Heteroaggregation of engineered nanoparticles (ENPs) with suspended particulate matter (SPM) ubiquitous in natural waters often dominates the transport behaviour and overall fate of ENPs in aquatic ...environments. In order to provide meaningful exposure predictions and support risk assessment for ENPs, environmental fate and transport models require quantitative information about this process, typically in the form of the so-called attachment efficiency for heteroaggregation
α
hetero
. The inherent complexity of heteroaggregation-encompassing at least two different particle populations, various aggregation pathways and several possible attachment efficiencies (
α
values)-makes its theoretical and experimental determination challenging. In this frontier review we assess the current state of knowledge on heteroaggregation of ENPs with a focus on natural surface waters. A theoretical analysis presents relevant equations, outlines the possible aggregation pathways and highlights different types of
α
. In a second part, experimental approaches to study heteroaggregation and derive
α
values are reviewed and three possible strategies are identified: i) monitoring changes in size, ii) monitoring number or mass distribution and iii) studying indirect effects, such as sedimentation. It becomes apparent that the complexity of heteroaggregation creates various challenges and no single best method for its assessment has been developed yet. Nevertheless, many promising strategies have been identified and meaningful data can be derived from carefully designed experiments when accounting for the different concurrent aggregation pathways and clearly stating the type of
α
reported. For future method development a closer connection between experiments and models is encouraged.
Heteroaggregation of engineered nanoparticles with suspended particulate matter in theory and practice: a roadmap for understanding and determining attachment efficiencies.
Particulate emissions from vehicle exhaust catalysts are the primary contributors to platinum group elements (PGEs) being released into roadside environments, especially platinum (Pt) particles. With ...increasing traffic density, it is essential to quantify the emission, accumulation, and potential health effects of traffic-emitted Pt particles. In this study, three procedures were investigated to extract Pt nanoparticles (NPs) from sediments and characterize them by single-particle inductively coupled plasma time-of-flight mass spectrometry (spICP-TOF-MS). For this purpose, a reference sediment sample was spiked with manufactured Pt NPs. Pt NPs’ extraction recoveries reached from 50% up to 102%, depending on the extraction procedure and whether the particle mass or number was used as the metric. Between 17% and 35% of the Pt NPs were found as unassociated Pt NPs and between 31% and 78% as Pt NPs hetero-aggregated with other sediment particles. Multi-elemental analysis of Pt-containing NPs in the pristine sediment revealed frequently co-occurring elements such as Au, Bi, and Ir, which can be used to determine a natural background baseline. Our results demonstrated that spICP-TOF-MS elemental characterization allows for distinguishing anthropogenic Pt NPs from the natural background. In the future, this could enable the sensitive monitoring of PGE release from anthropogenic sources such as vehicle exhausts.
•Suspended Particulate Matter analogues to study particulate contaminant interactions.•Analogue flocs represent characteristics of natural SPM relevant for agglomeration.•Components reflect ...heterogeneous physicochemical surface properties of natural SPM.•Composition and structure of analogues resemble natural riverine SPM.•Analogues can be reproducibly generated and are stable during handling in the lab.
Aquatic fate models and risk assessment require experimental information on the potential of contaminants to interact with riverine suspended particulate matter (SPM). While for dissolved contaminants partition or sorption coefficients are used, the underlying assumption of chemical equilibrium is invalid for particulate contaminants, such as engineered nanomaterials, incidental nanoparticles, micro- or nanoplastics. Their interactions with SPM are governed by physicochemical forces between contaminant-particle and SPM surfaces. The availability of a standard SPM material is thus highly relevant for the development of reproducible test systems to evaluate the fate of particulate contaminants in aquatic systems. Finding suitable SPM analogues, however, is challenging considering the complex composition of natural SPM, which features floc-like structures comprising minerals and organic components from the molecular to the microorganism level. Complex composition comes with a heterogeneity in physicochemical surface properties, that cannot be neglected. We developed a procedure to generate SPM analogue flocs from components selected to represent the most abundant and crucial constituents of natural riverine SPM, and the process-relevant SPM surface characteristics regarding interactions with particulate contaminants. Four components, i.e., illite, hematite, quartz and tryptophan, combined at environmentally realistic mass-ratios, were associated to complex flocs. Flocculation was reproducible regarding floc size and fractal dimension, and multiple tests on floc resilience towards physical impacts (agitation, sedimentation-storage-resuspension, dilution) and hydrochemical changes (pH, electrolytes, dissolved organic matter concentration) confirmed their robustness. These reproducible, ready-to-use SPM analogue flocs will strongly support future research on emerging particulate contaminants.
