indicates that the pollution of heavy metals Cu and Ni in the soil may have the same source. Sampling point 2 is near the Jinchuan Group Metallurgical Plant, tailings pond, Jinchuan Group Copper Slag Mining, and residential areas. The high concentration of heavy metals in this area may be due to long-term irrigation with sewage and the emission of waste gases from the metallurgical plant, causing heavy metals to settle in the soil through the atmosphere[14].
As can be seen from Fig. 4, pollution is mainly concentrated in sampling points 1, 2, 3 and 14. Sampling point 9, 13, and 15 have mild Cu pollution, accounting for 20%; sampling point 3 has moderate Cu pollution, accounting for 6.67%; sampling point 1 and 14 have moderate Cu pollution, accounting for 13.33%; sampling point 2 has severe pollution, accounting for 6.67%; the remaining sampling points are not polluted, accounting for 53.33%. Sampling point 9, 11, 12, and 15 have mild Ni pollution, accounting for 26.67%; sampling point 1, 3, and 14 have moderate pollution, accounting for 20%; sampling point 2 has severe pollution, accounting for 6.67%. The remaining locations are uncontaminated, accounting for 46.67%. These data indicate that only sites 1, 2, 3, and 14 are severely contaminated with Cu and Ni, Other locations have less or no pollution.
3.3. Distribution characteristics of Cu and Ni in different plant parts
The content of heavy metals in each component of corn is shown in Fig. 5. The average content in the roots of corn samples is Ni(12.99mg/kg) > Cu(9.20mg/kg); the average content in the stalk1 of corn is Cu(1.89mg/kg) > Ni(0.79mg/kg); the average content in the stalk2 of corn is Cu(3.55mg/kg) > Ni(1.39mg/kg); the average content in the leaves of corn is Cu(23.43mg/kg) > Ni(13.84mg/kg); the average content in the corncobs is Cu(3.04mg/kg) > Ni (0.1mg/kg); the average content in the husks is Cu(4.68mg/kg) > Ni(2.47mg/kg); the average content in the grains of corn is Cu(0.64mg/kg) > Ni(0.37mg/kg); the average content in the tassel of corn is Cu(23.62mg/kg) > Ni(21.67mg/kg).
Different heavy metals are distributed differently in corn, with Cu showing the following distribution in corn organs: tassel > leaves > roots > husks > stalk 2 > corncobs > stalk 1 > grains, which is consistent with the results of Su Chun-tian et al[33]. Ni shows the following distribution in corn organs: tassel > leaves > roots > husks > stalk 2 > stalk 1 > grains > corncobs; it can be seen that heavy metals are mainly concentrated in the anther and leaves, which is consistent with the results of Li Ye-pu et al[19]. The reason why the heavy metals in the corn anther are higher than those in other parts (except root and leaf) may be that the corn anther growth period is shorter (10–15 d), and it needs a large amount of nutrients in a short time. Meanwhile, pollutants can enter the anther along with nutrients. Pollutants enter the leaves through the soil-root-leaf and atmospheric-leaf routes. Xiao-Hu Li found that the heavy metal content in the dust on the surface of the slag pile was relatively high. The maximum concentrations of Cu and Ni were 4698.70 and 2310.86 mg kg− 1, respectively, with an average of 1744.87 and 1172.14 mg kg− 1[14]. This can explain why the pollutant content in the leaves is higher than that in other organs[19]. It can be seen that although the distribution of Cu and Ni in corn plants is different, the general trend of distribution is consistent, and both heavy metals are easily accumulated in the tassel of corn.
Corn is the main food for local residents and livestock feed, and the quality of food safety affects the health of local residents. The Cu content in corn grains ranges from 0 to 1.38 mg kg− 1, with an average of 0.64 mg kg− 1. Because there is no specific limit for Cu in corn in the latest national standard for food safety (GB 2762 − 2022), we refer to the food copper limit standard of 10 mg kg− 1 for grain as a reference value. All 15 sampling points had corn grain copper content that did not exceed this limit. The Ni content in corn grains ranges from 0 to 1.52 mg kg− 1, with an average of 0.37 mg kg− 1. We refer to the food safety standard for Ni limit of 1 mg kg− 1 for oils and fats as a reference value. Only sampling points 1 (1.09 mg kg− 1) and 2 (1.52 mg kg− 1) exceeded the limit, and the rest were less than 1 mg kg− 1. The non-compliance rate was 13.33%. This shows that soil pollution does not necessarily mean that corn crops are polluted, but sampling points 1 and 2 have corn grain Ni pollution, and sampling points 1 and 2 have heavy soil Cu and Ni pollution and pollution. This area is not suitable for growing corn crops.
