REEs content in study soils
The total concentration of REEs (ΣREEs) in study soils ranged from 168.58 to 1915.68 mg/kg, with an average of 546.71 mg/kg (Table S3), exceeding the natural background levels in Chinese soil (197.3 mg/kg) and Jiangxi soil (243.4 mg/kg) (Wang et al., 2022). The hierarchy of average concentrations for individual REEs is as follows: Ce > Y > Nd > La > Sc > Gd > Pr > Sm > Dy > Er > Yb > Tb > Ho > Eu > Lu > Tm. Notably, Ce, Y, Nd, and La collectively contributed over 80% of the total REE concentration, with Ce being the most prevalent, ranging from 55.18 mg/kg to 458.31 mg/kg. The concentrations of HREEs varied from 44.80 to 771.74 mg/kg with an average of 175.64 mg/kg, whereas LREEs ranged from 119.50 to 1068.59 mg/kg with an average of 348.61 mg/kg. Moreover, the Y was the most abundant HREE, comprising 23.63% of total REEs, while the HREEs accounted for 32.13%, indicating typical of a Y-enriched ion-adsorption rare earth deposit.
Distribution characteristics of REEs in study soils
The distribution of REEs in the study soils was characterized by the ratios of LREE/HREE, NASC-normalized La/Sm and Gd/Yb, along with the anomalies of Ce and Eu (Table 1). The ratios of LREE/HREE, ranging from 1.02 to 7.10 with an average of 2.94, suggest a higher content of LREEs relative to HREEs. However, these ratios are significantly lower than those in northern China, indicating a comparative enrichment of HREEs in the study area (Liang et al., 2014). The slope of LREE and HREE concentration curves can be reflected by normalized (La/Sm)N and (Gd/Yb)N ratios, respectively (Schilling & Winchester, 1966). In this study, the (Gd/Yb)N ratio of 3.15 points to a high degree of internal fractionation of HREEs compared to LREEs, which had a (La/Sm)N ratio of 1.16. This aligns with the broader distribution pattern of "light north, heavy south" across China.
Table 1
Geochemical characteristic parameters of soil rare earth elements in the study area
Statistics | ΣLREEs/ΣHREEs | (La/Sm)N | (Gd/Yb)N | δCe | δEu |
Minimum | 1.02 | 0.74 | 1.43 | 0.56 | 0.13 |
Maximum | 7.10 | 1.69 | 5.55 | 1.14 | 0.35 |
Mean | 1.98 | 1.16 | 3.15 | 0.84 | 0.25 |
SD | 1.88 | 0.29 | 1.14 | 0.16 | 0.06 |
Median | 2.62 | 1.17 | 3.22 | 0.81 | 0.26 |
Note: SD: Standard deviation. |
Ce and Eu can exist in multiple valence states (Ce4+ and Eu2+), differentiating their fractionation behavior from other REEs. The anomalies of Ce and Eu are indicative of specific geochemical processes and sources of REEs (Yu et al., 2022). In our study, all soil samples consistently showed negative Eu and Ce anomalies, with mean values of 0.25 and 0.84, respectively. The δCe/δEu ratio in studied soil averaged 3.36, suggesting a predominance of reducing conditions, as this ratio exceeds 1. Under such conditions, Eu3+ can be reduced to Eu2+ and potentially lost, especially under strong reducing conditions. Meanwhile, positive Ce anomalies often correlate with high sediment alkalinity (Kim et al., 2012). As soil acidity increases, the transformation of Ce3+ to Ce4+ occurs, often alongside the precipitation of iron or manganese oxides, contributing to the observed negative Ce anomalies. Consequently, the studied soil exhibited marked negative δEu and slightly negative δCe anomalies, attributable to mild acidic and strongly reducing conditions.
Pollution and potential ecological risks in study soils
The pollution status of REEs was assessed using Igeo, which provided insights into the ecological risks of soil contamination. The hierarchy of average Igeo values for REEs ranged from Gd (1.51) to Tm (-0.29), with Gd reaching moderate pollution levels (Fig. 1a). The results indicated that Nd (0.83) and Y (0.79), both HREEs, displayed similar distribution patterns, ranging from no pollution to high pollution across all sample sites. Seven other elements had average Igeo values above zero (Tb (0.68), Pr (0.56), La (0.21), Ce (0.13), Dy (0.11), Sc (0.05)), indicating varying levels of pollution from none to moderate. Approximately one-third of the sampling sites were considered unpolluted, with only two out of 21 sites (S20 and S7) showing moderate pollution with Igeo values exceeding 1. The remaining sites indicated between unpollution to moderate pollution categories. The LREEs primarily revealed the lower contamination categories, in contrast to the broader dispersion observed for HREEs, which contributed more significantly to soil pollution.
