4.6 Article

Capture and Release of Orthophosphate by Fe-Modified Biochars: Mechanisms and Environmental Applications

Journal

ACS SUSTAINABLE CHEMISTRY & ENGINEERING
Volume 9, Issue 2, Pages 658-668

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.0c06108

Keywords

autothermal pyrolysis; biochar; phosphate; ligand exchange; slow-release fertilizer; agricultural effluents

Funding

  1. Agriculture and Food Research Initiative Competitive grant from the USDA National Institute of Food and Agriculture [2018-10008-28616]

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This study engineered biochar for enhanced phosphorus sorption affinity by pre-treating corn stover biomass with FeSO4 and using autothermal pyrolysis. The resulting biochar (ISIB) showed significantly higher P sorption capacity compared to non-treated biochar, with inner-sphere surface complexation and surface precipitation as the main sorption mechanisms. ISIB was effective in removing P from agricultural effluent, suggesting its potential use as a slow-release P fertilizer.
Biochars have been suggested to have P capture potential from effluent streams and to recycle the captured P to agricultural soils. However, most biochars have low P sorption capacity. The objective of this study was to engineer biochar for enhanced P sorption affinity. Biochar was produced from corn stover biomass pre-treated with FeSO4 (ISIB) using autothermal (airblown) pyrolysis at 500 degrees C. Point of zero charge (pH(ZPC)) shifted from 8.48 to 4.31, indicating that Fe treatment increased the dominance of acid functional groups. Batch equilibration isotherm study showed that ISIB had 11-12 times more P sorption capacity (3763 versus 46,300 mg kg(-1) and 6704 versus 48,821 mg kg(-1) for non-oxidized and oxidized conditions, respectively), while P desorption rate was similar to 1/3 relative to the control biochar. A column leaching study also shows that ISIB was effective for removing P from simulated agricultural effluent. XRD (X-ray diffraction) and SEM-EDS (scanning electron microscopy-energy-dispersive X-ray spectrometry) analyses showed the P sorption was predominately through inner-sphere surface complexation followed by surface precipitation and that P is preferentially sorbed by hematite (alpha-Fe2O3) relative to magnetite (FeIII2O3 + FeIIO) or maghemite (gamma-Fe2O3). This study demonstrates that ISIB can be produced by pyrolyzing corn stover with FeSO4, and the resulting ISIB is effective for adsorption and recycling of P. When loaded with P, the ISIB can potentially be used as a slow-release P fertilizer.

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