Rational design of analytical criteria to perform dissolution testing of nanomaterials: the relevance of juice composition for hazard identification and grouping.

Even small changes in physicochemical properties of nanoforms (NFs), can drive differences in their environmental fate and hazard. The large number of new materials being developed means it will not be feasible to test and characterise the fate, behaviour and (eco)toxicity of each individual NF. This is further amplified by transformations of NFs over their lifecycle, changing the processes governing their risk. A common complexity arises from dissolution, where the combined toxicity of the exposure arises from both the solutes and any remaining particles contribution to the overall toxicity of the exposure. For efficient and effective risk assessment, it is the most relevant form of the NF for a given exposure that should be targeted for testing and assessment. In aquatic systems, functional fate processes (including dissolution, dispersion stability and chemical and biological transformations) determine the NF’s exposure relevant form. Whilst transformations in the environment alter the initial properties of an NF, different NFs may follow a shared functional fate pathway and ultimately present a similar fate and hazard profile in the environment. Therefore, these processes may be used to scientifically justify grouping NFs and read-across for specific endpoints from data rich NF(s) to verified members of the group that have not been tested yet. Integrated Approaches to Testing and Assessment (IATA) have been used in other regulatory contexts to support the collection and integration of relevant existing information as well as the targeted generation of new data to support grouping and read-across. Here, a new IATA is presented consisting of decision nodes focused on dissolution, dispersion stability, chemical transformations and the relative contribution to toxicity of the particle and dissolved component of the overall exposure. The IATA focuses on the fate of NFs in aquatic systems outside of the body, but it can be considered a template for future assessment of in vivo kinetics, which will require further development. Guidance on tiered testing approaches and thresholds for grouping within each decision node are critically discussed. Worked examples for ecotoxicity of metal oxide NFs in aqueous systems (in microbial communities isolated from soils and for lettuce plants in hydroponic systems) demonstrate successful identification of the exposure relevant form of the NF in these case studies and allows for different grouping of NFs through application of the IATA.

A 2‐year sampling campaign was realized on French Mediterranean beach (Palavas‐les‐Flots Hérault) in order to measure the concentration of UV filters released from the sunscreen used by bathers. Multiple factors suspected of playing determining roles in the UV filter pattern in water were explored, such as the seasonal and daily time evolutions, or the vertical and horizontal distributions, and they were regarded through the UV filter characteristics.

Nanoforms (NFs) of a substance may be distinguished from one another through differences in their physicochemical properties. When registering nanoforms of a substance for assessment under the EU REACH framework, five basic descriptors are required for their identification: composition, surface chemistry, size, specific surface area and shape. To make the risk assessment of similar NFs efficient, a number of grouping frameworks have been proposed, which often require assessment of similarity on individual physicochemical properties as part of the group justification. Similarity assessment requires an understanding of the achievable accuracy of the available methods. It must be demonstrated that measured differences between NFs are greater than the achievable accuracy of the method, to have confidence that the measured differences are indeed real. To estimate the achievable accuracy of a method, we assess the reproducibility of six analytical techniques routinely used to measure these five basic descriptors of nanoforms: inductively coupled plasma mass spectrometry (ICP-MS), Thermogravimetric analysis (TGA), Electrophoretic light scattering (ELS), Brunauer-Emmett-Teller (BET) specific surface area and transmission and scanning electron microscopy (TEM and SEM). Assessment was performed on representative test materials to evaluate the reproducibility of methods on single NFs of substances. The achievable accuracy was defined as the relative standard deviation of reproducibility (RSDR) for each method. Well established methods such as ICP-MS quantification of metal impurities, BET measurements of specific surface area, TEM and SEM for size and shape and ELS for surface potential and isoelectric point, all performed well, with low RSDR, generally between 5 and 20%, with maximal fold differences usually <1.5 fold between laboratories. Applications of technologies such as TGA for measuring water content and putative organic impurities, additives or surface treatments (through loss on ignition), which have a lower technology readiness level, demonstrated poorer reproducibility, but still within 5-fold differences. The expected achievable accuracy of ICP-MS may be estimated for untested analytes using established relationships between concentration and reproducibility, but this is not yet the case for TGA measurements of loss on ignition or water content. The results here demonstrate an approach to estimate the achievable accuracy of a method that should be employed when interpreting differences between NFs on individual physicochemical properties.

