Environmental Technologies for Contaminated Solids, Soils and Sediments
4th cohort

Joyabrata Mal

Microbial Synthesis of Chalcogenide Nanoparticles


Recent years have seen a growing interest in the application of chalcogenide nanoparticles (NPs) (e.g. Se, Te) in various industrial sectors including energy, steels, glass and petroleum refining. The fluorescent metal chalcogenide (e.g. CdSe, CdTe) NPs are used in solar cells, optoelectronic sensors and also in the field of biology and medicine for imaging or sensing including biolabelling. Moreover, due to the high toxicity of chalcogen oxyanions (i.e., selenite, selenate, tellurite and tellurate), their release in the environment is of great concern. Thus, emphasize was given in this thesis on the development of a novel microbial synthesis process of chalcogenide NPs by combining biological treatment of Se/Te-containing wastewaters with biorecovery of Se/Te in the form of Se/Te chalcogenides NPs.

A special focus was given to study the effect of heavy metal (e.g. Cd, Zn and Pb) co-contaminants on selenite bioreduction by anaerobic granular sludge. Anaerobic granular sludge capable of reducing selenite to selenide in the presence of Cd was enriched for the microbial synthesis of CdSe NPs. It was evident that when Cd is present along with selenite, it either forms a Se-Cd complex by adsorption onto biogenic Se(0) nanoparticles after Se-oxyanion bioreduction or it reacts with aqueous selenide (HSe) to form CdSe. The absorption and fluorescence spectra of the aqueous phase confirm the presence of CdSe NPs. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis support this finding. The formation of an alloyed layer of CdSxSe1-x at the interface between the CdSe core and CdS shell in the sludge was also observed. Detailed studies on the extracellular polymeric substances (EPS) reveal that the protein and polysaccharide-like content increased in the EPS extracted from enriched sludge while humic-like substances decreased. Size exclusion chromatography (SEC) of EPS further reveals a distinct fingerprint for proteins and humic-like substances, with increase in high molecular weight protein-like and the appearance of new peaks for humic-like substances in the EPS after the enrichment.

An upflow anaerobic granular sludge bed (UASB) reactor was used for the first time for continuous removal of tellurite from synthetic wastewater and the recovery of Te as biogenic Te(0). Energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and Raman spectroscopic analysis of biomass confirmed the deposition of Te(0) in the biomass. It was evident that the majority of the Te(0) was trapped predominantly in the EPS surrounding the biomass, which can be easily separated by centrifugation.