Nanomaterial (NM) aggregation is a key process determining their environmental, fate behavior and effects. Nanomaterials are typically engineered to remain kinetically stable; however, in environmental and toxicological media, NMs are prone to aggregation. The aggregation kinetics of NM is typically quantified by measuring their attachment efficiency (α) and critical coagulation concentration (CCC). Several studies measured α and CCC for Ag NMs with a major focus on investigating the effects of ionic strength, ion valency and natural organic matter, with few studies investigating other environmental factors such as light and dissolved oxygen and none investigating the effect of particle size, buffer type and concentration, or surface coverage by capping agent. A survey of recent research articles reporting CCC values for Ag NMs reveals substantial variation in experimental conditions and particle stability with CCC values of monovalent and divalent counterions covering a wide range (ca. 25 to infinity for monovalent counterions and 1.6 to infinity for divalent counterions). Here, we rationalize the differences in the CCC values for Ag NMs based on the variability in the experimental conditions, which includes NM and medium physicochemical properties. Capping agents determines NM stability mechanism with citrate, sodium dodecyl sulfate (SDS), and alginate stabilizing NM by electrostatic mechanism; whereas polyvinylpyrrolidone (PVP), casein, dextrin, tween, branched polyethyleneimine (BPEI), and Gum Arabic stabilizing NMs by steric mechanisms. The CCC values for Ag NMs with different capping agents follow the order citrate∼alginate∼SDS

Properties of NOM-corona formulas forming AgNOM-corona determined by FT-ICR-MS.

Cystine is widely used in cell culture media. Cysteine, the reduced form of cystine, is widely used to scavenge dissolved Ag in eco-toxicological studies to differentiate dissolved vs. nanoparticle uptake and toxicity. However, little is known about the impact of cysteine and cystine on the aggregation behavior of Ag NPs, in particular as a function of Ag NP concentration. Herein, we investigate how cystine (0-300μM) affects the stability of citrate-, polyvinylpyrrolidone-, and polyethylene glycol-coated silver nanoparticles (cit-Ag NPs, PVP-Ag NPs and PEG-Ag NPs, respectively) with and without Suwannee River fulvic acid (SRFA) as a function of Ag NPs concentration using UV-vis spectroscopy at environmentally and ecotoxicologically relevant Ag NP concentrations (ca. 125-1000μgL(-1)). The results demonstrate, for the first time, the concentration-dependent aggregation of cit-Ag NPs in the presence of cystine with a shift in the critical coagulation concentration (CCC) to lower cystine concentrations at lower cit-Ag NP concentrations. At the highest cit-Ag NP concentration (1000μgL(-1)), reaction limited aggregation was only observed and no CCC was measured. SRFA slowed the aggregation of cit-Ag NPs by cystine and aggregation occurred in reaction limited aggregation (RLA) regime only. No CCC value was measured in the presence of SRFA. Cystine replaces citrate, PVP and PEG coatings, resulting in aggregation of both electrostatically and sterically stabilized Ag NPs. These findings are important in understanding the factors determining the behavior of Ag NPs in cell culture media. Also due to the similarity between cystine and cysteine, these results are important in understanding the uptake and toxicity of Ag NPs vs. Ag ions, and suggest that the reduction of the toxicity of Ag NPs in the presence of cysteine could be due to a combined effect of scavenging Ag(+) ions and Ag NP aggregation in the presence of cysteine.

The attachment efficiency (α) is an important parameter that can be used to characterize nanoparticle (NPs) aggregation behavior and has been a topic of discussion of several papers in the past few years. The importance of α is because it is one of the key parameters that can be used to model NP environmental fate and behavior. This study uses UV-vis and laser Doppler electrophoresis to monitor the aggregation behavior of citrate-coated silver nanoparticles (cit-AgNPs) induced by Na and Ca as counter ions in the presence and absence of Suwannee River fulvic acid (SRFA) as a surrogate of natural organic matter and different concentrations of phosphate buffer (0-1mM). Results demonstrate that phosphate buffer, which serves to maintain pH nearly constant over the course of a reaction, is an important determinant of NP aggregation behavior. Increasing phosphate buffer concentration results in a decrease in the critical coagulation concentrations (CCC) of cit-AgNPs to lower counter ion concentration and an increase of α at the same counter ion concentration, both in the absence and presence of SRFA. SRFA stabilizes AgNPs and increases the CCC to higher counter ion concentrations. The outcome of this study can be used to rationalize the variation in α and CCC values reported in the literature for NPs with similar physicochemical properties, where different α and CCC values are reported when different types of buffers and buffer concentrations are used in different studies.