Before placing a new nanoform (NF) on the market, its potential adverse effects must be evaluated. This may e.g. be done via hazard and risk assessment. Grouping and read-across of NFs is a possible strategy to reduce resource consumption, maximising the use of existing data for assessment of NFs. The GRACIOUS project provides a framework in which possible grouping and read-across for NFs is mainly based on an evaluation of their similarity. The impact of NFs on human health and the environment depends strongly on the concentration of the NF and its physicochemical properties, such as chemical composition, size distribution, shape, etc. Hence, knowledge of the most relevant physicochemical properties is essential information for comparing similarity. The presented work aims to refine existing proposals for sets of descriptors (descriptor array) that are needed to describe distinct NFs of a material to identify the most relevant ones for grouping and read-across. The selection criteria for refining this descriptor array are explained and demonstrated. Relevant protocols and methods are proposed for each physicochemical property. The required and achievable measurement accuracies of the refined descriptor array are reviewed, as this information is necessary for similarity assessment of NFs based on individual physicochemical properties.

Nanoparticles (NPs) can be produced via physical, chemical, or biological approaches. Yet, the impact of the synthesis approaches on the environmental fate and effects of NPs is poorly understood. Here, we synthesized AgNPs through chemical and biological approaches (cit-AgNPs and bio-AgNPs), characterized their properties, and toxicities relative to commercially available Ag nanopowder (np-AgNPs) to the clam Mercenaria mercenaria. The chemical synthesis is based on the reduction of ionic silver using sodium borohydride as a reducing agent and trisodium citrate as a capping agent. The biological synthesis is based on the reduction of ionic silver using biomolecules extracted from an atoxigenic strain of a filamentous fungus Aspergillus parasiticus. The properties of AgNPs were determined using UV-vis, dynamic light scattering, laser Doppler electrophoresis, (single particle)-inductively coupled plasma-mass spectroscopy, transmission electron microscopy, and asymmetric flow-field flow fractionation. Both chemical and biological synthesis approaches generated spherical AgNPs. The chemical synthesis produced AgNPs with narrower size distributions than those generated through biological synthesis. The polydispersity of bio-AgNPs decreased with increases in cell free extract (CFE):Ag ratios. The magnitude of the zeta potential of the cit-AgNPs was higher than those of bio-AgNPs. All AgNPs formed aggregates in the test media i.e., natural seawater. Based on the same total Ag concentrations, all AgNPs were less toxic than AgNO3. The toxicity of AgNPs toward the juvenile clam, Mercenaria mercenaria, decreased following the order np-AgNPs > cit-AgNPs > bio-AgNPs. Expressed as a function of dissolved Ag concentrations, the toxicity of Ag decreased following the order cit-AgNPs > bio-AgNPs > AgNO3 ~ np-AgNPs. Therefore, the toxicity of AgNP suspensions can be attributed to a combined effect of dissolved and particulate Ag forms. These results indicate that AgNP synthesis methods determine their environmental and biological behaviors and should be considered for a more comprehensive environmental risk assessment of AgNPs.

