No abstract

Knowledge of dissolution, aggregation, and stability of nanoagrochemicals in root exudates (RE) and soil leachate will contribute to improving delivery mechanisms, transport in plants, and bioavailability. We characterized aggregation, stability, and dissolution of four nanoparticles (NPs) in soybean RE and soil leachate: nano-CeO 2 , nano-Mn 3 O 4 , nano-Cu(OH) 2 , and nano-MoO 3 . Aggregation differed considerably in different media. In RE, nano-Cu(OH) 2 , and nano-MoO 3 increased their aggregate size for 5 days; their mean sizes increased from 518 ± 43 nm to 938 ± 32 nm, and from 372 ± 14 nm to 690 ± 65 nm, respectively. Conversely, nano-CeO 2 and nano-Mn 3 O 4 disaggregated in RE with time, decreasing from 289 ± 5 nm to 129 ± 10 nm, and from 761 ± 58 nm to 143 ± 18 nm, respectively. Organic acids in RE and soil leachate can be adsorbed onto particle surfaces, influencing aggregation. Charge of the four NPs was negative in contact with RE and soil leachate, due to organic matter present in RE and soil leachate. Dissolution in RE after 6 days was 38%, 1.2%, 0.5%, and <0.1% of the elemental content of MoO 3 , Cu(OH) 2 , Mn 3 O 4 , and CeO 2 NPs. Thus, the bioavailability and efficiency of delivery of the NPs or their active ingredients will be substantially modified soon after they are in contact with RE or soil leachate.

Metabolomics is an emerging tool to understand the potential implications of nanotechnology, particularly for agriculture. Although molybdenum (Mo) is a known plant micronutrient, little is known of its metabolic perturbations. Here, corn and wheat seedlings were exposed to MoO 3 nanoparticles (NPs) and the corresponding bioavailable Mo 6+ ion at moderate and excessive levels through root exposures. Physiologically, corn was more sensitive to Mo, which accumulated up to 3.63 times more Mo than wheat. In contrast, metabolomics indicated 21 dysregulated metabolites in corn leaves and 53 in wheat leaves. Five more metabolomic pathways were perturbed in wheat leaves compared to corn leaves. In addition to the overall metabolomics analysis, we also analyzed individual metabolite classes (e.g., amino acids, organic acids, etc.), yielding additional dysregulated metabolites in plant tissues: 7 for corn and 7 for wheat. Most of these were amino acids as well as some sugars. Additional significantly dysregulated metabolites (e.g., asparagine, fructose, reduced glutathione, mannose) were identified in both corn and wheat, due to Mo NP exposure, by employing individual metabolite group analysis. Targeted metabolite analysis of individual groups is thus important for finding additional significant metabolites. We demonstrate the value of metabolomics to study early stage plant responses to NP exposure.

Metal-based nanoparticles (NPs) can be found in wastewater streams, which are significant pathways for the release of NPs to the environment. Determination of the NPs concentration in wastewater streams is important for performing appropriate ecotoxicological evaluations. The aim of this work was to determine the incidence of NPs from 13 different elements throughout the wastewater treatment process by using single particle inductively coupled plasma mass spectrometry (spICP-MS). The incidence was determined in samples of the influent, post-primary treatment and effluent of the activated sludge process, as well as in the reclaimed water of a full-scale wastewater treatment plant (WWTP). In addition, concentration of NPs was determined in the waste activated sludge and in the anaerobic digester. The concentration of metal-based NPs in the influent wastewater were between 1,600 and 10,700 ng/L for elements such as Ti, Fe, Ce, Mg, Zn and Cu, while that for Ni, Al, Ag, Au, Co and Cd was below 100 ng/L. Concentrations in reclaimed water ranged between 0.6 and 721 ng/L, ranked as MgResults indicated that the activated sludge process and reclaimed water system removed 84-99% of natural and engineered metal-based NPs from influent to reclaimed water, except for Mg, Ni and Cd where the removal ranged from 70 to 78%. The highest concentrations of NPs were found in the waste activated sludge and anaerobic sludge, ranging from 0.5 to 39,900 ng/L. The size distribution of NPs differed in different wastewater streams within the WWTP, resulting in smaller particles in the effluent (20-180 nm) than in the influent (23-233 nm) for most elements. Conversely, NPs were notably larger in the waste activated sludge samples than in the anaerobic sludge or wastewater, since conditions in the secondary treatment lead to precipitation of several metal-based NPs. The incidence of metalbased NPs from 13 elements in wastewater decreased significatively after the conventional wastewater treatment train. However, anaerobic digesters store high NPs concentrations. Hence, the disposal of sludge needs to take this into account to evaluate the risk of the release of NPs to the environment.

