Optimizing bone and biomass co-torrefaction parameters: High-performance arsenic removal from wastewater via co-torrefied bone char.

This study aimed to investigate bone char's physicochemical transformations through co-torrefaction and co-pyrolysis processes with biomass. Additionally, it aimed to analyze the carbon sequestration process during co-torrefaction of bone and biomass and optimize the process parameters of co-torrefaction. Finally, the study sought to evaluate the arsenic sorption capacity of both torrefied and co-torrefied bone char. Bone and biomass co-torrefaction was conducted at 175 °C-300 °C. An orthogonal array of Taguchi techniques and artificial neural networks (ANN) were employed to investigate the influence of various torrefaction parameters on carbon dioxide sequestration within torrefied bone char. A co-torrefied bone char, torrefied at a reaction temperature of 300 °C, a heating rate of 15 °C·min-1, and mixed with 5 g m of biomass (wood dust), was selected for the arsenic (III) sorption experiment due to its elevated carbonate content. The results revealed a higher carbonate fraction (21%) in co-torrefied bone char at 300 °C compared to co-pyrolyzed bone char (500-700 °C). Taguchi and artificial neural network (ANN) analyses indicated that the relative impact of process factors on carbonate substitution in bone char followed the order of co-torrefaction temperature (38.8%) > heating rate (31.06%) > addition of wood biomass (30.1%). Co-torrefied bone chars at 300 °C exhibited a sorption capacity of approximately 3 mg g-1, surpassing values observed for pyrolyzed bone chars at 900 °C in the literature. The findings suggest that co-torrefied bone char could serve effectively as a sorbent in filters for wastewater treatment and potentially fulfill roles such as a remediation agent, pH stabilizer, or valuable source of biofertilizer in agricultural applications.

A comprehensive study of artificial neural network for sensitivity analysis and hazardous elements sorption predictions via bone char for wastewater treatment.

Using bone char for contaminated wastewater treatment and soil remediation is an intriguing approach to environmental management and an environmentally friendly way of recycling waste. The bone char remediation strategy for heavy metal-polluted wastewater was primarily affected by bone char characteristics, factors of solution, and heavy metal (HM) chemistry. Therefore, the optimal parameters of HM sorption by bone char depend on the research being performed. Regarding enhancing HM immobilization by bone char, a generic strategy for determining optimal parameters and predicting outcomes is crucial. The primary objective of this research was to employ artificial neural network (ANN) technology to determine the optimal parameters via sensitivity analysis and to predict objective function through simulation. Sensitivity analysis found that for multi-metals sorption (Cd, Ni, and Zn), the order of significance for pyrolysis parameters was reaction temperature > heating rate > residence time. The primary variables for single metal sorption were solution pH, HM concentration, and pyrolysis temperature. Regarding binary sorption, the incubation parameters were evaluated in the following order: HM concentrations > solution pH > bone char mass > incubation duration. This approach can be used for further experiment design and improve the immobilization of HM by bone char for water remediation.

First principal observation documenting the three-dimensional uptake of cadmium and spatial distribution of cadmium hydroxyapatite mineral in bone char.

The 3-D matrix scale ion-exchange mechanism was explored for high-capacity cadmium (Cd) removal using bone chars (BC) chunks (1-2 mm) made at 500 °C (500BC) and 700 °C (700BC) in aqueous solutions. The Cd incorporation into the carbonated hydroxyapatite (CHAp) mineral of BC was examined using a set of synchrotron-based techniques. The Cd removal from solution and incorporation into mineral lattice were higher in 500BC than 700BC, and the diffusion depth was modulated by the initial Cd concentration and charring temperature. A higher carbonate level of BC, more pre-leached Ca sites, and external phosphorus input enhanced Cd removal. The 500BC showed a higher CO32-/PO43- ratio and specific surface area (SSA) than the 700BC, providing more vacant sites by dissolution of Ca2+. In situ observations revealed the refilling of sub-micron pore space in the mineral matrix because of Cd incorporation.The X-ray nanodiffraction (XND) analyses revealed that Cd was mainly removed from water by incorporation into the mineral lattice of 500BC via ion exchange, rather than surface sorption and precipitation, and the mineral phase was transformed from hydroxyapatite (HAp) to cadmium hydroxyapatite (Cd-HAp). The Rietveld's refinement of X-ray diffraction (XRD) data resolved up to 91% of the crystal displacement of Ca2+ by Cd2+. The specific phase and stoichiometry of the new Cd-HAp mineral was dependent on the level of ion exchange. This mechanistic study confirmed that 3-D ion exchange was the most important path for heavy metal removal from aqueous solution and immobilization in BC mineral matrix, and put forward a novel and sustainable remediation strategy for Cd removal in wastewater and soil clean-up.

