Colloidal fraction on pomelo peel-derived biochar plays a dual role as electron shuttle and adsorbent in controlling arsenic transformation in anoxic paddy soil.

Arsenic release and reduction in anoxic environments can be mitigated or facilitated by biochar amendment. However, the key fractions in biochars and how they control arsenic transformation remain poorly understood. In this study, a biochar produced from pomelo peel was rich in colloids and was used to evaluate the roles of the colloidal and residual fractions of biochar in arsenic transformation in anoxic paddy soil. Bulk biochar showed a markedly higher maximum adsorption capacity for As(III) at 1732 mg/kg than for As(V) at 75.7 mg/kg, mainly because of the colloidal fraction on the surface. When compared with the control and treatments with the colloidal/residual fraction, the addition of bulk biochar facilitated As(V) reduction and release in the soil during days 0-12, but decreased the dissolved As(III) concentration during days 12-20. The colloidal fraction revealed significantly higher electron donating capacity (8.26 µmole-/g) than that of bulk biochar (0.88 µmole-/g) and residual fraction (0.65 µmole-/g), acting as electron shuttle to promote As(V) reduction. Because the colloidal fraction was rich in aliphatic carbon, fulvic acid-like compounds, potassium, and calcium, it favored As(III) adsorption when more As(III) was released, probably via organic-cation-As(III) complexation. These findings provide deeper insight into the role of the colloidal fraction of biochar in controlling anaerobic arsenic transformation, which will be helpful for the practical application of biochar in arsenic-contaminated environments.

Effects of zero-valent iron added in the flooding or drainage process on cadmium immobilization in an acid paddy soil.

Zero-valent iron (ZVI) is a promising material for the remediation of Cd-contaminated paddy soils. However, the effects of ZVI added during flooding or drainage processes on cadmium (Cd) retention remain unclear. Herein, Cd-contaminated paddy soil was incubated for 40 days of flooding and then for 15 days of drainage, and the underlying mechanisms of Cd immobilization coupled with Fe/S/N redox processes were investigated. The addition of ZVI to the flooding process was more conducive to Cd immobilization. Less potential available Cd was detected by adding ZVI before flooding, which may be due to the increase in paddy soil pH and newly formed secondary Fe minerals. Moreover, the reductive dissolution of Fe minerals promoted the release of soil colloids, thereby increasing significantly the surface sites and causing Cd immobilization. Additionally, the addition of ZVI before flooding played a vital role in Cd retention after soil drainage. In contrast, the addition of ZVI in the drainage phase was not conducive to Cd retention, which might be due to the rapid decrease in soil pH that inhibited Cd adsorption and further immobilization on soil surfaces. The findings of this study demonstrated that Cd availability in paddy soil was largely reduced by adding ZVI during the flooding period and provide a novel insight into the mechanisms of ZVI remediation in Cd-contaminated paddy soils.

A small extent of seawater intrusion significantly enhanced Cd uptake by rice in coastal paddy fields.

Paddy fields located around estuaries suffer from seawater intrusion, and how and to what extent salinity levels influence Cd accumulation in rice grains is still unclear. Pot experiments were carried out by cultivating rice under alternating flooding and drainage conditions with different salinity levels (0.2‰, 0.6‰ and 1.8‰). The Cd availability was greatly enhanced at 1.8‰ salinity due to the competition for binding sites by cations and the formation of Cd complexation with anions, which also contributed to Cd uptake by rice roots. The soil Cd fractions were investigated and found that the Cd availability significantly decreased during flooding stage, while it rapidly increased after soil drainage. During drainage stage, Cd availability was greatly enhanced at 1.8‰ salinity mainly attributed to the formation of CdCln2-n. The kinetic model was established to quantitatively evaluate Cd transformation, and it found that the release of Cd from organic matter and Fe-Mn oxides was greatly enhanced at 1.8‰ salinity. The results of pot experiments showed that there was a significant increase in Cd content in rice roots and grains in the treatment of 1.8‰ salinity, because the increasing salinity induced an increase in Cd availability and upregulation of key genes regulating Cd uptake in rice roots. Our findings elucidated the key mechanisms by which high salinity enhanced Cd accumulation in rice grains, and more attention should be given to the food safety of rice cultivated around estuaries.

