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Purpose Biochar amendments can alter phosphorus (P) availability in soils, though the influencing mechanisms are not yet fully understood. This work investigated the adsorption and desorption of P on ferrihydrite (F, a Feoxide widely distributed in surface environments) in order to evaluate the interactions between P and Fe-oxide in the absence or presence of biochar (F or ferrihydrite-biochar (F-B) interaction) in soils. Materials and methods Biochar was produced by pyrolysis of rice straw at 600°C in steel ring furnaces. Two-line ferrihydrite was synthesized by dropwise addition of 1 mol L −1 KOH into Fe(NO 3 ) 3 solution until the pH reached 7-8 while stirring vigorously. An F-B complex was prepared under similar conditions, except that a mixture of 10 g biochar and the Fe(NO 3 ) 3 solution was used as the starting material instead of Fe(NO 3 ) 3 alone. A batch equilibration method was used to determine sorption or desorption of P. The mechanisms of P adsorption on F and F-B complex materials were discussed. Results and discussion Adsorption of P on F decreased as the pH was increased from 3.0 to 10, but the adsorption capacity of F decreased by about 30-40% in the presence of biochar. The P chemisorption rates on F also decreased in the presence of biochar. The Freundlich model showed that the active adsorption sites on the surface of the F-B complex were energetically heterogeneous. The desorbability of adsorbed P on F was enhanced by combination with biochar. The mechanisms of P adsorption on F and F-B complex materials are different.Conclusions The results showed that the amount and rate of P adsorption on the surface of ferrihydrite decreased with the presence of biochar, and the desorbability of adsorbed P on ferrihydrite can be enhanced when combined with biochar. Thus, the presence of biochar can decrease P adsorption on the Fe-oxides and enhance P availability in soils.

Summary• In order to gain insights into the transport and distribution of arsenic (As) in intact rice (Oryza sativa) plants and its unloading into the rice grain, we investigated the spatial distribution of As and the temporal variation of As concentration in whole rice plants at different growth stages. To the best of our knowledge, this is the first time that such a study has been performed.• Inductively coupled plasma mass spectroscopy (ICP-MS) and high-performance liquid chromatography (HPLC)-ICP-MS were used to analyze total As concentration and speciation. Moreover, synchrotron-based X-ray fluorescence (SXRF) was used to investigate in situ As distribution in the leaf, internode, node and grain.• Total As concentrations of vegetative tissues increased during the 2 wk after flowering. The concentration of dimethylarsinic acid (DMA) in the caryopsis decreased progressively with its development, whereas inorganic As concentration remained stable. The ratios of As content between neighboring leaves or between neighboring internodes were c. 0.6. SXRF revealed As accumulation in the center of the caryopsis during its early development and then in the ovular vascular trace.• These results indicate that there are different controls on the unloading of inorganic As and DMA; the latter accumulated mainly in the caryopsis before flowering, whereas inorganic As was mainly transported into the caryopsis during grain filling. Moreover, nodes appeared to serve as a check-point in As distribution in rice shoots.

The relationship between vacant Mn structural sites in birnessites and heavy-metal adsorption is a current and important research topic. In this study, two series of birnessites with different average oxidation states (AOS) of Mn were synthesized. One birnessite series was prepared in acidic media (49.6–53.6 wt.% Mn) and the other in alkaline media (50.0–56.2 wt.% Mn). Correlations between the Pb2+ adsorption capacity and the d110 interlayer spacing, the AOS by titration, and the release of Mn2+, H+, and K+ during adsorption of Pb2+ were investigated. The maximum Pb2+ adsorption by the birnessites synthesized in acidic media ranged from 1320 to 2457 mmol/kg with AOS values that ranged from 3.67 to 3.92. For birnessites synthesized in alkaline media, the maximum Pb2+ adsorption ranged from 524 to 1814 mmol/kg, with AOS values between 3.49 and 3.89. Birnessite AOS values and Pb2+ adsorption increased as the Mn content decreased. The maximum Pb2+ adsorption to the synthetic birnessites calculated from a Langmuir fit of the Pb adsorption data was linearly related to AOS. Birnessite AOS was positively correlated to Pb2+ adsorption, but negatively correlated to the d110 spacing. Vacant Mn structural sites in birnessite increased with AOS and resulted in greater Pb2+ adsorption. Birnessite AOS values apparently reflect the quantity of vacant sites which largely account for Pb2+ adsorption. Therefore, the Pb2+ adsorption capacity of birnessite is mostly determined by the Mn site vacancies, from which Mn2+, H+, and K+ released during adsorption were derived.