Stormwater conveys natural and engineered (nano)-particles, like any other pollutants, from urban areas to water resources. Thus, the use of stormwater green infrastructures (SGI), which infiltrate and treat stormwater, can potentially limit the spread of engineered (nano)-particles in the environment. However, the concentration of engineered (nano)-particles in soil or biofilter media used in SGI has not been measured due to difficulties in distinguishing natural vs. engineered (nano)-particles. This study reports, for the first time, the concentration and size distribution of TiO2 engineered (nano)-particles in soils collected from SGI. The concentrations of TiO2 engineered (nano)-particles were determined by mass balance calculations based on shifts in elemental concentration ratios, i.e., Ti to Nb, Ti to Ta, and Ti to Al in SGI soils relative to natural background elemental ratios. The concentrations of TiO2 engineered (nano)-particles in SGI soils varied between 550 ± 13 and 1800 ± 200 mg kg-1. A small fraction of TiO2 engineered (nano)-particles could be extracted by ultrapure water (UPW) and Na4P2O7; however, the concentration of TiO2 engineered (nano)-particles was higher in the Na4P2O7-extracted suspensions than in UPW-extracted suspensions. The concentration of TiO2 in the nanosize range increased with the increase in extractant (Na4P2O7) volume to soil mass ratio due to the increased disaggregation of soil heteroaggregates. The size distribution of TiO2 engineered (nano)-particles in the < 450 nm Na4P2O7-extracted suspension from one of the SGI soils was determined by asymmetrical flow-field flow fractionation coupled to inductively coupled plasma-mass spectrometer, and was found to vary in the range of 25-200 nm with a modal size of 50 nm. These results demonstrated that the increase in the Ti to natural tracers (e.g., Nb, Ta, and Al) elemental ratios in the SGI soil relative to bulk soil can be used to estimate the concentration of TiO2 engineered (nano)-particles in SGI.

Quantification of engineered nanomaterials (ENMs) concentrations in surface waters remains one of the key challenges in environmental nanoscience and nanotechnology. A promising approach to estimate metal and metal oxide ENM concentrations in complex environmental samples is based on the increase in the elemental ratios of ENM-contaminated samples relative to the corresponding natural background elemental ratios. This contribution evaluated the detection and quantification of Ag, CeO2, and Fe2O3 ENMs spiked in synthetic soft, or in natural river waters using the elemental ratio approach, and evaluated the effect of extractants including sodium hydroxide (NaOH), sodium oxalate (Na2C2O4) and sodium pyrophosphate (Na4P2O7) on the recovery of ENMs from the spiked waters. The extracted ENM concentrations were higher in Na4P2O7-extracted suspensions than in NaOH- and Na2C2O4-extracted suspensions due to the higher efficiency of Na4P2O7 to break up natural and engineered nanomaterial heteroaggregates. The size distributions of the extracted suspensions were determined by asymmetrical flow-field flow fractionation coupled to inductively coupled plasma-mass spectrometer (AF4-ICP-MS). These size distribution analysis demonstrated that Ag ENMs were extracted from the spiked liver water as both primary particles and small (<100 nm) aggregates, whereas CeO2 ENMs were extracted from the spiked river water as aggregates of particles in the size range 0-200 nm. The number particle size distribution of the extracted suspensions confirmed that Ag ENMs were extracted as a mixture of primary and aggregated Ag ENMs. Small Ag ENMs (Le. <20 nm) were detected by AF4-ICP-MS, but these particles were not detected by single particle (sp)-ICP-MS due to high size detection limit of sp-ICP-MS. This study illustrates that the elemental ratio approach is a promising approach to detect and quantify ENMs in surface waters. This study also illustrates the need fora multi-method approach, including extraction, filtration. AF4-ICP-MS and sp-ICP-MS, to detect, quantify, and characterize ENMs in surface waters. (C) 2020 Elsevier B.V. All rights reserved.