The ecological risk of REEs is shown in Fig. 2b. Based on the results, all REEs had average \(\:{E}_{r}^{i}\) values lower than 40.0, indicating a low ecological risk. The cumulative average RI values for 21 soil sites ranged from 82.32 to 573.29, ranging between 150 and 300, indicating that the overall mining area is at a moderate risk. According to criteria, two of 21 sites (S20 and S7) had RI values (573.29 and 418.41, respectively) above 300, indicating a considerable ecological risk of REEs in these sites. At the same time, 57% of the sites were medium risk, while the rest were low risk. Eu, Ho, Lu, Dy and Gd were identified as primary contributors to ecological risk, with numerous sites exhibiting medium risks due to high concentrations and toxicity coefficients of these elements (Nkrumah et al., 2021), posing potential threats to the ecosystem. To sum up, the Igeo and RI assessments suggest that the soil in the study area generally faces low to moderate ecological risks, with sites S7 and S20 requiring further attention and potential remediation.
Transport and impact of REE in soil-plant system
REEs may disrupt plant ion transport, influencing its growth by modifying nutrient uptake and physiological functions. Study indicates that REEs absorbed from the soil tend to accumulate in the edible parts of crops, potentially increasing human exposure through diet (Li et al., 2013). Thus, the present study detected REE concentrations in 19 vegetable samples, finding a range from 0.52 to 78.93 mg/kg and an average of 23.17 mg/kg (Table S4). These levels substantially surpass the Chinese National Standard of 0.7 mg/kg fresh weight (GB2762-2005) and those found in commercially available vegetables in China, which range from 0.28 to 1.40 mg/kg (Jiang et al., 2012). In the examined mining area, REE concentrations in vegetables were also markedly higher than those reported from other mining areas in Fujian (3.58 mg/kg) and Jiangxi provinces (6.55 mg/kg) (Zhang et al., 2000b; Li et al., 2013), akin to findings from a HREEs mine in Longnan county ranging from 1.55 to 78.57 mg/kg (Jin et al., 2014). The uptake and translocation of REEs across plant species are diverse, typically, LREEs are more easily enriched in plants compared to HREEs (McLennan and Taylor, 2012). Consistently, we found that over 50% of the total REEs in vegetables were attributed to La and Ce in this study (Table S4).
Besides these differences in enrichment, this study observed varying REE absorptive capacities across different vegetable species. We categorized the vegetable samples into three groups: root vegetables, leafy vegetables, and solanaceous vegetables. Solanaceous vegetables exhibited the lowest REE concentrations, ranging from 0.52 to 3.09 mg/kg with an average of 1.81 mg/kg. In contrast, root vegetables had higher concentrations, ranging from 6.11 to 78.93 mg/kg with an average of 25.69 mg/kg. Leafy vegetables presented concentrations between 0.61 and 47.40 mg/kg, averaging 25.67 mg/kg (Table S5). Consistent with the results reported by Zhang et al, our findings show comparable REE content in both leafy and root vegetables, suggesting that roots and lush foliage facilitate greater REE uptake from soils (Zhang et al., 2000a).
REE accumulation in vegetables near mining sites correlates with soil bioavailability. We conducted a systematic analysis using Spearman correlation matrices to investigate the migration characteristics of REEs in different vegetables. Our findings indicated significant positive correlations between the soil concentrations of Pr, Nd, Sm, Dy, Ho, Er and Tb and their presence (P < 0.05) in leafy vegetables (Fig. 3a). Root vegetables showed significant correlations with all soil REEs except Ce and Tm (P < 0.05, Fig. 3b) and solanaceae vegetables correlated significantly with all soil REEs except Tm, Lu, and Sc (P < 0.05, Fig. 3c). These findings suggest selective absorption and accumulation of REEs by different vegetable species.
Principal component analysis (PCA) of soil and vegetable samples revealed two distinct clusters along the first two principal components (PC1 and PC2), explaining 86.6% and 8.9% of the variance, respectively (Fig. 3). This analysis confirmed consistent REE distribution patterns across different sites, emphasizing their ecological interconnectedness. Notably, the PCA indicated distinct groupings of LREE and HREE in PC2, with Sc and Y being the most significant variable. Excluding Sc and Y, the remaining REEs significantly influenced PC1, demonstrating unique REE patterns for each vegetable variety despite identical soil and climate conditions.
