Boris L. T. Lau

Relative Importance of the Humic and Fulvic Fractions of Natural Organic Matter in the Aggregation and Deposition of Silver Nanoparticles

As engineered nanoparticles (NPs) are increasingly used, their entry into the environment has become an important topic for water sustainability. Recent investigations point to the critical role of natural organic matter (NOM) in altering the persistence of NPs by complexing with their surfaces. The NP-NOM complex, in turn, is the new entity that may potentially influence subsequent fate of NPs. To understand the relative impact of humic (HA) and fulvic fraction of NOM on the stability and mobility of silver nanoparticles (AgNPs), a combination of dynamic light scattering and quartz crystal microgravimetry with dissipation monitoring was used. In the absence of unbound NOM, (1) surface modification on either AgNP or silica substrate by different NOM fractions could lead to substantial changes in the extent and kinetics of AgNP aggregation and deposition, and (2) HA has a greater capability to enhance the transport of AgNPs by reducing their aggregation and deposition. With unbound NOM, HA seems to compete more successfully for binding sites on the substrate under electrostatically favorable conditions and formed a steric layer to prevent subsequent deposition of AgNPs. These findings highlighted the importance of NOM fraction in the overall environmental partitioning of AgNPs.

Effects of Humic Substances on Precipitation and Aggregation of Zinc Sulfide Nanoparticles

Nanoparticulate metal sulfides such as ZnS can influence the transport and bioavailability of pollutant metals in anaerobic environments. The aim of this work was to investigate how the composition of dissolved natural organic matter (NOM) influences the stability of zinc sulfide nanoparticles as they nucleate and aggregate in water with dissolved NOM. We compared NOM fractions that were isolated from several surface waters and represented a range of characteristics including molecular weight, type of carbon, and ligand density. Dynamic light scattering was employed to monitor the growth and aggregation of Zn-S-NOM nanoparticles in supersaturated solutions containing dissolved aquatic humic substances. The NOM was observed to reduce particle growth rates, depending on solution variables such as type and concentration of NOM, monovalent electrolyte concentration, and pH. The rates of growth increased with increasing ionic strength, indicating that observed growth rates primarily represented aggregation of charged Zn-S-NOM particles. Furthermore, the observed rates decreased with increasing molecular weight and aromatic content of the NOM fractions, while carboxylate and reduced sulfur content had little effect. Differences between NOM were likely due to properties that increased electrosteric hindrances for aggregation. Overall, results of this study suggest that the composition and source of NOM are key factors that contribute to the stabilization and persistence of zinc sulfide nanoparticles in the aquatic environment.

Silver nanoparticle-alginate composite beads for point-of-use drinking water disinfection.

Silver nanoparticles (AgNPs)-alginate composite beads were synthesized using three different approaches as filler materials of packed columns for simultaneous filtration-disinfection as an alternative portable water treatment process. The prepared composite beads were packed into a column through which Escherichia coli containing water was filtered to evaluate the disinfection efficacy. Excellent disinfection performance (no detectable viable colony) was achieved with a hydraulic retention time (HRT) as short as 1 min (the shortest tested) with the SGR (Simultaneous-Gelation-Reduction) and AR (Adsorption-Reduction) beads that were prepared using in situ reduction of Ag(+). Comparatively, the SGR beads released significantly less Ag(+)/AgNPs than the AR beads did within the same HRT. From the results of this study it was identified that SGR may be the best choice among all three different synthesis approaches in that the SGR beads can achieve satisfactory bactericidal performance with a relatively low material consumption rate.

When nanoparticles meet biofilms—interactions guiding the environmental fate and accumulation of nanoparticles

Bacteria are essential components of all natural and many engineered systems. The most active fractions of bacteria are now recognized to occur as biofilms, where cells are attached and surrounded by a secreted matrix of “sticky” extracellular polymeric substances. Recent investigations have established that significant accumulation of nanoparticles (NPs) occurs in aquatic biofilms. These studies point to the emerging roles of biofilms for influencing partitioning and possibly transformations of NPs in both natural and engineered systems. While attached biofilms are efficient “sponges” for NPs, efforts to elucidate the fundamental mechanisms guiding interactions between NPs and biofilms have just begun. In this mini review, special attention is focused on NP–biofilm interactions within the aquatic environment. We highlight key physical, chemical, and biological processes that affect interactions and accumulation of NPs by bacterial biofilms. We posit that these biofilm processes present the likely possibility for unique biological and chemical transformations of NPs. Ultimately, the environmental fate of NPs is influenced by biofilms, and therefore requires a more in-depth understanding of their fundamental properties.