No abstract

The concentration of silver nanoparticles (nano-Ag) in aqueous media influences the kinetics of ion release; hence, the transformation and stability of nano-Ag are also influenced. The stability, dissolution and further transformation of nano-Ag in aqueous media at predicted environmental concentrations (PECs) mg/L may differ from that reported at higher concentrations. Analytical techniques characterizing nanoparticles (NPs) at mg/L have advantages and limitations, including an inherent bias based on theoretical and analytical considerations, as well as the matrix effects. In this work, we applied nanoparticle tracking analysis (NTA), single particle ICP-MS (sp-ICP-MS), and localized surface plasmon resonance (LSPR) analysis to study the stability and dissolution of nano-Ag with different nominal sizes (20, 40, 80 and 100 nm) at PECs in synthetic wastewater (SWW). The influence of the main wastewater constituents, such as organic matter, Cl À , S 2À , PO 4 3À and NH 4 þ , on the stability and dissolution of nano-Ag (40 nm) at PECs was also determined. Diagrams of the predominant species of silver exposed to major ligands were generated using MINTEQ. After 5 h in SWW, 20 nm nano-Ag dissolved 19.27% and 40 nm nano-Ag dissolved 14.8%. Aggregates of Ag particles were clearly noted for 80 and 100 nm nano-Ag after 5 h of exposure to SWW. Aggregates size also ranged very similar for both techniques, NTA and sp-ICP-MS, 29e211 nm and 38e241 for NTA and 48e210 and 50e220 nm, for sp-ICP-MS, respectively. Monodispersed size distribution (22e85 nm) and low dissolution (up to 5.1%) of nano-Ag at PECs were observed in presence of organic matter (5e800 mg/L) and PO 4 3À (9.5e47.5 mg/L), while precipitation and higher dissolution (up to 74.9%) were observed in media containing either Cl À (0.07e10.64 g/L), S 2À (0.32 e32.1 mg/L) or NH 4 þ (36e90 mg/L), respectively. Speciation diagrams predict the formation of Ag 2 S (s) and AgCl (s) , and soluble species such as AgCl x (xÀ1)-, AgNH 3 þ and Ag(NH 3) 2þ when Ag þ at PECs in wastewater. The NTA and sp-ICP-MS were suitable techniques for sizing nano-Ag in wastewater at PECs at experimented nominal sizes. sp-ICP-MS was also useful to quantify the coexistence of Ag þ and nano-Ag. The LSPR analysis served to determine the relative persistence of original nano-Ag at PECs in the wastewater during the first 5 h after spiking.

Quantitatively monitoring the presence of engineered, natural, or incidental nanoparticles (NPs) is essential to understand their potential environmental and ecotoxicological implications. In particular, a significant number of NPs may travel through wastewater treatment plants (WWTPs), as a conduit to their release to the environment, either in treated effluent or in wastewater sludge (biosolids). Here we developed a fast and simple protocol for full quantitative multielement analysis of metallic or metal-containing NPs in wastewater and sludge samples via single-particle ICP-MS. We employed centrifugation to separate NPs from wastewater sludge, with high recoveries (>84%) for Au and Ag NPs, which have rather high densities (19.3 and 10.5 g cm–3, respectively). In wastewater samples, particle mass concentrations ranged from <1 ng/L for Cd-based NPs to almost 100 μg/L for Mg particles. Particles from most elements detected in wastewater were <100 nm in size, although TiO2 in raw wastewater was around 250 nm in size, and Mg was >1500 nm in size, well beyond the nanoscale. The efficiency of removal of NPs throughout the WWTP was significantly dependent on the type of metal-containing particles and the influent concentration.

Ferrofluids are colloidal suspensions of iron oxide nanoparticles (IONPs) within aqueous or nonaqueous liquids that exhibit strong magnetic properties. These magnetic properties allow ferrofluids to be manipulated and controlled when exposed to magnetic fields. This review aims to provide the current scope and research opportunities regarding the methods of synthesis of nanoparticles, surfactants, and carrier liquids for ferrofluid production, along with the rheology and applications of ferrofluids within the fields of medicine, water treatment, and mechanical engineering. A ferrofluid is composed of IONPs, a surfactant that coats the magnetic IONPs to prevent agglomeration, and a carrier liquid that suspends the IONPs. Coprecipitation and thermal decomposition are the main methods used for the synthesis of IONPs. Despite the fact that thermal decomposition provides precise control on the nanoparticle size, coprecipitation is the most used method, even when the oxidation of iron can occur. This oxidation alters the ratio of maghemite/magnetite, influencing the magnetic properties of ferrofluids. Strategies to overcome iron oxidation have been proposed, such as the use of an inert atmosphere, adjusting the Fe­(II) and Fe­(III) ratio to 1:2, and the exploration of other metals with the oxidation state +2. Surfactants and carrier liquids are chosen according to the ferrofluid application to ensure stability. Hence, a compatible carrier liquid (polar or nonpolar) is selected, and then, a surfactant, mainly a polymer, is embedded in the IONPs, providing a steric barrier. Due to the variety of surfactants and carrier liquids, the rheological properties of ferrofluids are an important response variable evaluated when synthesizing ferrofluids. There are many reported applications of ferrofluids, including biosensing, medical imaging, medicinal therapy, magnetic nanoemulsions, and magnetic impedance. Other applications include water treatment, energy harvesting and transfer, and vibration control. To progress from synthesis to applications, research is still ongoing to ensure control of the ferrofluids’ properties.