Amro M. El Badawy

IMPACT OF ENVIRONMENTAL CONDITIONS (PH, IONIC STRENGTH, AND ELECTROLYTE TYPE) ON THE SURFACE CHARGE AND AGGREGATION OF SILVER NANOPARTICLES SUSPENSIONS

The impact of capping agents and environmental conditions (pH, ionic strength, and background electrolytes) on surface charge and aggregation potential of silver nanoparticles (AgNPs) suspensions were investigated. Capping agents are chemicals used in the synthesis of nanoparticles to prevent aggregation. The AgNPs examined in the study were as follows: (a) uncoated AgNPs (H(2)-AgNPs), (b) electrostatically stabilized (citrate and NaBH(4)-AgNPs), (c) sterically stabilized (polyvinylpyrrolidone (PVP)-AgNPs), and (d) electrosterically stabilized (branched polyethyleneimine (BPEI)-AgNPs)). The uncoated (H(2)-AgNPs), the citrate, and NaBH(4)-coated AgNPs aggregated at higher ionic strengths (100 mM NaNO(3)) and/or acidic pH (3.0). For these three nanomaterials, chloride (Cl(-), 10 mM), as a background electrolyte, resulted in a minimal change in the hydrodynamic diameter even at low pH (3.0). This was limited by the presence of residual silver ions, which resulted in the formation of stable negatively charged AgCl colloids. Furthermore, the presence of Ca(2+) (10 mM) resulted in aggregation of the three previously identified AgNPs regardless of the pH. As for PVP coated AgNPs, the ionic strength, pH and electrolyte type had no impact on the aggregation of the sterically stabilized AgNPs. The surface charge and aggregation of the BPEI coated AgNPs varied according to the solution pH.

An evidence-based environmental perspective of manufactured silver nanoparticle in syntheses and applications: a systematic review and critical appraisal of peer-reviewed scientific papers.

BACKGROUND Most recently, renewed interest has arisen in manufactured silver nanomaterials because of their unusually enhanced physicochemical properties and biological activities compared to the bulk parent materials. A wide range of applications has emerged in consumer products ranging from disinfecting medical devices and home appliances to water treatment. Because the hypothesized mechanisms that govern the fate and transport of bulk materials may not directly apply to materials at the nanoscale, there are great concerns in the regulatory and research communities about potential environmental impacts associated with the use of silver nanoparticles. In particular, the unlimited combinations of properties emerging from the syntheses and applications of silver nanoparticles are presenting an urgent need to document the predominant salt precursors, reducing agents and stabilizing agents utilized in the synthesis processes of silver nanoparticles to guide the massive efforts required for environmental risk assessment and management. OBJECTIVES The primary objective of this study is to present an evidence-based environmental perspective of silver nanoparticle properties in syntheses and applications. The following specific aims are designed to achieve the study objective: Aim 1--to document the salt precursors and agents utilized in synthesizing silver nanoparticles; Aim 2--to determine the characteristics of silver nanoparticles currently in use in the scientific literature when integrated in polymer matrices to form nanocomposites and combined with other metal nanoparticles to form bimetallic nanoparticles; Aim 3--to provide a summary of the morphology of silver nanoparticles; and (4) Aim 4--to provide an environmental perspective of the evidence presented in Aims 1 to 3. METHODS A comprehensive electronic search of scientific databases was conducted in support of the study objectives. Specific inclusion criteria were applied to gather the most pertinent research articles. Data and information extraction relied on the type of synthesis methods, that is, synthesized silver nanoparticles in general and specific applications, nanocomposites, and bimetallic techniques. The following items were gathered for: type of silver salt, solvent, reducing agent, stabilizing agent, size, and type of application/nanocomposite/bimetallic, and template (for nanocomposites). The description of evidence was presented in tabular format. The critical appraisal was analyzed in graphical format and discussed. RESULTS An analysis of the scientific literature suggests that most synthesis processes produce spherical silver nanoparticles with less than 20nm diameter. Silver nanoparticles are often synthesized via reduction of AgNO(3), dissolution in water, and utilization of reductants also acting as capping or stabilizing agents for the control of particle size to ensure a relatively stable suspension. Two of the most commonly used reductants and stabilizing agents are NaBH(4) and citrate which yield particles with a negative surface charge over the environmental pH range (3-10). The environmental perspectives of these parameters are discussed. CONCLUDING REMARKS It is expected that the antibacterial property of bulk silver is carried over and perhaps enhanced, to silver nanoparticles. Therefore, when one examines the environmental issues associated with the manufacture and use of silver nanoparticle-based products, the antibacterial effects should always be taken into account particularly at the different stages of the product lifecycle. Currently, there are two arguments in the scientific literature about the mechanisms of antimicrobial properties of silver nanoparticles as they relate to colloidal silver particles and inonic silver. Methodologies of risk assessment and control have to account for both arguments.

