Hydrothermal carbonization and pyrolysis in wetland engineering: Carbon sequestration, phosphorus recovery, and structural characterization of willow-based chars with X-ray μ-computed tomography

[Display omitted] •EWS-pyrochars are a ready-to-integrate opportunity for soil amendment.•Novel 3D-images reveal the char’s porosity, structure, thickness-mesh, and Feret-diameter.•High aromaticity: overall sp2 C-atoms at 63 % in pyrochar vs. 43 % in hydrochars.•High P-retention: 92 % in EWS-pyrochars, near-total in hydrochars.•Hydrochars from a 10-hectare willow may sequester 80-tons of carbon and recover 334 kg of P annually. Willows from engineered wetland systems (EWS) offer a sustainable approach to wastewater treatment and biomass production. Our study assesses their potential for nutrient recovery and carbon sequestration using slow pyrolysis (600 °C) and hydrothermal carbonization (250 °C). Here, we propose EWS-pyrochars as a ready-to integrate opportunity for soil amendment, as they exhibit a predominant CO2 release and the absence of harmful compounds in pyrolysis-chromatograms, indicating higher stability than hydrochars. Using sequential P-extractions, we observed a high bioavailability in the willow-woodchips and a significant P-retention in EWS-chars—up to 92 % in pyrochars and near-complete retention in hydrochars, along with a higher labile-P fraction of 21 % in hydrochars than 5 % in pyrochars. Utilizing X-ray-based techniques, Raman spectroscopy, scanning electron microscopy, and gas physisorption, we characterized the EWS-chars' structures. We revealed innovative 3D-visualizations, which transcend previous literature by providing insights into the chars' internal porosity and quantifying, for the first time, their carbonaceous structural thickness via a meshing algorithm and the mean Feret diameter. EWS-pyrochars exhibit remarkable aromaticity with a higher concentration of overall sp2 C-atoms at 63 % vs. 43 % in hydrochars. Moreover, unlike hydrochars, which depict occluded porosity, EWS-pyrochars exhibited 92 % water storage-like pores. Although hydrochars indicated lower carbonization and thermal stability than pyrochars, their higher carbon retention (55 vs. 41 % in pyrochar) suggest superior annual benefits—on a 10 ha EWS scale—of 80-tons of carbon sequestration and 334 kg of phosphorus recovery versus 60-tons of carbon and 298 kg of phosphorus with pyrochars. Our findings suggest innovative materials for resource recovery, advancing the engineered wetland systems field, shifting their traditional use, and opening the opportunity for future integration into biorefineries.