Assessing the fractionation and bioavailability of heavy metals in soil-rice system and the associated health risk.

This study developed a method to build relationships between chemical fractionations of heavy metals in soils and their accumulations in rice and estimate the respective contribution of each geochemical speciation in the soils from the Yangtze River Delta, China. In contaminated areas, residue and humic acid-bound fractions in soils were the main phases for most heavy metals. The mobility of heavy metals was in this following order: Cd > Pb ≈ Zn > Ni > As ≈ Cr > Hg. Transfer factors calculated by the ratios of specific fractionations of heavy metals in the soil-rice system were used to assess the capability of different metal speciation transfer from soil to rice. The carbonate and Fe/Mn oxyhydroxides bound phase had significant positive correlations with total metal concentrations in rice. Hg uptake by rice might be related to the exchangeable and carbonate-bound fractions of soil Hg. Results of PCA analysis of transfer factors estimated that the labile fractions (i.e. water soluble, exchangeable and carbonate bound) contributed more than 40% of the heavy metal accumulations in rice. Effect of organic matter and residue fraction on metals transfer was estimated to be ~ 25 to ~ 30% while contribution of humic acid and Fe/Mn oxyhydroxides-bound fractions was estimated to be ~ 20 to ~ 30%. Modified risk assessment code (mRAC) and ecological contamination index (ECI) confirmed that the soil samples were polluted by heavy metals. Soil Cd contributed more than 80% of mRAC. Contrarily, the main contributors to ECI were identified as As, Hg, Pb and Zn. The average values of total target hazard quotient (TTHQ) and Risktotal were above 1 and 10-4 respectively, implying people living in the study area were exposed to both non-carcinogenic and carcinogenic risk. As and Pb were the main contributor to high TTHQ value while As, Cd and Cr in rice contributed mostly to Risktotal value. Spatial changes of ecological risk indexes and human health risk indexes showed that the samples with high TTHQ values distributed in the area with high values of mRAC. Likewise, the area with high ECI values and with high carcinogenic risk overlapped.

Evaluation of various approaches to predict cadmium bioavailability to rice grown in soils with high geochemical background in the karst region, Southwestern China.

Evaluating the bioavailability of Cd to rice (Oryza sativa L.) was essential in the karst region, Southwestern China, where the soils have previously been shown to be anomalously enriched in Cd through geogenic processes. In this research, we examined the bioavailability of Cd to rice samples collected from 278 sites in Guangxi province, where rice is the most widely cultivated cereal crop that is responsible for the largest human dietary exposure to Cd. Both soil chemical extraction and soil-plant transfer modelling approaches were used to predict the bioavailability to rice. Some of the soil types were highly enriched in Cd, but their bioavailability was low, since the soil carbonates raised soil pH and remarkably reduced Cd bioavailability. In contrast, acidic soils (Ca was largely leached) with relatively low total Cd, the grown rice plants accumulated higher Cd in their grains. Results from CaCl2 extraction experiments provided good predictions for Cd in rice grain grown in soils of different types. Stepwise multiple regressions revealed soil pH and soil Ca content were the dominant factors that control the transfer of Cd from soil to rice. An extended Freundlich-type model and a polynomial surface model provided good prediction for Cd in rice grains. The diffusive gradients in thin films (DGT) technique gave the best estimation of soil Cd bioavailability, whereas water-extracted soil solution Cd provided relatively poor fits. Regional soil threshold that derived using the models, can avoid exceedance of Cd in rice and thereby enable local agricultural practitioners or authorities to develop appropriate management for croplands with high Cd background.