France, Hamant Edward

Innovative strategies to manage copious waste streams by upcycling feedstocks to valorized products which are then used in environmental remediation applications is an attractive circular economy model. This thesis explores this approach using waste wood generated from the milling of Chlorocardium rodiei (greenheart), a tropical hardwood species abundant in Guyana. We evaluate the thermochemical conversion of this feedstock, using phosphoric acid as the activant, to super activated carbons with surface areas of more than 2200 m2/g. Owing to the presence of surface heteroatoms, these adsorbents are amenable to further surface modifications including base-treatment, O-functionalization and N-functionalization. Using a facile oxidation procedure and shrimp waste-based dopants, we increase oxygen and nitrogen content by 8-fold and 5-fold respectively. These increases are realized without catastrophic loss of surface area and porosity as generally occurs with many reported functionalization approaches. Functionalized materials demonstrated efficient removal of both metal ions and the chlorinated herbicides 2,4-dichlorophenoxy acetic acid and paraquat. Pristine and base-washed ACs removed more than 90% of iron, aluminum and manganese from natural pit-lake waters. O-functionalized adsorbents also showed excellent removal efficiencies for aluminum and lead but only removed moderate amounts of manganese. Nitrogen-enriched composites fabricated with the addition of commercial chitosan removed 67% 2,4-D and 89% paraquat from model solutions at environmentally relevant concentrations of 4 ppm and 40 ppm respectively. Their versatility is further demonstrated in their ability to remove both herbicides from binary mixtures albeit to different extents. Shrimp chitin-based composites were most effective at removing 2,4-D from model solutions with a maximum adsorption capacity of 101 mg/g. Both surface area and surface nitrogen had strong influences on the adsorption capacity of adsorbents. Mechanistically, physisorption interactions predominate the synergistic or antagonistic interaction between N-functionalized composites and herbicide species. These green adsorbent materials, fabricated from sustainable biopolymers, are promising candidates for diverse environmental remediation applications.

Author Keywords: adsorption, Environmental remediation, N-functionalization, O-functionalization, tropical hardwood waste, waste valorization