Characterization of natural nanomaterial (NNM) physicochemical properties - such as size, size distribution, elemental composition and elemental ratios - is often hindered by lack of methods to disperse NNMs from environmental samples. This study evaluates the effect of extractant composition, pH. and ionic strength on soil NNM extraction in term of recovery and release of primary particles/small aggregate sizes (i.e., <200 nm). The extracted NNMs were characterized for hydrodynamic diameter and zeta potential by dynamic light scattering and laser Doppler electrophoresis, natural organic matter desorption by UV-Vis spectroscopy, element composition by inductively coupled plasma-mass spectroscopy (ICP-MS), size based elemental distribution by field flow fractionation coupled to ICP-MS, and morphology by transmission electron microscopy. The extracted NNM concentrations increased following the order of NaOH <= Na2CO3 < Na2C2O4 < Na4P2O7, Na4P2O7 was the most efficient extractant and results in 2-12 folds higher NNM extraction than other extractants. The Na4P2O7 extracted NNMs exhibited narrower size distribution with smaller modal size relative to NaOH, Na2CO3, Na2C2O4 extracted NNMs. Thus. Na4P2O7 enhances the extraction of primary NNMs and/or smaller NNM aggregates (i.e., size <200 nm). Na4P2O7 promote soil microaggregates breakup and release of NNMs by reducing free multivalent cation concentration in soil pore water by forming metal-phosphate complexes and by enhancing NNM surface charge via phosphate sorption on NNM surfaces. Additionally, the extracted NNM concentrations increased with the increase in extractant concentration and pH, except at 100 mM where the high ionic strength might have induced NNM aggregation. The improved NNM-extraction will improve the overall understanding of the physicochemical properties of NNMs in environmental systems. This study presents the key properties of NNMs that can be used as background information to differentiate engineered nanomaterials (ENMs) from NNMs in complex environmental media. (C) 2019 Elsevier B.V. All rights reserved.

Sanitary sewer overflows (SSOs) are a common problem across the United States. An estimated 23,000-75,000 SSOs occurred annually in 2004 discharging between 11 and 38 billion liters of untreated wastewater to receiving waters. SSOs release many contaminants, including engineered nanomaterials (ENMs), to receiving water bodies. Measuring ENM concentrations in environmental samples remains a key challenge in environmental nanotechnology and requires the distinction between natural and engineered particles. This distinction between natural and engineered particles is often hampered by the similarities in the intrinsic properties of natural and engineered particles such as particle size, composition, density, surface chemistry, and by the limitations of the available nanometrology tools. To overcome these challenges, we applied a multi-method approach to measure the concentrations and properties of TiO2 engineered particles (e.g., ENMs and pigments) including 1) multi-element single particle-inductively coupled plasma-mass spectrometry (ME-SP-ICP-MS) to identify elemental associations and to determine elemental ratios in natural particles, 2) total elemental concentrations and ratios calculated from total metal concentrations measured following total sample digestion to estimate engineered particle concentrations, and 3) transmission electron microscopy (TEM) to characterize engineered particle size and morphology. ME-SP-ICP-MS analysis revealed that natural TiO2 particles are often associated with at least one of the following elements Al, Fe, Ce, Si, La, Zr, Nb, Pb, Ba, Th, Ta, W and U, and that elemental ratios of Ti to these elements is typical of riverine particulates and the average crustal ratios, except for Pb likely due to anthropogenic Pb contamination. High TiO2 engineered particle concentrations up to 100 μg L-1 were found in SSOs-impacted surface waters. TEM analysis demonstrated the presence of regular-shape TiO2 particles in SSOs-impacted surface waters. This study provides a comprehensive approach for measuring TiO2 engineered particle concentrations in surface waters. The quantitative data produced in this work can be used as input for modeling studies and pave the road toward routine monitoring of ENMs in environmental systems, validation of ENM fate models, and more accurate ENM exposure and risk assessment.