The impact of stabilization mechanism on the aggregation kinetics of silver nanoparticles.

The use of silver nanoparticles (AgNPs) for various applications is growing drastically. The increase in use will eventually lead to their release into the environment. The tendency of AgNPs to aggregate and the kinetics of aggregation are major factors that govern their fate in the environment. Dynamic light scattering (DLS) was utilized to investigate the electrolyte-induced aggregation kinetics (NaNO₃, NaCl and Ca(NO₃)₂) of coated and uncoated AgNPs which are electrostatically (H₂-AgNPs and Citrate-AgNPs), sterically (polyvinylpyrrolidone (PVP)-AgNPs) and electrosterically (branched polyethyleneimine (BPEI)-AgNPs) stabilized. The aggregation kinetics of the electrostatically stabilized AgNPs was in agreement with the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and the AgNPs exhibited both reaction-limited and diffusion-limited regimes. The H₂-AgNPs had critical coagulation concentrations (CCC) of 25, 30 and 3mM in the presence of NaNO₃, NaCl and Ca(NO₃)₂ salts, respectively. The Citrate-AgNPs had CCC of 70, 70 and 5 mM in the presence of NaNO₃, NaCl and Ca(NO₃)₂ salts, respectively. The values of the Hamaker constant for the electrostatically stabilized AgNPs were also determined and the values were in agreement with the reported values for metallic particles. The aggregation kinetics for both the sterically and electrosterically stabilized AgNPs (PVP-AgNPs and BPEI-AgNPs) was not in agreement with the DLVO theory and the particles were resistant to aggregation even at high ionic strength and electrolyte valence. The PVP-AgNPs and the BPEI-AgNPs had no critical aggregation concentration value at the investigated ionic strength values.

Synchrotron Speciation of Silver and Zinc Oxide Nanoparticles Aged in a Kaolin Suspension

Assessments of the environmental fate and mobility of nanoparticles must consider the behavior of nanoparticles in relevant environmental systems that may result in speciation changes over time. Environmental conditions may act on nanoparticles to change their size, shape, and surface chemistry. Changing these basic characteristics of nanoparticles may result in a final reaction product that is significantly different than the initial nanomaterial. As such, basing long-term risk and toxicity on the initial properties of a nanomaterial may lead to erroneous conclusions if nanoparticles change upon release to the environment. The influence of aging on the speciation and chemical stability of silver and zinc oxide nanoparticles in kaolin suspensions was examined in batch reactors for up to 18 months. Silver nanoparticles remained unchanged in sodium nitrate suspensions; however, silver chloride was identified with the metallic silver nanoparticles in sodium chloride suspensions and may be attributed to an in situ silver chloride surface coating. Zinc oxide nanoparticles were rapidly converted via destabilization/dissolution mechanisms to Zn(2+) inner-sphere sorption complexes within 1 day of reaction and these sorption complexes were maintained through the 12 month aging processes. Chemical and physical alteration of nanomaterials in the environment must be examined to understand fate, mobility, and toxicology.

Changes in silver nanoparticles exposed to human synthetic stomach fluid: Effects of particle size and surface chemistry

The significant rise in consumer products and applications utilizing the antibacterial properties of silver nanoparticles (AgNPs) has increased the possibility of human exposure. The mobility and bioavailability of AgNPs through the ingestion pathway will depend, in part, on properties such as particle size and the surface chemistries that will influence their physical and chemical reactivities during transit through the gastrointestinal tract. This study investigates the interactions between synthetic stomach fluid and AgNPs of different sizes and with different capping agents. Changes in morphology, size and chemical composition were determined during a 30 min exposure to synthetic human stomach fluid (SSF) using Absorbance Spectroscopy, High Resolution Transmission Electron and Scanning Electron Microscopy (TEM/SEM), Dynamic Light Scattering (DLS), and Nanoparticle Tracking Analysis (NTA). AgNPs exposed to SSF were found to aggregate significantly and also released ionic silver which physically associated with the particle aggregates as silver chloride. Generally, the smaller sized AgNPs (<10nm) showed higher rates of aggregation and physical transformation than larger particles (75 nm). Polyvinylpyrrolidone (pvp)-stabilized AgNPs prepared in house behaved differently in SSF than particles obtained from a commercial source despite having similar surface coating and size distribution characteristics.