3.4 Spatial distribution characteristics of heavy metals in various organs of corn
The spatial distribution characteristics of heavy metals can be used to evaluate the possible sources of soil heavy metal pollution. The distribution of heavy metals in various organs of maize is shown in Fig. 6, where different concentrations of heavy metals are displayed in different colors, with green indicating low concentrations and red indicating high concentrations.
The distribution of Ni concentration in corn kernels is similar to that in soil, with high concentrations concentrated in sampling points 1 and 2. The distribution of Ni content in soil and corn kernels is highly similar, indicating that soil Ni pollution can predict Ni pollution in corn kernels. The distribution of Cu content in corn kernels is different from that in soil, with high concentrations of Cu in corn kernels located at sampling point 14. This spatial difference between soil and corn kernels may be due to differences in soil physicochemical properties and bioavailability of heavy metals in soil[4].
The Cu content in roots, leaves, and seed coats is similar to the distribution of Cu and Ni in the soil, with two high-concentration areas in the roots. The distribution of Cu and Ni in stem 1 is similar to that in the soil, but there are differences between them. The high-concentration areas are mainly concentrated at point 15. The distribution of Cu in stem 2 is similar to that in the soil, with high concentrations at points 1, 2, 12, and 13. The high-concentration areas of Ni in stem 2 are concentrated at points 2. The high-concentration areas of Cu in corn cob are at points 14 and 15, and the high-concentration areas of Ni are at point 10. The high-concentration areas of Cu and Ni in male inflorescences are located at points 7. Such differences may be due to long-term agricultural cultivation, as the agricultural soil in Jinchuan District, Jinchang City has been affected by human activities[4]. The distribution pattern of metals may be affected by various pollution sources, such as sewage irrigation containing heavy metals[38], long-term fertilization on soil[39], and the emission of heavy metals from coal and industrial waste gases that are transported to the soil through atmospheric dust[40].
To further understand the relationship between heavy metal content in corn kernels and soil, a correlation analysis was conducted between heavy metal content in rice kernels and soil (Fig. 7), and the Pearson correlation coefficient was used to analyze the impact of soil on heavy metal content in corn kernels. The results showed that soil Ni and soil Cu showed a highly significant positive correlation (P < 0.01), and grain Cu and grain Ni also showed a highly significant level (P < 0.01). These correlations suggest that heavy metals may have homology; There is a highly significant correlation (P < 0.01) between soil Ni and soil Ni. This result indicates that an increase in soil Ni heavy metal concentration will significantly increase the Ni content in seeds, which is consistent with the previous conclusion. Zhou Yan et al. also obtained similar results[41]; There is a highly significant correlation between soil Cu and grain Ni, indicating that the size of grain Ni content is related to the size of soil Cu content, which may be because copper is an essential nutrient element for crops[42]. The correlation between soil Cu and grain Cu is not significant, indicating that the Cu content in the soil has not reached the toxic range. In the absence of Cu element, plant roots can resist the transportation of Cu to the aboveground part of the plant. The absorption of heavy metals by plants depends on their activity, and is also greatly influenced by soil pH and organic matter content[43].
3.5. BCFs and TFs of Cu and Ni
The average enrichment coefficients of heavy metals Cu and Ni in different organs of corn are shown in Table 4. From Table 4, it can be seen that the average enrichment coefficients of Cu in the organs of corn are as follows: tassel > leaves > roots > stalk 2 > corncobs > husks > stalk 1 > grains; the average enrichment coefficients of Ni in the organs of corn are as follows: tassel > roots > leaves > stalk 2 > stalk 1 > husks > grains > corncobs. The organs of corn with the strongest ability to enrich Cu and Ni are tassel, with enrichment coefficients of 0.6106 and 0.5282, respectively. There are also differences among the elements, such as the strong enrichment of Cu in leaves and tassel, and the weak enrichment in corn grains. The enrichment of Ni in roots and tassel is strong, while it is weak in corn cores. The order of enrichment of the heavy metal elements in the roots is Ni > Cu, while in other organs it is Cu > Ni. This may be because the aboveground parts except the roots are also polluted by Cu in atmospheric deposition[14]. The average enrichment coefficients of corn plants are in the order of Cu > Ni, which is consistent with the study of Jiangyun Liu et al[34].