Characterization and understanding of natural nanomaterials (NNMs) properties is essential to differentiate engineered nanomaterials (ENMs) from NNMs. However, NNMs in environmental samples typically occur as heteroaggregates with other particles, e.g., NNMs, ENMs, and larger particles. Therefore, there is a need to isolate NNMs into their primary particles to better characterize their physicochemical properties. Here, we evaluated the efficiency of sodium hydroxide, sodium oxalate, and sodium pyrophosphate to extract NNMs from surface waters. The extracted NNMs were characterized for total metal concentration by inductively coupled plasma-mass spectrometry (ICP-MS) following full digestion; size distribution, elemental composition and ratios by flow-field flow fractionation (AF4)-ICP-MS; and morphology by transmission electron microscopy (TEM). Sodium pyrophosphate extraction resulted in the highest NNM concentration and the smallest NNM size distribution. Sodium hydroxide and sodium oxalate extraction generated heteroaggregates with a broad size distribution. The NNM extraction efficiency increased with extractant (sodium oxalate and sodium pyrophosphate) concentration. The concentration of metals in the sodium pyrophosphate-extracted NNMs compared to the total metal concentration was element-dependent and varied from as high as >80% for Cu, Zn, and Sr to as low as <5% for Al, Ti, and Nb. This study provides a simple protocol for NNM extraction from complex environmental samples and provides a better understanding of NNM physicochemical properties. The presented NNM extraction protocol forms the basis for ENM extraction from natural waters.

Increasing amounts of engineered nanomaterials such as TiO 2 and CeO 2 are released into air, waters, soils, and sediments. However, assessing the human-made origin of those nanomaterials is rather difficult because Ti- and Ce-rich particles are naturally present in soils and sediments at concentrations typically much higher than estimated concentrations of engineered nanomaterials. In addition, analysis is complicated by the interactions and aggregation of nanoparticles with environmental particles. Therefore, more knowledge on the properties of natural nanomaterials is needed to distinguish engineered nanomaterials in natural systems. Here, we extracted soil nanomaterials with six extractants and compared recovery and disaggregation to primary particles. Nanomaterials were characterized for hydrodynamic diameter and zeta potential by dynamic light scattering, size-based elemental distribution by field-flow fractionation coupled with inductively coupled plasma-mass spectroscopy, and morphology by transmission electron microscopy. Results show that nanomaterial concentrations increased from CH 3 COOH–NaCl–water (lowest), to water or NaCl–water, Na 2 CO 3 , Na 4 P 2 O 7 , and NaCl–Na 4 P 2 O 7 (highest). Na 4 P 2 O 7 was the most efficient extractant that induced the release of primary nanomaterials from microaggregates. Although sodium carbonate extracted relatively high concentrations of nanomaterials, the extracted nanomaterials occurred mainly as aggregates of primary nanomaterials. Ultrapure water, sodium chloride and acetic acid resulted in poor nanomaterial extraction and broad size distributions. Elemental ratios illustrate that Ti is associated with Nb, Ta, and V, and that Ce is associated with rare earth elements such as La, Eu, Y, Ho, Er, Tm, and Yb. Our findings indicate that size, size distribution, and elemental ratios can be used as fingerprints to differentiate engineered nanomaterials such as TiO 2 and CeO 2 from natural nanomaterials in complex media.

Detection, characterization, and quantification of engineered nanomaterials (ENMs) in aquatic systems is a topic of high interest because ENMs are being released increasingly into the environment. In the natural environment, ENMs form heteroaggregates with natural particles which complicates their characterization and quantification. This study investigates the influence of sodium pyrophosphate (NaPP) and sodium oxalate (NaOx) on TiO2 ENM stability in the presence of montmorillonite, natural organic matter (Suwannee River humic acids, SRHA), and CaCl2 with the aim to propose a fundamental protocol for the extraction of ENMs from natural waters. NaPP, not only prevents aggregation, but also rapidly induces TiO2 ENM disaggregation and release from TiO2-clay heteroaggregates -previously formed in presence of CaCl2 and SRHA-in the form of individual particles, or small aggregates. The recovery of TiO2 ENMs in a montmorillonite dispersion in presence of SRHA and CaCl2 was > 90% for the < 100 nm size fraction, independent of the CaCl2 concentration. In contrast, without NaPP treatment, no TiO2 ENMs smaller than 100 nm were recovered in presence of divalent cations without SRHA, and < 15% TiO2 ENMs were recovered in the < 100 nm fraction in the presence of divalent cations and SRHA. NaOx did not affect the stability of TiO2 ENMs in the absence of electrolytes and did not stabilize TiO2 ENMs in presence of divalent electrolyte. These findings provide a proof-of-concept for the application of NaPP for the extraction of TiO2 ENMs, and potentially other ENMs, from ENM-natural particle heteroaggregates. Release of ENMs in the form of individual particles, or small aggregates is essential to facilitate ENM characterization and quantification in complex environmental media.

