Monitoring of physico-chemical parameters and the behaviour of zinc oxide nanoparticles in a simulated wastewater treatment plant

M.Sc. (Chemistry)In this study the stability as well as the fate and behavior of ZnO engineered nanoparticles (ENPs) in municipal wastewater systems were investigated. The first part of the study examined the influence of pH and ionic strength on the stability of ZnO ENPs in domestic wastewater to elucidate the dynamic changes on the ENPs physicochemical characteristics (e.g. aggregation or dissolution). The ZnO ENPs obtained commercially were characterized using transmission electron microscopy (TEM), X-ray diffraction spectroscopy (XRD), dynamic light scattering (DLS), BET surface area determination, and energy dispersive X-ray spectrometry (EDS). Results derived from inductively coupled plasma optical emission spectrometry (ICP-OES) for zinc analysis indicated a decrease on the released zinc concentration from wastewater as the pH and ionic strength increased. Conversely, an increase on zinc concentration from the sludge was observed. The findings suggest the removal of ZnO ENPs from the influent wastewater as the sludge settled out, and the removal efficiency was directly proportional to ionic strength and pH. In addition, the ZnO ENPs suspension in the wastewater was used to monitor the particle size distribution using the dynamic light scattering analysis (DLS). The formation of agglomerates was observed which the TEM and EDS analysis confirmed to be ZnO aggregates. The distribution of zinc in the sludge was investigated using XRD analysis and the findings indicated partial sedimentation of ZnO ENPs as the sludge settled out. The second part of the study assessed the fate and behavior of ZnO ENPs in wastewater treatment systems. This study was carried out in a simulated activated sludge wastewater treatment plant (AS WWTP), constructed in accordance to the Organization for Economic Co-operation and Development (OECD 303 A) guidelines. Results from the ICP-OES analysis for zinc indicated 50 – 200 μgL-1 and about 3 000 mgkg-1 were released into the effluent and sludge, respectively, after spiking the influent wastewater with 5 mgL-1 ZnO ENPs. Moreover, we noted that increasing the ZnO ENPs concentration up to 20 mgL-1 resulted in a linear increase in the zinc releases into effluent wastewater. However, the increase was insignificant in comparison to the zinc found in the control unit. Therefore, the findings indicated that ZnO ENPs had stronger affinity for the suspended bio-solids during wastewater treatment, and postulated that the ENPs removal from the influent wastewater was due to bio-sorption, and bio-solid settling mechanisms. These were confirmed by results from XRD and diffuse reflectance spectroscopy (DRS) analysis of the sludge as they showed the presence of ZnO in the sludge. The dissolved organic carbon (DOC) and chemical oxygen demand (COD) were concurrently monitored during the ENPs exposure studies to indirectly assess the ZnO ENPs impact to the bacterial degradation of the organic matter. An average of 43 and 91 % for DOC and COD removal efficiencies, respectively, were observed throughout the study. Overall, from results obtained indicated the suitability of the OECD 303 A method to assess the fate and behavior of ZnO ENPs in WWTPs. Secondly, in light of low concentrations of ZnO ENPs found in the treated effluent due to their removal with the waste activated sludge (WAS), suggest low likelihood of ZnO ENPs release and dispersion into the aquatic systems from WWTPs as point sources. Finally, the elevated concentrations of ZnO ENPs in the sludge therefore necessitates additional treatment steps to ensure mitigation of possible dispersion of ENPs from various disposal mechanisms such as landfilling, incineration, and agricultural applications