An investigation into silver nanoparticles removal from water during sand filtration and activated carbon adsorption
Clarke, Emma Victoria Faye
Thesis or dissertation
University of Exeter
Reason for embargo
An 18 month embargo was requested upon submission of this thesis on 31 October 2016. This embargo request letter was submitted along with the thesis and signed off by the Primary Supervisor, Dr Diego Gomez. The reason for this embargo is to support my current efforts in publishing work presented in the thesis.
Wastewater treatment plants (WwTP) act as the principle buffer between anthropogenic sources of Silver Nanoparticles (AgNPs) and environmental targets. AgNPs, given their effective anti-microbial properties, have the potential to negatively impact WwTP processes and organisms within the natural environment. A clear understanding of the fate and transport of AgNPs as they pass through WwTPs is crucial in evaluating AgNPs impacts for WwTP process, the natural environment and in the development of a comprehensive environmental risk assessment for AgNPs. The main aim of this thesis was to carry out an analysis on the fate, transport and transformation of AgNPs through WwTP relevant filtration medias in order to understand more about the toxicological implications for both WwTP processes and receiving environments. AgNPs were synthesised in-house, via an in-situ reduction method, which produced a homogeneous dispersion of nanoparticles of average particle diameter 9.98nm, with a standard deviation of 3.11nm. Column studies and adsorption isotherm experiments were conducted to investigate the fate and transport of silver nitrate, AgNPs and bulk silver across media beds of quartz sand and granulated activated carbon (GAC), both chosen for their relevance in wastewater treatment protocols. TEM imaging and EDS analysis was employed to characterise the AgNPs physically and elementally within the column influents and effluents. An original contribution made to the existing knowledge on AgNPs is that in contrast to bulk silver and silver nitrate, uncoated AgNPs were observed to be highly mobile through the quartz sand media. This high mobility was in contrast with the prior expectation that van der Waals forces of attraction between the positively charged AgNPs and the negative charge of the silica surfaces within the sand bed would lead to some measure of retention within the column matrix. The resulting high mobility of the AgNPs was attributed to particle surface contamination of boride ions originating from the reduction agent used during the synthesis process. This highlights (and reinforces) the importance of better understanding on the implications of the various methods of synthesis and use of capping agents for AgNPs characteristics and the impact this has on fate and transport. AgNPs were also noted to have been significantly altered after their passage through the quartz sand media, with up to 83% of the sample increasing in size, from 9.98nm to an average of 18.26nm and a maximum of 144nm. Particle size measurements were made using the measuring tool available in the GNU Image Manipulation Program (GIMP). This size increase was attributed to the formation of nano-alloy clusters with residual gold and iron compounds, naturally present within the sand bed. In the case of silver-gold alloy clusters, this is expected to exhibit positive implications for future environmental fates of the resulting AgNPs, where the presence of gold in alloy clusters has been observed to significantly deactivate AgNPs silver ion release. In contrast to the sand, it was observed that the GAC was an effective absorber of AgNPs. However, this was observed to be a size dependant relationship, where the GAC was not observed to be effective for adsorption of bulk silver at particle sizes of 300 – 800nm. In this thesis, in addition to the experimental work, a novel, low complexity technique was developed for the detection and quantification of AgNPs in laboratory aqueous solutions. This protocol utilises a laboratory bench top photometer and gave AgNPs concentration results that reliably and accurately reflected that of ICP-MS and ICP-OES results within a detection range of 0.01 and 20mg/L; where the correlation coefficient between the instrument absorbance response and ICP-MS/OES concentration (at 450nm) was R2 0.994.
College of Engineering, Mathematics and Physical Sciences, University of Exeter.
Gomez, Diego E.
Tyler, Charles R.
PhD in Engineering