Key Factors Controlling the Transport of Silver Nanoparticles in Porous Media

The current study investigated the mobility of four silver nanoparticles (AgNPs) stabilized using different capping agents and represent the common stabilization mechanisms as well as surface charging scenarios in reactive and nonreactive porous media. The AgNPs were (1) uncoated H2-AgNPs (electrostatically stabilized) and (2) citrate coated AgNPs (Citrate-AgNPs) (electrostatically stabilized), (3) polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) (sterically stabilized), and (4) branched polyethyleneimine coated AgNPs (BPEI-AgNPs) (electrosterically stabilized). The porous media were (1) quartz sand (QS), (2) ferrihydrite-coated sand (FcS), and (3) kaolin-coated sand (KcS). The H2-AgNPs and Citrate-AgNPs were readily mobile in QS but significantly retained in FcS and KcS with more deposition achieved in the KcS media. The deposition of the H2-AgNPs and Citrate-AgNPs followed the order of KcS > FcS > QS. The PVP-AgNPs breakthrough occurred more rapid as compared to the H2-AgNPs and Citrate-AgNPs but the deposition of PVP-AgNPs followed the same order of the electrostatically stabilized AgNPs (KcS > FcS > QS). The BPEI-AgNPs were readily mobile regardless of the porous media reactivity. Physicochemical interactions were the dominant filtration mechanism in the majority of the investigated cases but straining played the major role in the deposition of the electrostatically stabilized H2-AgNPs and Citrate-AgNPs in the KcS media. The results highlight the importance of both the stabilization mechanism and capping agent chemistry as key factors governing the transport of AgNPs in the environment.

Rapid screening of aquatic toxicity of several metal-based nanoparticles using the MetPLATE™ bioassay

Current understanding of potential toxicity of engineered nanomaterials to aquatic microorganisms is limited for risk assessment and management. Here we evaluate if the MetPLATE™ test can be used as an effective and rapid screening tool to test for potential aquatic toxicity of various metal-based nanoparticles (NPs). The MetPLATE bioassay is a heavy metal sensitive test based on β-galactosidase activity in Escherichia coli. Five different types of metal-based NPs were screened for toxicity: (1) citrate coated nAg (Citrate-nanosilver), (2) polyvinylpyrrolidone coated nAg (PVP-nAg), (3) uncoated nZnO, (4) uncoated nTiO(2) and (5) 1-Octadecylamine coated CdSe Quantum Dots (CdSe QDs); and compared with their corresponding ionic salt toxicity. Citrate-nAg was further fractionated into clean Citrate-nAg, unclean Citrate-nAg and permeate using a tangential flow filtration (TFF) system to eliminate residual ions and impurities from the stock Citrate-nAg suspension and also to differentiate between ionic- versus nano-specific toxicity. Our results showed that nAg, nZnO and CdSe QDs were less toxic than their corresponding ionic salts tested, while nano- or ionic form of TiO(2) was not toxic as high as 2.5 g L(-1) to the MetPLATE™ bacteria. Although coating-dependent toxicity was noticeable between two types of Ag NPs evaluated, particle size and surface charge were not adequate to explain the observed toxicity; hence, the toxicity appeared to be material-specific. Overall, the toxicity followed the trend: CdCl(2)>AgNO(3)>PVP-nAg>unclean Citrate-nAg>clean Citrate-nAg>ZnSO(4)>nZnO>CdSe QDs>nTiO(2)/TiO(2). These results indicate that an evaluation of β-galactosidase inhibition in MetPLATE™ E. coli can be an important consideration for rapid screening of metal-based NP toxicity, and should facilitate ecological risk assessment of these emerging contaminants.

Comment on "120 Years of nanosilver history: implications for policy makers".