Interaction of natural organic matter (NOM) with engineered nanoparticles (NPs) determine NP fate, transport, and environmental persistence. However, the effect of NOM chemical composition, structure, and concentration on aggregation kinetics and dissolution behavior of silver nanoparticles (AgNPs) are still poorly understood because of heterogeneity and variability in NOM and AgNP properties. Here, aggregation behavior of citrate-coated silver nanoparticles (cit-AgNPs with a z-average diameter of 18nm) was investigated in the presence of l-cysteine (l-cys) and N-acetyl l-cysteine (NAL-cys) using UV-vis spectroscopy. We also investigated the effect of Suwannee River fulvic acid (SRFA) and a NOM isolated from the Yukon River (YRNOM) on the stability of cit-AgNPs. The dissolution of cit-AgNPs decreased with increased L-cys and NAL-cys concentration from 0 to 10μM. The critical coagulation concentration (CCC) of cit-AgNPs decreased in the presence of l-cys and increased in the presence of NAL-cys. Similarly, l-cys destabilizes cit-AgNPs in the presence of SRFA. The differences in the stability of cit-AgNPs in the presence of l-cys and NAL-cys can be attributed to the differences in the functional groups in these two cysteine molecules. l-cys has both negatively charged carboxylic group and a positively charged amine group, resulting in bridging between different particles. NAL-cys is a derivative of cysteine wherein an acetyl group is attached to the nitrogen atom thus shielding the positive charge on the amine group and therefore eliminating the bridging interaction mechanism. SRFA and YRNOM enhanced the stability of cit-AgNPs and increased the CCC value to higher counter ion concentrations. The concentration of SRFA (1-5mgL) did not affect the CCC, whereas the increased concentration of YRNOM increased the CCC of cit-AgNPs to high Na concentrations likely due to increased sorption of higher molecular weight compounds on the surface of cit-AgNPs. The outcome of this study suggests the importance of understanding the molecular properties of NOM (e.g. functional groups and molecular weight) in determining cit-AgNP environmental behaviors.

Manufactured silver nanoparticles (Ag NPs) have long been used as antimicrobials. However, little is known about how these NPs affect fungal cell functions. While multiple previous studies reveal that Ag NPs inhibit secondary metabolite syntheses in several mycotoxin producing filamentous fungi, these effects are associated with growth repression and hence need sublethal to lethal NP doses, which besides stopping fungal growth, can potentially accumulate in the environment. Here we demonstrate that citrate-coated Ag NPs of size 20 nm, when applied at a selected nonlethal dose, can result in a >2 fold inhibition of biosynthesis of the carcinogenic mycotoxin and secondary metabolite, aflatoxin B in the filamentous fungus and an important plant pathogen, Aspergillus parasiticus, without inhibiting fungal growth. We also show that the observed inhibition was not due to Ag ions, but was specifically associated with the mycelial uptake of Ag NPs. The NP exposure resulted in a significant decrease in transcript levels of five aflatoxin genes and at least two key global regulators of secondary metabolism, laeA and veA, with a concomitant reduction of total reactive oxygen species (ROS). Finally, the depletion of Ag NPs in the growth medium allowed the fungus to regain completely its ability of aflatoxin biosynthesis. Our results therefore demonstrate the feasibility of Ag NPs to inhibit fungal secondary metabolism at nonlethal concentrations, hence providing a novel starting point for discovery of custom designed engineered nanoparticles that can efficiently prevent mycotoxins with minimal risk to health and environment.

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Background: Car wash wastewater contains several contaminants such as organic matter, oil, grease, detergents and phosphates, all of which are harmful for the environment. In this study, the application of electrocoagulation (EC) to treat car wash wastewater has been studied, and the operating parameters optimized. The electro-Fenton (EF) for further contaminant removal was also investigated. Methods: In EC process, the effect of pH, current density, and the reaction time of the removal efficiency of chemical oxygen demand (COD), phosphate, and turbidity were investigated using the response surface methodology (RSM). The electrochemical cell consisted of four iron electrodes that were connected to a power supply using a monopolar arrangement. In the EF process, the effect of pH, reaction time, and hydrogen peroxide concentration on COD removal efficiency were probed. Results: The optimum pH, current density, and the reaction time for the EC process were 7.3, 4.2 mA cm-2 and 20.3 minutes, respectively. Under these conditions, the COD, phosphate, and turbidity removal percentages were 80.8%, 94.9% and 85.5%, respectively, and the specific energy consumption was 1.5 kWh m-3. For the EF process, the optimum pH, reaction time, current and hydrogen peroxide dosage were 3, 10 minutes, 2 A and 500 mg L-1 , respectively. The EF showed higher COD removal efficiency (85.6%) with a lower specific energy consumption (0.5 kWh m-3) and reaction time compared to the EC. Conclusion: This study shows that both EC and EF can effectively treat car wash wastewater with high removal efficiency within a short reaction time.