Risk Assessment of Heavy Metal(loid)S Contamination in Agricultural Soil-Crop Systems in a Black Shale High Geologic Background Area

Zou H., Ren B.

Studies on soil contamination caused by waste sites near antimony mining areas are scarce. For environmental protection, it is critical to investigate the contamination levels, spatial distribution, and ecological risk assessment of heavy metals (HMs) in the surface soils of different land use types around waste sites and to identify related potential sources. In this study, the pollution status, spatial distribution, sources and ecological risks of Hg, Pb, Cd, Cr, As and Sb in the surface soils of built-up areas, woodlands and croplands around the waste sites of antimony mining areas were resolved for the first time by combining self-organizing maps (SOM), K-means clustering, geographic information systems (GIS) and positive matrix factorization (PMF). According to the analysis results of soil samples, the average abundance order of HMs is: Sb > As > Cd > Pb > Cr > Hg. The cumulative geological index defines Sb as a severe pollution level. The pollution index shows that Sb and Cd in all samples are above the severe pollution level. The pollution load index shows that 67.7% of soil samples are heavily polluted. SOM and K-means divided the studied elements into three clusters and were combined with GIS analysis to from Cd as cluster 1, Sb and As as cluster 2, and Pb, Hg and Cr as cluster 3. The PMF analysis yielded three potential sources of heavy metals: natural sources dominated by Hg, Pb and Cr (48.6%), direct sources caused by the accumulation of waste sites represented by Sb and As (32.9%) and mixed sources caused by human activities and transportation represented by Cd (18.5%). Ecological risk shows that the risk of construction area is prominent, and Sb is the main contribution element of high risk. This study combines multiple methods to investigate the current status of heavy metal pollution in the soil environment around antimony mine slag sites, providing a theoretical basis for better research on the pollution of heavy metals in the soil around antimony mine slag sites and source control, and contributing to the scarcity of antimony mine slag site pollution research.

Cui J., Zhou X., Chen Y., Zhang C., Xiao T., Wang Q., Zhou X., Chan T.

The high geogenic levels of trace metal(loid)s preserved within black shale can be released during natural weathering, causing global concern. Currently, the accumulation, speciation and potential mobilization of two highly toxic metal(loid)s, arsenic (As) and antimony (Sb), from black shale to soils remain unresolved, which hinders the evaluation of their potential risk to surrounding environments. Here, we demonstrate the geochemical enrichment, species transformation, and leaching behavior of As and Sb by applying weathering-induced alteration, sequential extraction and synchrotron-based X-ray absorption near edge spectroscopy (XANES) in the analysis of a range of black shale and weathered samples from two profiles collected from typical Cambrian sedimentary strata of the Pearl River Delta, southern China. The results showed significant accumulation of trace metal(loid)s, including As (43.8–458.0 mg/kg), Sb (7.2–34.5 mg/kg), Cu (8.8–451.0 mg/kg) and Ni (22.2–108.0 mg/kg), in the black shale and weathered products, and high enrichment factors for As (22.0–266.8) and Sb (1.2–6.4) were observed, consistent with the very high degrees of weathering (chemical index of alteration: 83–91). Arsenic in the shale was dominated by arsenate (46–85%), as identified using XANES, and this was resulted from extensive weathering, which facilitated the oxidation of arsenite and arsenopyrite species. Accordingly, significant decreases in sulfide-associated As and Sb were observed in highly weathered products. As a result, As and Sb were primarily in the immobilizable fractions associated with amorphous and well-crystallized Fe/Mn oxides, largely due to the increased formation of secondary Fe (oxyhydr)oxides, including goethite-like minerals, which mainly derived from the oxidative weathering of chlorite-like minerals. Nevertheless, high concentrations of As (

Zhang J., Guan H., Wang T., Du S., Xu J., Liu X.