Studies have shown that different plant organs have different biological utilization rates of heavy metals, and the root system has the highest absorption and bioaccumulation rate of heavy metals[35]. Based on this study, it can be inferred that in the corn-soil system of the arid oasis city in northwest China, the tassel of corn have a stronger ability to enrich Cu and Ni than other organs. The migration coefficients of Cu and Ni in different organs of maize are shown in Table 5, from which we can see that: the migration coefficients are similar to the accumulation coefficients, and both Cu and Ni elements show strong migration ability in the anther and leaves. This indicates that it is easier for Cu and Ni elements to migrate from the underground parts to the leaves and tassel. The migration coefficients of Cu and Ni in corn kernels are 0.1255 and 0.0337, respectively, indicating that heavy metals are difficult to migrate from the roots to the corn grains. This may be because the roots are the first barrier for heavy metals to transfer to the edible parts of the plant[36]. The migration coefficients of Cu and Ni in maize organs are all expressed as: Cu > Ni.
Table 4
Bio-concentration factors (BCFs) in different organs of corn crops
| | roots | stalk 1 | corncobs | grains | husks | stalk 2 | leaves | tassel |
Cu | Maximum | 0.1642 | 0.2105 | 0.1237 | 0.0281 | 0.1203 | 0.2315 | 0.6192 | 4.3154 |
Minimum | 0.0468 | 0.0022 | 0.0055 | - | 0.0103 | 0.0103 | 0.1262 | 0.0107 |
Mean | 0.0929 | 0.0305 | 0.0605 | 0.0114 | 0.0543 | 0.0543 | 0.2902 | 0.6106 |
Ni | Maximum | 1.1224 | 0.0430 | 0.0279 | 0.0314 | 0.0538 | 0.0763 | 0.2143 | 3.9412 |
Minimum | 0.0280 | - | - | - | - | - | 0.0771 | 0.0053 |
Mean | 0.1803 | 0.0141 | 0.0020 | 0.0048 | 0.0111 | 0.0212 | 0.1250 | 0.5282 |
Table 5
Translocation factors (TFs) in different organs of corn crops
| | stalk 1 | corncobs | grains | husks | stalk 2 | leaves | tassel |
Cu | Maximum | 3.3735 | 1.2735 | 0.3878 | 1.9277 | 2.6786 | 6.1224 | 44.4444 |
Minimum | 0.0387 | 0.0984 | - | 0.1014 | 0.1483 | 1.2440 | 0.1908 |
Mean | 0.3970 | 0.6394 | 0.1255 | 0.6345 | 0.7322 | 3.2109 | 6.6992 |
Ni | Maximum | 0.4817 | 0.1810 | 0.1606 | 0.6057 | 0.6534 | 2.7500 | 33.7423 |
Minimum | - | - | - | - | - | 0.1872 | 0.0808 |
Mean | 0.1098 | 0.0130 | 0.0337 | 0.1191 | 0.1685 | 1.1796 | 4.8011 |
3.6 Health risk assessment of corn grains
The health risk assessment of residents in the study area was conducted using the US Environmental Protection Agency (USEPA) recommended health risk model[29], with Ni RfD set at 0.02 and Cu RfD set at 0.037mg (kg · d). The health risk assessment results of heavy metal exposure in corn kernels in the study area are shown in Fig. 8. The average HQ values of children in Jinchuan District, Jinchang City through ingestion of Cu and Ni are 0.10731982 and 0.114583333, respectively, while the average HQ values of adults through ingestion of Cu and Ni are 0.036795367 and 0.039285714. The non carcinogenic risk index Ni for children and adults is slightly higher than Cu, indicating that Ni has a slightly higher non carcinogenic risk than Cu. It was found that the risk index of children is generally higher than that of adults, which is consistent with previous research results[18]. This may be due to the underdeveloped metabolic organs such as liver and kidney in children, which have weaker detoxification and excretion functions for toxic and harmful substances, making them more sensitive to environmental pollution[41]. The HQ values of heavy metals for both adults and children are less than 1, indicating that although there are multiple sampling points in the study area with moderate to severe soil pollution, there is no significant health risk for adults and children.