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Environmental exposure modeling has been used extensively in the last years to obtain estimates of environmental concentrations of engineered nanomaterials (ENMs). In this perspective piece, we ...explore the issues when aiming to validate modeled environmental concentrations and propose options for both modelers and analytical chemists on how to proceed in the future to better compliment one another's efforts. In this context, validation means to determine the degree to which the simulation results from a model are accurate representations of the real world by comparison with analytical data. Therefore, for such a model validation procedure, analytical methods need to be available which provide information in the same subject area. Currently, a major issue with nanometrology is that a multitude of nanomaterials are present in natural systems but only some are ENMs; various other particles of natural origin are abundant in the same systems. The analytical tools available are not yet capable to distinguish the natural from engineered nanomaterials at the low ENM concentrations expected in complex environmental matrices. However, both modeling and analytical studies are able to provide an orthogonal view on nanomaterials: modeling is able to yield estimates of the presence of ENMs in various environmental compartments while analytics can provide physical characterization of ENMs in these systems with hints towards the total nanomaterial concentration. While we need to make strides to improve the two approaches separately, using the resulting data together in a mutually supportive way will advance the field of ENM risk assessment.
Validation of modeled environmental concentrations of nanomaterials is currently not possible.
The potential environmental and human health risks from microplastic (1 µm to 1 mm) and nanoplastic (<1 µm) particles (MNPs) is receiving increasing attention from scientists and the public ...
Humic acid-coated goethite nanoparticles (HA-GoeNPs) have been recently proposed as an effective reagent for the in situ nanoremediation of contaminated aquifers. However, the effective dosage of ...these particles has been studied only at laboratory scale to date. This study investigates the possibility of using HA-GoeNPs in remediation of real field sites by mimicking the injection and transport of HA-GoeNPs under realistic conditions. To this purpose, a three-dimensional (3D) transport experiment was conducted in a large-scale container representing a heterogeneous unconfined aquifer. Monitoring data, including particle size distribution, total iron (Fetot) content and turbidity measurements, revealed a good subsurface mobility of the HA-GoeNP suspension, especially within the higher permeability zones. A radius of influence of 2 m was achieved, proving that HA-GoeNPs delivery is feasible for aquifer restoration. A flow and transport model of the container was built using the numerical code Micro and Nanoparticle transport Model in 3D geometries (MNM3D) to predict the particle behavior during the experiment. The agreement between modeling and experimental results validated the capability of the model to reproduce the HA-GoeNP transport in a 3D heterogeneous aquifer. Such result confirms MNM3D as a valuable tool to support the design of field-scale applications of goethite-based nanoremediation.
The dissolution of metal-based engineered nanomaterials (ENMs) in aquatic environments is an important mechanism governing the release of toxic dissolved metals. For the registration of ENMs at ...regulatory bodies such as REACH, their dissolution behavior must therefore be assessed using standardized experimental approaches. To date, there are no standardized procedures for dissolution testing of ENMs in environmentally relevant aquatic media, and the Organisation for Economic Co-operation and Development (OECD) strongly encourages their development into test guidelines. According to a survey of surface water hydrochemistry, we propose to use media with low concentrations of Ca
and Mg
for a better simulation of the ionic background of surface waters, at pH values representing acidic (5 < pH < 6) and near-neutral/alkaline (7 < pH < 8) waters. We evaluated a continuous flow setup adapted to expose small amounts of ENMs to aqueous media, to mimic ENMs in surface waters. For this purpose, silver nanoparticles (Ag NPs) were used as model for soluble metal-bearing ENMs. Ag NPs were deposited onto a 10 kg.mol
membrane through the injection of 500 µL of a 5 mg.L
or 20 mg.L
Ag NP dispersion, in order to expose only a few micrograms of Ag NPs to the aqueous media. The dissolution rate of Ag NPs in 10 mM NaNO
was more than two times higher for ~2 µg compared with ~8 µg of Ag NPs deposited onto the membrane, emphasizing the importance of evaluating the dissolution of ENMs at low concentrations in order to keep a realistic scenario. Dissolution rates of Ag NPs in artificial waters (2 mM Ca(NO
)
, 0.5 mM MgSO
, 0-5 mM NaHCO
) were also determined, proving the feasibility of the test using environmentally relevant media. In view of the current lack of harmonized methods, this work encourages the standardization of continuous flow dissolution methods toward OECD guidelines focused on natural aquatic environments, for systematic comparisons of nanomaterials and adapted risk assessments.