Selenium (Se) is the essential component of selenoenzymes and contributes to antioxidant defenses. The capability of Se to antagonize the toxicity of heavy metals makes it an essential trace element for human and plant health. Soils derived from black shales are naturally enriched with Se; however, these soils often contain high geological cadmium (Cd), due to the weathering of black shales rich in Cd and Se. Cadmium, as a known Group I carcinogen, could induce damage to various organs. This therefore poses a major challenge for safe cultivation of Se-rich land resources. In this study, a total of 247 paired soil-crop samples were collected from a typical farmland derived from black shales. The concentrations of Cd and Se in the samples were analyzed by inductively coupled plasma mass spectroscopy and atomic fluorescence spectrometry. Monte Carlo simulation was applied to evaluate potential health risks associated with Cd exposure. Cadmium was the critical pollutant in the study area, with the average value of 1.53 mg/kg. Moreover, both children and adults living in the area had a significant non-carcinogenic health risk. Additional health risk assessments revealed that diet was the main contributor for both children and adults among the four pathways (diet > soil ingestion > soil dermal adsorption > soil inhalation). Furthermore, our results revealed that leguminous vegetables and maize were ideal for this site due to their high Se and low Cd accumulation abilities. These findings provide support for adjusting planting structure by variety screening to mitigate the health risk induced by Cd.

Zou H., Ren B., Deng X., Li T.

Few studies have addressed the contamination of surface soils around antimony tailings ponds, and studying the contamination levels and sources of potentially toxic elements (PTEs) in soils around antimony tailings ponds and assessing the associated environmental risks are key steps in conducting environmental protection. Therefore, this study is the first to investigate the current status, spatial distribution, potential sources and ecological risks of Pb, Sb, Cr, Zn, Cd, As and Cu contamination in surface soils in woodlands, grasslands, farmlands and construction areas around the Longwangchi antimony tailings pond in Hunan, China. According to the analytic results of soil samples, the order of PTEs in terms of average concentration is: Sb > Zn > Cu > Pb > As > Cr > Cd. The cumulative index of land was applied to define Sb and Cd as extremely heavy pollution, and PLI divides the overall pollution level of soil into serious pollution levels. The ecological risk index was used to evaluate the risk characteristics of PTEs. The results showed that the ecological risk of Sb was particularly prominent, and 95% of the study area had reached a very high risk level. A quantitative comparison of ecological risk levels between different land uses revealed that there was a clear dividing line between regions, with built-up areas contributing the most to higher ecological risk at 8.89%, followed by 1.72% for grassland, 1.15% for agricultural land, and 0.57% for woodland. The visualization results of spatial distribution of PTEs exhibited that severe pollution occurred in the middle, north and southeast of the study area, and these distribution characteristics are mainly dictated by the polluted runoffs from tailings ponds and human activities. Principal component analysis (PCA) and positive matrix decomposition (PMF) were employed to identify the exact pollution sources, and the closer the determination coefficient (R2) of PMF was to 1, the finer the pollution sources analyzed. A total of six potential sources of PTEs were analyzed by PMF: 36% of tailings pond contamination and mining operations, 8% atmospheric deposition, 19% traffic emissions, 9% combustion emissions, 11% natural sources, and 17% inputs related to agricultural production. This study is a complement to the study of environmental pollution around antimony tailing ponds, providing evaluation criteria for the pollution identification indicators of antimony tailing ponds.

Wei W., Ling S., Wu X., Li X.

Heavy metal enrichment in soils has been linked to the weathering of lithologies with high geochemical backgrounds, such as black shale. Therefore, this study conducted a typical sampling of surface soils in a black shale catchment in southwestern China to characterize the accumulation and sources of the heavy metals As, Cd, Co, Cr, Cu, Ni, Pb, Zn, Mo and Tl. Elevated concentrations of most heavy metals in the soils underlain by black shale are determined to exceed the regional soil background values, even the risk screening values, especially for Mo, As and Cd. Sequential extraction analysis, together with previous results, reveals that most heavy metals in soils are mainly bound in the residual fraction (> 65 %) as a result of the fixation of stable aluminosilicates (e.g., clay minerals). In contrast, Cd mainly occurs in relatively labile proportions as exchangeable (24.42 %), carbonate (24.48 %) and Fe/Mn oxide fractions (26.60 %) due to the non-specific adsorption of soil colloids and the precipitation of carbonates and Fe/Mn oxides. Pb isotopic tracing and APCS/MLR receptor model suggest that heavy metals in the urban surface soils (SG1) have a mixed source of black shale weathering, vehicle exhaust and agricultural input, while heavy metals in the rural surface soils (SG2) are a geogenic source of black shale weathering. Overall, this study provides new insights into contamination management, land use planning and health risk assessment in regions with high geochemical backgrounds.

Natasha N., Shahid M., Murtaza B., Bibi I., Khalid S., Al-Kahtani A.A., Naz R., Ali E.F., Niazi N.K., Rinklebe J., Shaheen S.M.