Biomolecule–nanoparticle interactions: Elucidation of the thermodynamics by isothermal titration calorimetry

BACKGROUND Nanomaterials (NMs) are often exposed to a broad range of biomolecules of different abundances. Biomolecule sorption driven by various interfacial forces determines the surface structure and composition of NMs, subsequently governs their functionality and the reactivity of the adsorbed biomolecules. Isothermal titration calorimetry (ITC) is a nondestructive technique that quantifies thermodynamic parameters through in-situ measurement of the heat absorption or release associated with an interaction. SCOPE OF REVIEW This review highlights the recent applications of ITC in understanding the thermodynamics of interactions between various nanoparticles (NPs) and biomolecules. Different aspects of a typical ITC experiment that are crucial for obtaining accurate and meaningful data, as well as the strengths, weaknesses, and challenges of ITC applications to NP research were discussed. MAJOR CONCLUSIONS ITC reveals the driving forces behind biomolecule-NP interactions and the effects of the physicochemical properties of both NPs and biomolecules by quantifying the crucial thermodynamics parameters (e.g., binding stoichiometry, ΔH, ΔS, and ΔG). Complimentary techniques would strengthen the interpretation of ITC results for a more holistic understanding of biomolecule-NP interactions. GENERAL SIGNIFICANCE The thermodynamic information revealed by ITC and its complimentary characterizations is important for understanding biomolecule-NP interactions that are fundamental to the biomedical and environmental applications of NMs and their toxicological effects.

Effect of pathogen concentrations on removal of Cryptosporidium and Giardia by conventional drinking water treatment

The presence of waterborne enteric pathogens in municipal water supplies contributes risk to public health. To evaluate the removal of these pathogens in drinking water treatment processes, previous researchers have spiked raw waters with up to 10(6) pathogens/L in order to reliably detect the pathogens in treated water. These spike doses are 6-8 orders of magnitude higher than pathogen concentrations routinely observed in practice. In the present study, experiments were conducted with different sampling methods (i.e., grab versus continuous sampling) and initial pathogen concentrations ranging from 10(1) to 10(6) pathogens/L. Results showed that Cryptosporidium oocyst and Giardia cyst removal across conventional treatment were dependent on initial pathogen concentrations, with lower pathogen removals observed when lower initial pathogen spike doses were used. In addition, higher raw water turbidity appeared to result in higher log removal for both Cryptosporidium oocysts and Giardia cysts.

NanoEHS – defining fundamental science needs: no easy feat when the simple itself is complex

Nanotechnology is no longer in its infancy and has made significant advances since the implementation of the National Nanotechnology Initiative (NNI) in 2000. Incorporation of nanotechnology in many fields including information technology, medicine, materials, energy, catalysis and cosmetics has led to an increase in engineered nanomaterial (ENM) production, and consequently, increased nanomaterial use. In comparison, the generation of concrete and consistent evidence related to the environmental health and safety of nanomaterials (NanoEHS) is lacking. The main factors contributing to the slower progress in NanoEHS versus conventional EHS are related to the complexity, property transformations, life cycles and behavior of nanomaterials even in carefully controlled environments. Therefore, new systematic, integrated research approaches in NanoEHS are needed for overcoming this complexity and bridging current knowledge gaps. A workshop on “NanoEHS: Fundamental Science Needs” brought together scientists and engineers to identify current fundamental science challenges and opportunities within NanoEHS. Detailed discussions were conducted on identifying the fundamental properties that are critical in NanoEHS, differentiating between conventional and NanoEHS studies as well as understanding, the effect of dynamic transformations on nanometrology, role of dosimetry and mechanistic data gaps in nanotoxicology. An important realization that even simple nanoscale materials can be complex when considering NanoEHS implications was noted several times during the workshop. Despite this fact, a number of fundamental research areas to further the scientific foundation to address NanoEHS needs are suggested.