The recent expansion in the use of nanomaterials in consumer and industrial applications has led to a growing concern over their behavior, fate, and impacts in environmental systems. However, ...engineered nanoparticles comprise only a small fraction of the total nanoparticle mass in aquatic systems. Human activities, particularly in urban watersheds, are increasing the population of incidental nanoparticles and are likely altering the cycling of more abundant natural nanoparticles. Accurate detection, quantification, characterization, and tracking of these different populations is important for assessing both the ecological risks of anthropogenic particles, and their impact on environmental health. The urban portion of the South Platte watershed in Denver, Colorado (USA) was sampled for zinc to identify and quantify different nanomaterial sources. Single particle ICP-QMS was employed, to provide single elemental (Zn) signals arising from particle detection events. Coupling spICP-QMS to sample pre-fractionation (sedimentation, filtration) provided some insights into Zn association with nanoparticulate, colloidal, and suspended sediment phases. Single particle ICP-TOFMS (spICP-TOFMS) provided quantification across a large atomic mass range, yielding an even more detailed characterization (elemental ratios) on a particle-by-particle basis, providing some delineation of multiple sources of particles. Across the watershed, on average, 21% of zinc mass was present as zinc-only particles with a rather uniform mean size of 40.2 nm. Zinc that was detected with one or more other elements, primarily Al, Fe, and Si, is likely to be present as heteroagglomerates or within mineral colloids. Although spICP-TOFMS provides a substantial amount of information, it is still in its early stages as an analytical technique and currently lacks the requisite sensitivity to study the smallest of nanoparticles. As this technique continues to develop, it is anticipated that this methodology can be broadly applied to study sources, behavior and effects of a disparate variety of nanoparticles from both geogenic and anthropogenic origins.
The scientific community has invested effort into standardising methodologies for the regulatory ecotoxicity testing of engineered nanomaterials (ENMs), but the practical requirements for ...bioaccumulation testing of ENMs have been given less attention. A strategy for a tiered approach to bioaccumulation testing of ENMs using fish is proposed, with recommendations for its implementation by regulatory agencies. The strategy recognises that testing the many shapes, sizes and chemistries of ENMs as new substances
in vivo
would be an unrealistic workload. The approach therefore includes grouping/read-across methods and tools to screen out ENMs of negligible/low bioaccumulation potential. The strategy proposes reductions of animal use for
in vivo
testing and with greater consideration of
in vitro
methods. The first tier uses dissolution in water or lipids and particle settling rates as environmental chemistry triggers for 'ENMs of concern'. The first tier also involves a weight of evidence from these tests, plus using existing data sets from selected literature that meet data quality criteria for ENMs. Tier 2 involves new data generation using
in silico
models now being validated for ENMs, including QSARs and systems biology tools. Tier 2 also includes using existing experimental data, and an option to collect new data. These data can be on soils/sediments, microbial degradation, and bioaccumulation studies on invertebrates or fish cell lines. In tier 3, an
in chemico
digestibility assay simulating the gut lumen of fish is proposed to identify the bioaccessible fractions from an oral exposure to ENMs. If the digestibility assay is positive, then
in vitro
gut sacs from rainbow trout can be used to confirm accumulation by the gut mucosa. Only if both these tests in tier 3 are positive would the work proceed to the final
in vivo
test (tier 4) which is essentially the OECD TG 305 method for dietary bioaccumulation testing using fish, with some caveats and recommendations for ENMs. These include considerations of terminology, how to prepare contaminated food for dietary exposures, the additional controls and endpoints for ENMs, measuring ENMs in food and tissues to confirm the exposure, and the limitations of any subsequent calculation of the bioaccumulation potential.
The scientific community has invested effort into standardising methodologies for the regulatory ecotoxicity testing of engineered nanomaterials (ENMs), but the practical requirements for bioaccumulation testing of ENMs have been given less attention.
Foraminifera are unicellular organisms and play a pivotal role in the marine material cycles. Past observations have shown that the species Elphidium excavatum is the most common foraminifera in the ...Baltic Sea. Feeding experiments showed that the food uptake and thus the turnover of organic matter are influenced by changes of physical parameters (e.g., temperature, salinity). Since many areas of the Baltic Sea are strongly affected by anthropogenic activity and are strongly contaminated by heavy elements from shipping in the past, this study examined the effect of heavy elements pollution on the food uptake of the most common foraminiferal species of the Baltic Sea, E. excavatum which was a subject of several previous studies. Therefore, Baltic Sea seawater was enriched with metals at various levels above normal seawater levels and the uptake of 13C- and 15N-labelled phytodetritus was measured by isotope ratio mass spectrometry. For each combination of metal type, concentration and time point 20 individuals of E. excavatum (three replicates) were fed with the green algae Dunaliella tertiolecta. The effect of dose parameters was measured in a two-way analysis of variance. Significant differences of food uptake were observable at different types and levels of heavy elements in sea water. Even a 557-fold increase in the Pb concentration did not affect food uptake, whereas strong negative effects were found for higher levels of Zn (144 and 1044-fold) and especially for Cu (5.6 and 24.3-fold). In summary it can be stated, that an increase in the heavy elements pollution in the Kiel Fjord will lead to a significant reduction in the turnover of organic matter by foraminifera such as E. excavatum.
Foraminifera, Feeding experiments, Heavy metal, Toxic metal, Metabolism.
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