Human health Risk Assessment
REEs are increasingly recognized as emerging pollutants due to their environmental persistence, bioaccumulation, and chronic toxicity (Queiros et al., 2023; Wang et al., 2023). Concerningly, REEs may adversely affect childhood neurodevelopment, potentially leading to reduced IQ and memory deficits (Wei et al., 2020). Previous study suggested that a daily REE intake of up to 70 µg/kg is generally safe for human health, but levels between 100 and 110 µg/kg/day could cause subclinical damage (Zhu et al., 1997). Consequently, it is essential to closely monitor the REE intake of residents near mining areas, particularly children aged 2 to 12 years, who are particularly vulnerable to pollutants through ingestion pathway.
Our study estimated that daily intake of REEs through vegetables significantly exceeded the safe threshold of 70 µg/kg/day for all age and gender groups. Notably, children aged 2 to 12 years were at the highest risk, with intake levels reaching 2.29 times (ages 2 to 7) and 1.73 times (ages 8 to 12) the subclinical threshold (Table 2). In contrast, individuals over 13 years exhibited intake levels near the risk threshold, with minimal variation across genders. Regarding water sources, REE concentrations were lower than in other mining regions such as Dingnan and Longnan counties, ranging from 2.00 to 6.87 µg/L with an average of 4.09 µg/L (Jin et al., 2014; Liu et al., 2019). Although the average daily intake (ADI) of REEs from water was significantly below the recommended limits, suggesting minimal risk (Table 3), the ADI from vegetables in children and adults consistently reached up to three times the subclinical threshold, indicating significant health risks. When adjusting for consumption frequency of different vegetable species, the daily cumulative REEs intake from selected vegetables was 49.46 µg/kg/day (Table 4), nearing the tolerable ADI of 51.5 µg/kg·BW set by the China Scientific Committee (Yang et al., 2022). Pakchoi and radish, which contribute 76.99% to the dietary REE risk, are of primary concern for residents in mining areas. It is important to note that the daily dietary intake also includes grains, meats, fruits, and other foods. For instance, Jin et al. reported that the daily cumulative intake of REEs through various crops and well water in mining areas reached up to 295.33 µg/kg (Jin et al., 2014). Given the high REE levels observed in studied soil and vegetables, further comprehensive risk assessment of REEs in daily diet is warranted.
Table 2
EDI of total REEs via vegetable consumption in mining areas by different gender and age groups
Gender/age group | BWa (kg) | CRa (g) | EDI |
2 ~ 7 years | 17.9 | 194.8 | 252.2 |
8 ~ 12 years | 33.1 | 272.4 | 190.7 |
Male, 13 ~ 19 years | 56.4 | 396.7 | 163.0 |
Female, 13 ~ 19 years | 50.0 | 317.9 | 147.3 |
Male, 20 ~ 50 years | 63.0 | 436.4 | 160.5 |
Female, 20 ~ 50 years | 56.0 | 412.1 | 170.5 |
Male, 51 ~ 65 years | 65.0 | 477.9 | 170.4 |
Female, 51 ~ 65 years | 58.0 | 447.0 | 178.6 |
Male, > 65 years | 59.5 | 413.3 | 160.9 |
Female, > 65 years | 52.0 | 364.1 | 162.2 |
Note: EDI: estimated daily intake, µg/kg/day. a Data were from the fifth China total diet study. |
Table 3
Average daily intake dose of REEs of local children and adults in mining area via vegetables and water
Group | Sample | Average content (mg/kg) | Days of consumption (days/year) | Daily consumption (kg) | Average bodyweight (kg) | Average daily intake (µg/kg/day) |
Children Adult | Vegetables | 23.17 | 365 | 0.22 0.85 | 15 60 | 339.83 338.24 |
Children Adult | Water | 4.09a | 365 | 1.10b 1.60b | 15 60 | 0.30 0.10 |
Note: a The unit of REEs in water is µg/L; b The unit of REEs in water daily consumption is L. |
Table 4
Adjusted ADI of REEs based on consumption frequency of different vegetable species
Vegetable species | Average content (mg/kg) | Days of consumptiona (days/year) | Daily consumption (kg) | Average daily intake (µg/kg/day) | Proportion (%) |
Pakchoi | 33.78 | 180 | 0.10 | 27.76 | 56.13 |
Radish | 11.31 | 100 | 0.20 | 10.33 | 20.88 |
Spinach | 17.56 | 60 | 0.05 | 2.41 | 4.86 |
Bamboo shoot | 8.16 | 30 | 0.10 | 1.12 | 2.26 |
Celery | 50.47 | 60 | 0.05 | 6.91 | 13.98 |
Water fennel | 9.34 | 30 | 0.05 | 0.64 | 1.29 |
Red pepper | 1.81 | 180 | 0.02 | 0.30 | 0.60 |
Total | | | | 49.46 | 100.00 |
Note: a Data were from a study conducted by Jin et al (Jin et al., 2014). |