Cotton gin waste and walnut shells-derived biochar as low-cost solutions to removing pharmaceuticals from aqueous solutions

Authors: NDOUN, MARLENE CARLA - Pennsylvania State University; Knopf, Allan; PREISENDANZ, HEATHER - Pennsylvania State University; VOZENILEK, NATASHA - Pennsylvania State University; ELLIOTT, HERSCHEL - Pennsylvania State University; MASHTARE, MICHAEL - Pennsylvania State University; VELEGOL, STEPHANIE - Pennsylvania State University; Veith, Tameria - Tamie; Williams, Clinton

Submitted to: Chemosphere
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 4/1/2023
Publication Date: 4/8/2023
Citation: Ndoun, M., Knopf, A.L., Preisendanz, H.E., Vozenilek, N., Elliott, H.A., Mashtare, M.L., Velegol, S.B., Veith, T.L., Williams, C.F. 2023. Cotton gin waste and walnut shells-derived biochar as low-cost solutions to removing pharmaceuticals from aqueous solutions. Chemosphere. https://doi.org/10.1016/j.chemosphere.2023.138591.
DOI: https://doi.org/10.1016/j.chemosphere.2023.138591

Interpretive Summary: This study evaluated the ability for biochar produced from cotton gin waste (CG700) and walnut shells (WS800) to remove four pharmaceuticals, acetaminophen (ACT), sulfapyridine (SPY), ibuprofen (IBP) and docusate (DCT), from aqueous solution. Fixed-bed column experiments were performed to determine the difference in removal efficiency between the biochars and elucidate the effects of biochar properties on the adsorption capacity for the pharmaceuticals of interest. Results showed that CG700 had a greater affinity for removing DCT (99%) and IBP (50%), while WS800 removed 72% of SPY and 68% of ACT after 24 h and adsorption was influenced by the solution pH, surface area, net charge, and functional groups of the biochars. The mechanisms for removal included pore filling and diffusion, hydrophobic interactions, hydrogen bonding and '-' electron donor acceptor interactions. Overall, the results demonstrate that biochars from cotton gin waste and walnut shells could be used as cost-effective, environmentally friendly alternatives to activated carbon for the removal of pharmaceuticals from aqueous solutions.

Technical Abstract: Acetaminophen (ACT), sulfapyridine (SPY), ibuprofen (IBP) and docusate (DCT) are pharmaceuticals with widespread usage that experience incomplete removal in wastewater treatment systems. While further removal of these pharmaceuticals from wastewater effluent is desired prior to beneficial reuse, additional treatment technologies are often expensive and energy intensive. This study evaluated the ability for biochar produced from cotton gin waste (CG700) and walnut shells (WS800) to remove four pharmaceuticals (ACT, SPY, IBP, and DCT) from aqueous solution. Physico-chemical properties of the biochar were characterized by Brunauer-Emmett-Teller (BET) analysis, scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), and zeta potential. An increase in pyrolysis temperature during the production of WS800 led to an increase in the specific surface area and increased dehydration of the biochar represented by the loss of the OH-group. Fixed-bed column experiments were performed to determine the difference in removal efficiency between the biochars and elucidate the effects of biochar properties on the adsorption capacity for the pharmaceuticals of interest. Results showed that CG700 had a greater affinity for removing DCT (99%) and IBP (50%), while WS800 removed 72% of SPY and 68% of ACT after 24 h and adsorption was influenced by the solution pH, surface area, net charge, and functional groups of the biochars. The mechanisms for removal included pore filling and diffusion, hydrophobic interactions, hydrogen bonding and '-' electron donor acceptor interactions. To conduct predictive modeling of the column breakthrough curves, the Thomas, Adams-Bohart and Yoon Nelson models were applied to the experimental data. Results demonstrated that these models provided a poor fit for the description of asymmetrical breakthrough curves. Overall, the results demonstrate that biochars from cotton gin waste and walnut shells could be used as cost-effective, environmentally friendly alternatives to activated carbon for the removal of pharmaceuticals from aqueous solutions.