R Environmental Science and Technology published a policy analysis paper by Nowack et al. showing that nanosilver has been in commerce for more than 100 years. The authors argued that because these silver-based products have been safely used in the past, it would be a mistake to ignore this historical information and treat nanosilver as a “new chemical with new and unknown risks.” This rebuttal contends that most of the historical data cited byNowack et al. are of limited value for assessing new products containing nanosilver and, as a result, product specific information is required when evaluating the risk posed by using these products. Nowack et al. state that “The more than 50-year use of these nanosilver products presents a unique opportunity for environmental scientists to study the effects of the discharge of nanosilver...and epidemiologists could study populations of homeowners using silver-based algicides.” We find that only 7 of the 92 registered silver-based products presented in this analysis are confirmed to contain nanosilver (Table 1 in ref 1) and only two of these have been in use formore than 20 years (Table 2 in ref 1). Algaedyn was registered with the United States Environmental Protection Agency (USEPA) under the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) in 1954 as an algicide for residential swimming pools. However, because the silver content of this product is limited (i.e., 0.8%), the annual mass of silver released and the exposure from its use are limited. In another argument, Nowack et al. suggest that historical work on the health effects of colloidal silver products support the claim of no adverse effects for consumer products containing nanosilver. Regulatory agencies like the USEPA have considered data on colloidal silver in deriving toxicological end points for silver. However, it is unclear if observations for silver-based health supplements are applicable for evaluating the safety of nanosilver in consumer products such as clothing and bedding where the exposure routes (ingestion vs dermal), exposure duration (periodic vs prolonged), and population sizes (limited vs widespread) are different. We do not believe that observations for colloidal-silver based health supplements are applicable for evaluating the safety of micrometerscale-silica decorated with nanosilver or spray applied nanosilver due to differences in physical properties. We note that there are cases where adverse health effects for colloidal silver and nanosilver have been observed, albeit under extreme use conditions. One person was reported to have developed epileptic seizures and coma followed by irreversible neurological toxicity after daily ingestion of colloidal silver for 4 months. And there is one case where a burn patient treated with a nanosilver-coated wound dressing developed clinical signs of argyria and liver toxicity. In an effort to resolve uncertainty regarding the safety of nanosilver, key questions about nanosilver were recently posed to an independent peer-review scientific panel. The Panel concluded that since the effects of nanosilver are dependent on its physical properties, these nanomaterials should be evaluated on a case-by-case basis. This conclusion is further supported by studies in the literature reporting that the toxicity of nanosilver depends on the morphology and surface properties of these nanoparticles. 10 Even though nanosilver has been safely used in some consumer products, it should not necessarily be inferred that all types of nanosilver are safe for use. In the past decade, the number of synthesis methods for nanosilver has drastically increased. One can expect future developments in the manufacture of silver nanoparticles and the ability to engineer and tune their characteristics in order to fit a wide spectrum of applications. Thus, the evaluation of risk for each nanosilver product should consider the physical, chemical, and possibly toxic characteristics unique to that product.

Characterization of salt cake from secondary aluminum production.

Salt cake is a major waste component generated from the recycling of secondary aluminum processing (SAP) waste. Worldwide, the aluminum industry produces nearly 5 million tons of waste annually and the end-of-life management of these wastes is becoming a challenge in the U.S. and elsewhere. In this study, the mineral phases, metal content and metal leachability of 39 SAP waste salt cake samples collected from 10 different facilities across the U.S. were determined. The results showed that aluminum (Al), aluminum oxide, aluminum nitride and its oxides, spinel and elpasolite are the dominant aluminum mineral phases in salt cake. The average total Al content was 14% (w/w). The overall percentage of the total leachable Al in salt cake was 0.6% with approximately 80% of the samples leaching at a level less than 1% of the total aluminum content. The extracted trace metal concentrations in deionized water were relatively low (μgL(-1) level). The toxicity characteristic leaching procedure (TCLP) was employed to further evaluate leachability and the results indicated that the leached concentrations of toxic metals from salt cake were much lower than the EPA toxicity limit set by USEPA.

A system-of-systems approach as a broad and integrated paradigm for sustainable engineered nanomaterials.

There is an urgent need for a trans-disciplinary approach for the collective evaluation of engineered nanomaterial (ENM) benefits and risks. Currently, research studies are mostly focused on examining effects at individual endpoints with emphasis on ENM risk effects. Less research work is pursuing the integration needed to advance the science of sustainable ENMs. Therefore, the primary objective of this article is to discuss the system-of-systems (SoS) approach as a broad and integrated paradigm to examine ENM benefits and risks to society, environment, and economy (SEE) within a sustainability context. The aims are focused on: (a) current approaches in the scientific literature and the need for a broad and integrated approach, (b) documentation of ENM SoS in terms of architecture and governing rules and practices within sustainability context, and (c) implementation plan for the road ahead. In essence, the SoS architecture is a communication vehicle offering the opportunity to track benefits and risks in an integrated fashion so as to understand the implications and make decisions about advancing the science of sustainable ENMs. In support of the SoS architecture, we propose using an analytic-based decision support system consisting of a knowledge base and analytic engine along the benefit and risk informatics routes in the SEE system to build sound decisions on what constitutes sustainable and unsustainable ENMs in spite of the existing uncertainties and knowledge gaps. The work presented herein is neither a systematic review nor a critical appraisal of the scientific literature. Rather, it is a position paper that largely expresses the views of the authors based on their expert opinion drawn from industrial and academic experience.