There are scarce data about the accumulation pattern and risk assessment of potentially toxic elements (PTEs) in soil and associated potential ecological risks, especially in less-developed countries. This study aims to assess the pollution levels and potential ecological risks of PTEs (As, Cr, Cd, Cu, Ni, Mn, Pb and Zn) in wastewater-irrigated arable soils and different edible-grown plants in selected areas of Vehari, Pakistan. The results revealed that the values of PTEs in soil samples were higher than their respective limit values by 20% for As, 87% for Cd, 15% for Cu, 2% for Cr, 83% for Mn, 98% for Fe, and 7% for Zn. The values of soil risk indices such as the potential ecological risk (PERI >380 for all samples), pollution load index (PLI >4 for 94% of studied samples), and degree of contamination (Dc > 24 for all samples) showed severe soil contamination in the study area. Some vegetables exhibited a high metal accumulation index (e.g., 8.1 for onion), signifying potential associated health hazards. Thus, long-term wastewater irrigation has led to severe soil contamination, which can pose potential ecological risks via PTE accumulation in crops, particularly Cd. Therefore, to ensure food safety, frequent wastewater irrigation practices need to be minimized and managed in the study area.

Xie Q., Ren B.

Xikuangshan (XKS) is the world's largest antimony mining region, and its exploitation for hundreds of years has also resulted in serious soil erosion, fragile ecology, contaminated water, and shortage water. Through systematic and scientific collection samples from the rivers in XKS, the Nemerow index (NI), modified heavy metal pollution index (m-HPI), ecological risk index, and health risk indexeswere used to evaluate and analyze the water quality, pollution levels and risks of heavy metals (Sb, As, Mn, Pb, Zn, Hg, Cd) to ecology and humans in XKS. The results showed that the average concentrations of TN, TP, Sb, As and Hg in surface water were 0.48 mg/L (0–4.34 mg/L), 2.58 mg/L (0–4.34 mg/L), 1.05 mg/L (0.0009–5.33 mg/L), 1.06 mg/L (BDL–19.60 mg/L) and 0.00084 mg/L (LDBL–0.0036 mg/L), respectively, exceeding the limits of the Chinese surface water quality standards. Based on the m-HPI method, only 8.57% of the sampling points are classified as the worst water quality. However, according to the NI method, about 7.14% and 87.16% of the sampling points in the study area are moderately and severely polluted, respectively. The results of heavy metal pollution based on the NI evaluation is were more serious than that on the m-HPI method. The values of ecological risk assessment varied from 22.69 to 7351.20, revealed that heavy metals pose a very serious risk to the surface water ecosystem at more than 50% of the sampling sites, and Sb and As are the main pollutants, followed by Hg. The total non-carcinogenic risk index (TCR) for adults and children were 47.70 and 90.10 respectively, Sb and As is the main non-carcinogenic risk factor. For adults and children, the average carcinogenic risk (CR) of As was 6.49 × 10–3 and 1.05 × 10–2, respectively, and exceeded the threshold of 1 × 10–4, indicating a high carcinogenic risk.

Liu Y., Chen Z., Xiao T., Zhu Z., Jia S., Sun J., Ning Z., Gao T., Liu C.

The enrichment of cadmium (Cd) in black shale–derived soils is of increasing concern due to its wide occurrence, high Cd concentrations, and potential risks. However, characteristics of enrichment and environmental availability of Cd in these soils are not well understood, which has restricted pollution control and land management. In this study, agricultural soils with elevated Cd concentrations resulting from weathering of Cd-bearing black shale in southwestern China were collected and analyzed. The results showed that Cd could be retained in soils through mechanical inheritance and/or associated with secondary minerals and organic materials. Cd concentrations in soils of the study area ranged between 0.83 and 21.6 mg/kg (average of 5.20 mg/kg), exceeding the risk screening value for agricultural land in China. The heterogeneity of Cd in these soils was highly related to geochemical composition of parent rock and other natural factors. The 0.01 M CaCl2 and 0.05 M EDTA extraction showed that Cd in these soils had high environmental availability and potential risks. Mobile Cd pool (CaCl2 extractable Cd, average: 0.24 mg/kg) accounted for 0.07–38.9% of the total Cd, depending on soil pH. Mobilizable Cd pool (EDTA extractable Cd, average: 2.18 mg/kg) accounted for 22.0–100%. These results showed the significance of geochemical background on enrichment of Cd in soils, documented high environmental availability of Cd in black shale–derived soils, and influence of soil pH.