Multiple facets of TiO2 nanoparticle destabilization mechanisms in the presence of surfactant molecules and divalent cations.

Being able to reduce the size of a rheometer down to the micron scale is a unique opportunity to explore the mechanical response of expensive and/or confined liquids and gels. To this aim, we synthesize micron size wires with magnetic properties and examine the possibility of using them as microrheology probes. In this work, we exploit the technique of rotational magnetic spectroscopy by placing a wire in a rotating magnetic field and monitor its temporal evolution by time-lapse microscopy. The wire-based microrheology technique is tested on wormlike micellar surfactant solutions showing very different relaxation dynamics and viscosities. A model for the wire rotation is also developed and used to predict the wire behavior. It is shown that the rheological parameters of the surfactant solutions including the static shear viscosity, the entangled micellar network relaxation time and the elastic modulus are in good agreement with those of conventional rheometry.

Viscoelastic liquids are characterized by a finite static viscosity and a yield stress of zero, whereas soft solids have an infinite viscosity and a non-zero yield stress. The rheological nature of viscoelastic materials has long been a challenge and is still a matter of debate. Here, we provide for the first time the constitutive equations of linear viscoelasticity for magnetic wires in yield-stress materials, together with experimental measurements by using magnetic rotational spectroscopy (MRS). In MRS, the wires were subjected to a rotational magnetic field as a function of frequency and the motion of the wire was moni-tored by using time-lapse microscopy. The studied soft solids were aqueous dispersions of gel-forming polysaccharide (gellan gum) at concentrations above the gelification point. It was found that soft solids exhibited a clear and distinctive signature compared with viscous and viscoelastic liquids. In particular, the average wire rotation velocity equaled zero over a broad frequency range. We also showed that the MRS technique is quantitative. The equilibrium elastic modulus was retrieved from the wire oscillation amplitudes, and agrees with polymer-dynamics theory.

Agglomeration and disagglomeration processes are expected to play a key role on the fate of engineered nanoparticles in natural aquatic systems. These processes are investigated here in detail by studying first the stability of TiO2 nanoparticles in the presence of monovalent and divalent electrolytes at different pHs (below and above the point of zero charge of TiO2) and discussing the importance of specific divalent cation adsorption with the help of the DLVO theory as well as the importance of the nature of the counterions. Then the impact of one polysaccharide (alginate) on the stability of agglomerates formed under pH and water hardness representative of Lake Geneva environmental conditions is investigated. In these conditions the large TiO2 agglomerates (diameter > 1 μm) are positively charged due to Ca2 + and Mg2 + specific adsorption and alginate, which is negatively charged, adsorbs onto the agglomerate surface. Our results indicate that the presence of alginate at typical natural organic matter concentration (1–10 mg L− 1) strongly modifies the TiO2 agglomerate (50 mg L− 1) stability by inducing their partial and rapid disagglomeration. The importance of disagglomeration is found dependent on the alginate concentration with maximum of disagglomeration obtained for alginate concentration ≥ 8 mg L− 1 and leading to 400 nm fragments. From an environmental point of view partial restabilization of TiO2 agglomerates in the presence of alginate constitutes an important outcome. Disagglomeration will enhance their transport and residence time in aquatic systems which is an important step in the current knowledge on risk assessment associated to engineered nanoparticles.