The use and detection of quantum dots as nanotracers in environmental fate studies of engineered nanoparticles.

Investigations of the behavior and effects of engineered nanoparticles (ENPs) on human health and the environment need detailed knowledge of their fate and transport in environmental compartments. Such studies are highly challenging due to low environmental concentrations, varying size distribution of the particles and the interference with the natural background. A strategy to overcome these limits is to use mimics of ENPs with unique detectable properties that match the properties of the ENPs as nanotracers. A special class of ENPs that can be tracked are quantum dots (QDs). QDs are composed of different metals, metalloids, or more recently also carbon (e.g., graphene), that result in unique optical properties. This allows the tracking of such particles by fluorescence microscopic and photometric techniques. Many types of QDs consist of heavy elements, allowing to track and visualize these particles also by electron microscopy and to quantitate the particles indirectly based on these elements. QDs can also be surface modified in various ways which enable them to be used as a label or as traceable mimics for ENPs. This review reflects a broad range of methods to synthesize and modify QDs based on metals, metalloids, and graphene for studying the environmental fate of nanoparticles and discusses and compares analytical methods that can be used for tracking and quantifying QDs. In addition, we review applications of QDs as ENP mimics in environmental studies of surface waters, soils, microorganisms, and plants with respect to the applied analytical techniques.

Prospective Dynamic and Probabilistic Material Flow Analysis of Graphene-Based Materials in Europe from 2004 to 2030.

As industrial demand for graphene-based materials (GBMs) grows, more attention falls on potential environmental risks. The present article describes a first assessment of the environmental releases of GBMs using dynamic probabilistic material flow analysis. The model considered all current or expected uses of GBMs from 2004 to 2030, during which time there have already been significant changes in how the graphene mass produced is distributed to different product categories. Although the volume of GBM production is expected to grow exponentially in the coming years, outflow from the consumption of products containing GBMs shows only a slightly positive trend due to their long lifetimes and the large in-use stock of some applications (e.g., GBM composites used in wind turbine blades). From consumption and end-of-life phase GBM mass flows in 2030, estimates suggest that more than 50% will be incinerated and oxidized in waste plants, 16% will be landfilled, 12% will be exported out of Europe, and 1.4% of the annual production will flow to the environment. Predicted release concentrations for 2030 are 1.4 ng/L in surface water and 20 µg/kg in sludge-treated soil. This study's results could be used for prospective environmental risk assessments and as input for environmental fate models.

Evaluation of Marker Materials and Spectroscopic Methods for Tracer-Based Sorting of Plastic Wastes.

Plastics are a ubiquitous material with good mechanical, chemical and thermal properties, and are used in all industrial sectors. Large quantities, widespread use, and insufficient management of plastic wastes lead to low recycling rates. The key challenge in recycling plastic waste is achieving a higher degree of homogeneity between the different polymer material streams. Modern waste sorting plants use automated sensor-based sorting systems capable to sort out commodity plastics, while many engineering plastics, such as polyoxymethylene (POM), will end up in mixed waste streams and are therefore not recycled. A novel approach to increasing recycling rates is tracer-based sorting (TBS), which uses a traceable plastic additive or marker that enables or enhances polymer type identification based on the tracer's unique fingerprint (e.g., fluorescence). With future TBS applications in mind, we have summarized the literature and assessed TBS techniques and spectroscopic detection methods. Furthermore, a comprehensive list of potential tracer substances suitable for thermoplastics was derived from the literature. We also derived a set of criteria to select the most promising tracer candidates (3 out of 80) based on their material properties, toxicity profiles, and detectability that could be applied to enable the circularity of, for example, POM or other thermoplastics.

Recycling chains for lithium-ion batteries: A critical examination of current challenges, opportunities and process dependencies.

