Silver nanoparticles (AgNPs) are widely used in commerce, however, the effect of their physicochemical properties on toxicity remains debatable because of the confounding presence of Ag⁺ ions. Thus, we designed a series of AgNPs that are stable to surface oxidation and Ag⁺ ion release. AgNPs were coated with a hybrid lipid membrane comprised of L-phosphatidylcholine (PC), sodium oleate (SOA), and a stoichiometric amount of hexanethiol (HT) to produce oxidant-resistant AgNPs, Ag–SOA–PC–HT. The stability of 7-month aged, 20–100 nm Ag–SOA–PC–HT NPs were assessed using UV–Vis, dynamic light scattering (DLS), and inductively coupled plasma mass spectrometry (ICP-MS), while the toxicity of the nanomaterials was assessed using a well-established, 5-day embryonic zebrafish assay at concentrations ranging from 0–12 mg/L. There was no change in the size of the AgNPs from freshly made samples or 7-month aged samples and minimal Ag⁺ ion release (<0.2%) in fishwater (FW) up to seven days. Toxicity studies revealed AgNP size- and concentration-dependent effects. Increased mortality and sublethal morphological abnormalities were observed at higher concentrations with smaller nanoparticle sizes. This study, for the first time, determined the effect of AgNP size on toxicity in the absence of Ag⁺ ions as a confounding variable.

Copper based nanoparticles (NPs) are used extensively in industrial and commercial products as sensors, catalysts, surfactants, antimicrobials, and for other purposes. The high production volume and increasing use of copper-based NPs make their ecological risk a concern. Commonly used copper-based NPs are composed of metallic copper or copper oxide (Cu and CuO NPs); however, their environmental toxicity can vary dramatically depending on their physico-chemical properties, such as dissolution, aggregation behavior, and the generation of reactive oxygen species. Here, we investigated the NP dissolution, organismal uptake and aquatic toxicity of Cu and CuO NPs at 0, 0.1, 1, 5 or 10 mg Cu per L using a previously developed multi-species microcosm. This 5 day microcosm assay was comprised of C. reinhardtti, E. coli, D. magna, and D. rerio. We hypothesized that Cu and CuO NPs can elicit differential toxicity to the organisms due to alterations in particle dissolution and variations in organismal uptake. The actual concentrations of dissolved Cu released from the NPs were compared to ionic copper controls (CuCl₂) at the same concentrations to determine the relative contribution of particulate and dissolved Cu on organism uptake and toxicity. We found that both NPs had higher uptake in D. magna and zebrafish than equivalent ionic exposures, suggesting that both Cu-based NPs are taken up by organisms. Cu NP exposures significantly inhibited algal growth rate, D. magna survival, and zebrafish hatching while exposure to equivalent concentrations of CuCl₂ (dissolved Cu fraction) and CuO NPs did not. This indicates that Cu NPs themselves likely elicited a particle-specific mechanism of toxicity to the test organisms, or a combination effect from ionic Cu and the Cu NPs. Overall, this work was the first study to utilize a small-scale rapid assay designed to evaluate the fate and ecotoxicological impacts of Cu and CuO NPs in a mixed aquatic community.

Given the costs associated with designing novel active ingredients, new formulations focus on the use of other ingredients to modify existing formulations. Nanosized encapsulated pesticides offer a variety of enhanced features including controlled release and improved efficacy. Despite the presence of nanosized capsules in current-use pesticide formulations, the analytical and toxicological implications of encapsulation are uncertain. To explore this issue quantitatively, we fractionated the capsules of a commercially available encapsulated insecticide formulation (γ-cyhalothrin active ingredient) into two size ranges: a large fraction (LF), with an average hydrodynamic diameter (HDD) of 758 nm, and a small fraction (SF), with an average HDD of 449 nm. We developed a novel extraction method demonstrating a time-dependent inhibition of γ-cyhalothrin from capsules for up to 48 h. An acute immobilization test with a freshwater macroinvertebrate (Ceriodaphnia dubia) revealed that the SF was significantly more toxic than both the LF and the free γ-cyhalothrin treatment (EC50 = 0.18 µg/L, 0.57 µg/L, and 0.65 µg/L, respectively). These findings highlight that encapsulation of γ-cyhalothrin mitigates hydrophobic partitioning in a time-dependent manner and influences toxicity in a size-dependent manner. Recognizing the analytical and toxicological nuances of various nanosized capsules can contribute to innovation in pesticide formulations and may lead to more comprehensive pesticide regulation.

The decline in populations of insect pollinators is a global concern. While multiple factors are implicated, there is uncertainty surrounding the contribution of certain groups of pesticides to losses in wild and managed bees. Nanotechnology-based pesticides (NBPs) are formulations based on multiple particle sizes and types. By packaging active ingredients in engineered particles, NBPs offer many benefits and novel functions, but may also exhibit different properties in the environment when compared with older pesticide formulations. These new properties raise questions about the environmental disposition and fate of NBPs and their exposure to pollinators. Pollinators such as honey bees have evolved structural adaptations to collect pollen, but also inadvertently gather other types of environmental particles which may accumulate in hive materials. Knowledge of the interaction between pollinators, NBPs, and other types of particles is needed to better understand their exposure to pesticides, and essential for characterizing risk from diverse environmental contaminants. The present review discusses the properties, benefits and types of nanotechnology-based pesticides, the propensity of bees to collect such particles and potential impacts on bee pollinators.