Colloidal stability of self-assembled monolayer-coated gold nanoparticles: the effects of surface compositional and structural heterogeneity.

Surface heterogeneity plays an important role in controlling colloidal phenomena. This study investigated the self-aggregation and bacterial adsorption of self-assembled monolayer coated gold nanoparticles (AuNPs) with different surface compositional and structural heterogeneity. Evaluation was performed on AuNPs coated with (1) one ligand with charged terminals (MUS), (2) two homogeneously distributed ligands with respectively charged and nonpolar terminals (brOT) and (3) two ligands with respectively charged and nonpolar terminals with stripe-like distribution (OT). The brOT particles have less negative electrophoretic mobility (EPM) values, smaller critical coagulation concentration (CCC) and larger adsorption rate on Escherichia coli than that of AuNPs with homogeneously charged groups, in good agreement with DLVO predictions. Although the ligand composition on the surface of AuNPs is the same, OT particles have less negative EPM values and faster rate of bacterial adsorption, but much larger CCC compared to brOT. The deviation of OT particles from brOT and MUS in their self-aggregation behavior reflects the effects of surface heterogeneity on electrical double layer structures at the interface. Results from the present study demonstrated that, besides chemical composition, organization of ligands on particle surface is important in determining their colloidal stability.

Deposition of nanoparticles onto polysaccharide-coated surfaces: implications for nanoparticle–biofilm interactions

While environmental biofilms have recently been implicated as a potential major sink for nanoparticles (NPs), the mechanisms of interactions remain largely unknown. Polysaccharides are a common component of biofilm extracellular polymeric substances (EPS) and an initial point of contact for NPs in early NP–biofilm interactions. In this study, the significance of polysaccharide coatings on the deposition of hematite and silica NPs was examined by quartz crystal microgravimetry (QCM) and in-depth characterization of surface properties. NP deposition was shown to be largely governed by electrostatic forces. However, bulk surface zeta potential values of the tested polysaccharide-coated surfaces were not sufficient in describing the varying extent of NP deposition. Surface charge density and distribution both appeared to contribute to different NP deposition behaviors. These results suggest that nanometer to micrometer spatial characterization of biofilm surface properties, including chemical composition and charge, is necessary to improve our understanding of NP–biofilm interactions.

Particle uptake efficiency is significantly affected by type of capping agent and cell line

Surface‐functionalized silver nanoparticles (AgNPs) are the most deployed engineered nanomaterials in consumer products because of their optical, antibacterial and electrical properties. Almost all engineered nanoparticles are coated with application‐specific capping agents (i.e. organic/inorganic ligands on particle surface) to enhance their stability in suspension or increase their biocompatibility for biomedicine. The aim of this study was to investigate the contribution of the selected capping agents to their observed health impacts using realistic dose ranges. AgNPs capped with citrate, polyvinylpyrrolidone (PVP) and tannic acid were studied with human bronchoalveolar carcinoma (A549) and human colon adenocarcinoma (Caco‐2) cell lines and compared against exposures to Ag ions. Cellular uptake and cytotoxicity were evaluated up to 24 h. Tannic acid capped AgNPs induced higher cellular uptake and rate in both cell lines. Citrate‐capped and PVP‐capped AgNPs behaved similarly over 24 h. All three of the capped AgNPs penetrated more into the A549 cells than Caco‐2 cells. In contrast, the uptake rate of Ag ions in Caco‐2 cells (0.11 ± 0.0001 µg h–1) was higher than A549 cells (0.025 ± 0.00004 µg h–1). The exposure concentration of 3 mg l–1 is below the EC50 value for all of the AgNPs; therefore, little cytotoxicity was observed in any experiment conducted herein. Exposure of Ag ions, however, interrupted cell membrane integrity and cell proliferation (up to 70% lysed after 24 h). These findings indicate cellular uptake is dependent on capping agent, and when controlled to realistic exposure concentrations, cellular function is not significantly affected by AgNP exposure. Copyright