Lithium-ion batteries (LIBs) show high energy densities and are therefore used in a wide range of applications: from portable electronics to stationary energy storage systems and traction batteries used for e-mobility. Considering the projected increase in global demand for this energy storage technology, driven primarily by growth in e-vehicles, and looking at the criticality of some raw materials used in LIBs, the need for an efficient recycling strategy emerges. In this study, current state-of-the-art technologies for LIB recycling are reviewed and future opportunities and challenges, in particular to recover critical raw materials such as lithium or cobalt, are derived. Special attention is paid to the interrelationships between mechanical or thermal pre-treatment and hydro- or pyrometallurgical post-treatment processes. Thus, the unique approach of the article is to link processes beyond individual stages within the recycling chain. It was shown that influencing the physicochemical properties of intermediate products can lead to reduced recycling rates or even the exclusion of certain process options at the end of the recycling chain. More efforts are needed to improve information and data sharing on the exact composition of feedstock for recycling as well as on the processing history of intermediates to enable closed loop LIB recycling. The technical understanding of the interrelationships between different process combinations, such as pyrolytic or mechanical pre-treatment for LIB deactivation and metal separation, respectively, followed by hydrometallurgical treatment, is of crucial importance to increase recovery rates of cathodic metals such as cobalt, nickel, and lithium, but also of other battery components.

The current state of the art in internal additive materials and quantum dots for improving efficiency and stability against humidity in perovskite solar cells.

The remarkable optoelectronic capabilities of perovskite structures enable the achievement of astonishingly high-power conversion efficiencies on the laboratory scale. However, a critical bottleneck of perovskite solar cells is their sensitivity to the surrounding humid environment affecting drastically their long-term stability. Internal additive materials together with surface passivation, polymer-mixed perovskite, and quantum dots, have been investigated as possible strategies to enhance device stability even in unfavorable conditions. Quantum dots (QDs) in perovskite solar cells enable power conversion efficiencies to approach 20%, making such solar cells competitive to silicon-based ones. This mini-review summarized the role of such QDs in the perovskite layer, hole-transporting layer (HTL), and electron-transporting layer (ETL), demonstrating the continuous improvement of device efficiencies.

A critical review of the environmental impacts of manufactured nano-objects on earthworm species.

The presence of manufactured nano-objects (MNOs) in various consumer or their (future large-scale) use as nanoagrochemical have increased with the rapid development of nanotechnology and therefore, concerns associated with its possible ecotoxicological effects are also arising. MNOs are releasing along the product life cycle, consequently accumulating in soils and other environmental matrices, and potentially leading to adverse effects on soil biota and their associated processes. Earthworms, of the group of Oligochaetes, are an ecologically significant group of organisms and play an important role in soil remediation, as well as acting as a potential vector for trophic transfer of MNOs through the food chain. This review presents a comprehensive and critical overview of toxic effects of MNOs on earthworms in soil system. We reviewed pathways of MNOs in agriculture soil environment with its expected production, release, and bioaccumulation. Furthermore, we thoroughly examined scientific literature from last ten years and critically evaluated the potential ecotoxicity of 16 different metal oxide or carbon-based MNO types. Various adverse effects on the different earthworm life stages have been reported, including reduction in growth rate, changes in biochemical and molecular markers, reproduction and survival rate. Importantly, this literature review reveals the scarcity of long-term toxicological data needed to actually characterize MNOs risks, as well as an understanding of mechanisms causing toxicity to earthworm species. This review sheds light on this knowledge gap as investigating bio-nano interplay in soil environment improves our major understanding for safer applications of MNOs in the agriculture environment.

Static modelling of the material flows of micro- and nanoplastic particles caused by the use of vehicle tyres.

The emissions of tyre wear particles (TWPs) into the environment are increasing and have negative impacts on the environment and human health. The aim of this study was therefore to establish a mass balance for vehicle tyres und TWP emissions in Austria using static material flow analysis, which enabled a quantification of mass flows of rubber including carbon black as the most mass-relevant tyre filler. Vehicle-specific and mileage-dependent emission factors were used to calculate the TWP emissions. The results for the year 2018 indicate that 80% of the tyre rubber remained in use, while 14% was re-treaded, recycled, incinerated or exported as end-of-life tyres and 6% was emitted as TWPs to air, soil or surface water. Of these 21,200 t/y released and dissipative lost TWPs, 6% were microscale, with a possible size between 0.1 and 10 µm, and 0.3% were nanoscale below 0.1 µm. The mass balance on the substance level shows that the TWPs contained 5,500 t/y of carbon black emitted in the form of airborne TWPs (6%) or entering in the soil or surface waters (47% each). Regarding air pollution from road vehicles, about 3,600 t/y were non-exhaust emissions, including tyre, brake and road-surface wear, which contributed to 9% of total dust emissions across Austria. Scenario analysis for 2050 with regard to e-mobility and the European Green Deal reveals that non-exhaust emissions can only be significantly reduced by a general reduction of the mileage or an environmentally friendly tyre design. This modelling approach provides a solid basis for decision makers in traffic planning as well as for chemical risk assessment. However, dynamic models with higher temporal and spatial resolution are needed to predict future mass flows of TWPs and their environmental fate, including their degradation products and possible accumulation effects.