Yang Q., Yang Z., Filippelli G.M., Ji J., Ji W., Liu X., Wang L., Yu T., Wu T., Zhuo X., Zhang Q.

Karst environments are globally significant, and the soils that develop on these landscapes often have unique geochemical features, including elevated–levels of metals. However, it has not been determined whether the enrichment of metals in soils is mainly controlled by parent rocks or secondary enrichment during weathering. In this paper, we studied the control of the accumulation of heavy metals in soils by parent materials and/or the process of soil formation. We examined the un–weathered carbonate and clastic bedrocks, as well as surface soils in a typical karst area in Guangxi of China. The spatial distribution of heavy metal (Cd, As, Cr, Cu, Hg, Ni, Pb, and Zn) concentrations in soils was mainly controlled by the geological background. Except for Cd, the concentrations of heavy metals in carbonate rocks were much lower than those in clastic rocks, whereas the soils derived from the carbonate rocks were highly enriched with heavy metals than those in clastic area. The enrichment of Cd in surface soils from the carbonate substrates was the result of the dual effect of secondary enrichment and parent rock inheritance, whereas the enrichment of other metals was mainly the result of secondary enrichment. During the weathering process of carbonate bedrock, great majority of the quantities of inherent heavy metals were leached, with only 2% of Cd being retained in situ . The high concentrations of soil Fe, Al, and Mn oxides, organic carbon and clay content (Al 2 O 3 /SiO 2 ) were closely related to the enrichment of heavy metals in studied surface soils. • Geological background controlled spatial distribution of soil metal concentrations. • Secondary enrichment and bedrock inheritance caused Cd enrichment in karstic soil. • Secondary enrichment caused the other metal (As, Cr, Cu, Hg, Ni, Pb, and Zn) enrichment in karstic soil. • 2% of Cd being retained in situ during the weathering of carbonate bedrock. • Soil Fe/Al/Mn oxides, organic carbon and clay content controlled metal accumulation in soils.

Shi X., Ren B.

• Indirect three-dimensional soil manganese transport simulation. • Non-point source pollution caused by rain in abandoned mining areas can pollute soil and groundwater. • Highest manganese concentration is in the east and the west, and the lowest in the south and north. • Vertical transport is more important than horizontal transport in the regional study. • High concentration areas should be repaired first, and other mining areas should mind rainwater pollution.

Zhong C., Feng Z., Jiang W., Xiao L., Zhang X., Zhao Y., Lin Q.

Recently, the cadmium (Cd) accumulation in the black shale area has attracted increasing attentions, due to its extensive distribution and extremely high background values. The aim of our study is to explore the impacts of soil properties on Cd uptake by rice, and identify the key factors of Cd transfer from soil to rice in the black shale area. A total of 40 pairs of topsoil and rice samples were collected from the paddy fields in the black shale area and the control area. The relevant parameters in the soils, as well as the Cd concentrations in different rice tissues, were analyzed. The results show that 87.5% of the soil samples in the study area exceed the risk screening values of Cd, and 42% of the rice grain samples exceed the allowable limit of Cd. The key factor influencing Cd uptake by rice in this area is the soil phytoavailable Cd concentration. Compared to those in the control area, the soils in the black shale area have a much higher Cd level but a lower phytoavailability due to the higher pH, which is caused by carbonate. Even so, the level of Cd in the rice from the black shale area indicates a much higher ecological risk. Soil pH and iron (Fe) are the most important variables exhibiting direct effects on Cd fractions in soils. In light of the neutral or weakly alkaline soil in the black shale area, we concluded that increasing the soil pH was not a feasible way to reduce Cd levels in the rice in this area.

Wang H., Li X., Chen Y., Li Z., Hedding D.W., Nel W., Ji J., Chen J.

Basalt-derived agricultural soil is widely distributed around the world and is extensively used as a medium to plant many kinds of crops. Weathering of basalt can release heavy metals into the soils and may cause health risks via the food chain. However, the geochemical behavior and the potential human health risks of heavy metals remain poorly understood in these agro-systems. In this study, basalt bedrock, paired topsoil and crops (wheat and rice) samples were collected from a basaltic area located in Xuyi County, eastern China. Concentrations and bioavailability of heavy metals in the basalt-topsoil-crop system were measured to determine their geochemical behavior during the weathering and transfer processes as well as their potential risk to human health. Our results showed that basalt and topsoil were characterized by high levels of Ni, Cr and Zn. Topsoil and crop grains were highly polluted by Ni, and Ni accumulated more readily in rice grains than in wheat grains. Nickel, a high-risk metal in topsoil was mainly derived from the basalt bedrock, and its enrichment in topsoil was significantly related to the Fe oxide content of the soils. The accumulation of Ni in crop grains was mainly controlled by soil pH, and the 0.01 M CaCl2 extractable Ni was a good indicator in predicting Ni accumulation in crop grains. Risk analysis revealed that there are significant health risks to local inhabitants if rice grains contaminated with heavy metals are ingested. To our best knowledge, this is the first study to investigate the flow of heavy metals in a basalt-topsoil-crop-human system that focuses on geochemical behavior and human health risk. This study will aid the strategic design of evaluation and remediation protocols for basaltic soil.