Sustainable phosphorus management in soil using bone apatite.

Soil fertility and phosphorus management by bone apatite amendment are receiving increasing attention, yet further research is needed to integrate the physicochemical and mineralogical transformation of bone apatite and their impact on the supply and storage of phosphorus in soil. This study has examined bone transformation in the field over a span of 10-years using a set of synchrotron-based microscopic and spectroscopic techniques. Transmission X-ray microscopy (TXM) observations reveal the in-situ deterioration of bone osteocyte-canaliculi system and sub-micron microbial tunneling within a year. Extensive organic decomposition, secondary mineral formation and re-mineralization of apatite are evident from the 3rd year. The relative ratio of (v1 + v3) PO43- to v3 CO32- and to amide I increase, and the v3c PO43- peak exhibits a blue-shift in less than 3 years. The carbonate substitution of bone hydroxyapatite (HAp) to AB-type CHAp, and phosphate crystallographic rearrangement become apparent after 10 years' aging. The overall CO32- peak absorbance increases over time, contributing to a higher acid susceptibility in the aged bone. The X-ray Photoelectron Spectroscopy (XPS) binding energies for Ca (2p), P (2p) and O (1s) exhibit a red-shift after 1 year because of organo-mineral interplay and a blue-shift starting from the 3rd year as a result of the de-coupling of mineral and organic components. Nutrient supply to soil occurs within months via organo-mineral decoupling and demineralization. More phosphorus has been released from the bones and enriched in the associated and adjacent soils over time. Lab incubation studies reveal prominent secondary mineral formation via re-precipitation at a pH similar to that in soil, which are highly amorphous and carbonate substituted and prone to further dissolution in an acidic environment. Our high-resolution observations reveal a stage-dependent microbial decomposition, phosphorus dissolution and immobilization via secondary mineral formation over time. The active cycling of phosphorus within the bone and its interplay with adjacent soil account for a sustainable supply and storage of phosphorus nutrients.

Systematic changes of bone hydroxyapatite along a charring temperature gradient: An integrative study with dissolution behavior.

The applicability of bone char as a long-term phosphorus nutrient source was assessed by integrating their mineral transformation and physicochemical properties with their dissolution behavior. We have explored synchrotron-based spectroscopic and imaging techniques (FTIR, XRD, and TXM) to investigate the physicochemical changes of bone and bone char along a charring temperature gradient (300-1200 °C) and used a lab incubation experiment to study their dissolution behaviors in solutions of different pH (4, 6, and 6.9). The thermal decomposition of inorganic carbonate (CO32-) and the loss of organic components rendered a crystallographic rearrangement (blueshift of the PO43- peak) and mineral transformation with increasing temperatures. The mineral transformation from B-type to AB- and A-type carbonate substitution occurred mainly at <700 °C, while the transformation from carbonated hydroxyapatite (CHAp) to more mineralogically and chemically stable HAp occurred at >800 °C. The loss of inorganic carbonate and the increase of structural OH- with increasing temperatures explained the change of pH buffering capacity and increase of pH and their dissolution behaviors. The higher peak area ratios of phosphate to carbonate and phosphate to amide I band with increasing temperatures corroborated the higher stability and resistivity to acidic dissolution by bone chars made at higher temperatures. Our findings suggest that bone char made at low to intermediate temperatures can be a substantial source of phosphorus for soil fertility via waste management and recycling. The bone char made at 500 °C exhibited a high pH buffering capacity in acidic and near-neutral solutions. The 700 °C bone char was proposed as a suitable liming agent for raising the soil pH and abating soil acidity. Our study has underpinned the systematic changes of bone char and interlinked the charring effect with their dissolution behavior, providing a scientific base for understanding the applicability of different bone chars as suitable P-fertilizers.