Chromium transformation driven by iron redox cycling in basalt-derived paddy soil with high geological background values.

The flooding and drainage of paddy fields has great effects on the transformation of heavy metals, however, the transformation of Cr in basalt-derived paddy soil with high geological background values was less recognized. The typical basalt-derived paddy soil was incubated under alternating redox conditions. The Cr fractions and the dynamics of Fe/N/S/C were examined. The HCl-extractable Cr increased under anaerobic condition and then decreased during aerobic stage. The UV-vis spectra of the supernatant showed that amounts of colloids were released under anaerobic condition, and then re-aggregated during aerobic phase. The scanning transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) revealed that Fe oxides were reduced and became dispersed during anaerobic stage, whereas Fe(II) was oxidized and recrystallized under aerobic condition. Based on these results, a kinetic model was established to further distinguish the relationship between the transformation of Cr and Fe. During anaerobic phase, the reduction of Fe(III) oxides not only directly released the structurally bound Cr, but also enhanced the breakdown of soil aggregation and dissolution of organic matter causing indirect mobilization of Cr. During aerobic phase, the oxidation of Fe(II) and further recrystallization of newly formed Fe(III) oxides might induce the re-aggregation of soil colloids and further incorporation of Cr. In addition, the kinetic model of Cr and Fe transformation was further verified in the pot experiment. The model-based findings demonstrated that the Cr transformation in the basalt-derived paddy soil with high geological background values was highly driven by redox sensitive iron cycling.

Seawater intrusion induced cadmium activation via altering its distribution and transformation in paddy soil.

Seawater intrusion can cause environmental risks to paddy soils around estuaries, but the impacts on the availability of heavy metals are still unclear. River water and sea water were collected along the river of an estuary. A stirred-flow experiment was conducted to examine the Cd desorption behavior in Cd-contaminated paddy soil. While the pH increased with increasing salinity levels, more Cd was released with increasing salinity, suggesting that Cd competition by cations and complexation by anions, but not pH, dominated the release of Cd from soils. Moreover, paddy soil was incubated at different salinities under alternating redox conditions. The availability of Cd, as indicated by the diffusive gradients in thin film (DGT), became relatively high with increasing salinity levels during the initial anaerobic and later aerobic stages. The available Cd fractions substantially decreased under anaerobic condition, and then rapidly increased under aerobic condition. When oxygen was introduced into the system, Cd associated with organic matter and Fe-Mn oxides were released, and oxidative dissolution of Cd sulfides was observed, especially in the high salinity treatment. Seawater intrusion affects biogeochemical cycles and can promote rapid export of NH4+, Fe2+, and SO42- in paddy soils, especially in soils with high salinity. Our findings demonstrated that the high salinity content in paddy soil significantly enhanced the availability of Cd, especially during the drainage stage.

Effects of water salinity on cadmium availability at soil-water interface: implication for salt water intrusion.

Low-lying paddy fields in estuaries can be affected by salt water intrusion; however, it remains unclear how salt water intrusion influences the availability of heavy metals in paddy soil. In this study, batch adsorption and incubation experiments of soil were conducted with different salt water sampled along the estuary to investigate the effects of salt water intrusion on cadmium (Cd) availability. The surface complexation model (SCM) was established to assess the effects of pH on Cd adsorption behavior, which presented typical pH-dependent characteristics. The results of SCM also showed that Cd-chloro complexes became the dominant species when the ionic strength increased. The results of Cd fractions in the incubation experiments revealed a significant increase in dissolved Cd with increasing ionic strength. This may be attributed to the increased point of zero charge (pHpzc) in the presence of salt water with higher salinity, which likely formed more positive charges on soil surfaces, causing an inhibition of Cd adsorption via electrostatic repulsion. Moreover, higher concentrations of Cl- in salt water favored the formation of Cd-chloro complexes, facilitating Cd release from soil particles. This study provides mechanistic insights into the impact of salt water intrusion on Cd availability at the soil-water interface of paddy soil along the estuary.