Nganje T.N., Edet A., Cuthbert S., Adamu C.I., Hursthouse A.S.

Potentially toxic elements (PTEs) are present in some natural geological materials and the black shales of southeastern Nigeria provides an example of this. The concentration and distribution of these PTEs such as Cd and Pb in shale rocks and soil-water-plant systems are spatially examined in this study. Geochemical surveys were undertaken in 6 shale formations. Some PTEs are highly enriched in the black shales (Mo, Se, Tl, and Zn) and soils (As, Cd, Cr, Cu and Zn). Acknowledged pollution indices revealed various levels of soil, water and crop plants contamination by PTEs. Distribution of PTEs may be attributed to differences in geochemical nature of shale formations and degree of weathering. The concentrations may also be modified by varying degree of pedogenetic processes that may lead to mobility and redistribution of PTEs in soil. Health risk assessment of the population, based on the Hazard quotients (HQ) and indices (HI), identified minimal or no risk for drinking water consumption in the area. The cancer risk from As for individuals exposed through the soil and stream water pathways did not exceed the acceptable risk of 1 in 10,000 set for regulatory purposes. This study has provided data for the development, demobilization and implementation of a monitoring system and management of PTEs from shale bedrock.

Jiang F., Ren B., Hursthouse A., Deng R.

Thallium (Tl) has a high relative toxicity and is easily taken up by plants, but little is known about wider relationship with co-contaminants and in typical domestic food crops. We evaluated the extent of contamination, evidence for bioaccumulation in typical food crops (Chinese cabbage, green cabbage, chili, carrot, corn and rice), and subsequent contribution to health risks for 7 elements (Tl, As, Cd, Pb, Ni, Cu, Zn) associated with soil contamination in the local soils of a major Tl mine in Guizhou, southwest China. Derivation of relevant risk indicators from the bioconcentration factor (BCF), comprehensive crop pollution index (P), the target hazard quotient (THQ) (element), and the hazard index (HI) (all elements) were assessed as tools to support the evaluation. Our results showed that the degree of contamination and uptake by crops in the study area were: root vegetables > leaf vegetables > fruit vegetables > cereals. With the exception of corn, other crops pose a significant risk to human health which is dominated by the Tl content. In addition, the Cu in carrot samples suggests hyperaccumulation at the site and poses a high risk to human health. The results provide direct evidence of significant food chain exposure and identifies the need for Tl-focused management of soil/plant interaction and that strategy needs to also understand the implications for behavior of co-contaminants in the area.

Luo X., Ren B., Hursthouse A.S., Jiang F., Deng R.

The pollution from large-scale manganese mining and associated industries in Xiangtan (south Central China) has created a significant burden on the local environment. The proximity of mining, and other industrial activity to the local population, is of concern and impact of past industrial on the food chain was evaluated by the assessment of common food groups (rice, soybean, and sweet potato), and the associated soil and water in the region. We focused on specific potentially toxic elements (PTEs): Mn, Pb, Cd, Cr, Cu, and Zn associated with industrial activity, identifying the distribution of pollution, the potential significance of total health index (THI) for local people and its spatial distribution. The study area showed severe contamination for Mn, followed by Cd and Pb, while other PTEs showed relatively light levels of pollution. When analyzing the impact on crops exceeding the tolerance limit, the dominant PTEs were Mn, Cd, and Pb, with lower significance for Zn, Cu, and Cr. The average THI value for adults is 4.63, while for children, is 5.17, greatly exceeding the recommended limit (HQ > 1), confirming a significant health risk. In the spatial distribution of the THI, the region shows strong association with the transport and industrial processing infrastructure. Long-term management needs to consider remediation aligned to specific industrial operations and enhance contamination control measures of ongoing activity.