Investigations on inhibitory effects of nickel and cobalt salts on the decolorization of textile dyes by the white rot fungus Phanerochaete velutina.

Organic aromatic compounds used for dyeing and coloring in the textile industry are persistent and hazardous pollutants that must be treated before they are discharged into rivers and surface waters. Therefore, we investigated the potential of the white rot fungus Phanerochaete velutina to decolorize commonly used reactive dyes. The fungus decolorized in average 55% of Reactive Orange 16 (RO-16) after 14 days at a maximum rate of 0.09 d-1 and a half-life of 8 days. Furthermore, we determined the inhibitory effects of co-present inorganic contaminants Nickel (Ni) and Cobalt (Co) salts on the decolorization potential and determined IC50 values of 5.55 mg l-1 for Co and a weaker inhibition by Ni starting from a concentration of 20 mg l-1. In the decolorization assay for Remazol Brilliant Blue R (RBBR) we observed the interference of a metabolite of P. velutina, which did not allow us to investigate the kinetics of the reaction. The formation of the metabolite, however, could be used to obtain IC50 values of 3.37 mg l-1 for Co and 7.58 mg l-1 for Ni. Our results show that living white rot fungi, such as P. velutina, can be used for remediation of dye polluted wastewater, alternatively to enzyme mixtures, even in the co-presence of heavy metals.

A European nano-registry as a reliable database for quantitative risk assessment of nanomaterials? A comparison of national approaches.

Despite the fact that nanomaterials have been in use for decades and chemicals legislation is largely harmonised within the EU, quantitative and safety-relevant information on nanomaterials is still scarce. In particular, information about production volumes, their unique physicochemical properties (size, specific surface area, etc.) and nanomaterial exposure, which may lead to adverse effects on human health and the environment, is still lacking. While the latest amendments of the REACH Annexes have led to certain improvements, a harmonised EU-wide nano-registry would provide additional quantitative data for risk assessment but is not foreseeable for the near future. Since the European Commission, the European Parliament and some member states take contrasting approaches to the regulation of nanomaterials, France, Belgium, Denmark, Sweden and Norway (as a country of the European Economic Area), launched national mandatory reporting systems to collect quantitative information, thus fostering early risk assessment of nanomaterials. In this study, we compare national registries - based on a literature review and expert interviews - and show differences between the regulations under the respective national laws and REACH regulation. These include, for instance, thresholds for notification and level of detail on the specification of the nanomaterial, mixture and/or product, the definition of exceptions for the requirement to register and the timing of registration. As this heterogenous regulatory framework hinders comparability and potentially creates trade barriers, we argue that a harmonised EU-wide nano-registry would substantially improve the current situation by promoting the safe and sustainable handling of nanomaterials, increasing transparency and trust, and consequently nurturing innovation. Such an EU-wide nano-registry should both cover nanomaterials as substances or mixtures, such as in REACH registration, and the semi-/finished products they will be used in, since the exposure, and thus the hazardous potential of released nanomaterials during their life cycle, depends largely on the scope of application.

Mobility and fate of ligand stabilized semiconductor nanoparticles in landfill leachates.

Semiconductor quantum dots (QDs) are nanocrystals used in diverse optoelectronics. At the end of their useful life they are likely to end up in landfills, where they could be mobilzed by infiltrating rain water. In this work, spectroscopic and light scattering techniques were employed to investigate the environmental fate of QDs exposed to leachates from Austrian landfill sites containing municipal solid and bulky wastes. Brij-58-coated CdSe QDs, a model for surfactant stabilized hydrophobic nanoparticles, primarily sedimented before being degraded on a slower timescale in the course of 6 months. In contrast, N-acetyl-l-cystein-coated CdTe QDs, which represent electrostatically stabilized nanoparticles with a small covalently linked stabilizing molecule, mainly underwent a degradation mechanism that was accelerated by temperature. 71-95 % of this QD type was still dispersed in all leachates after 6 months at low temperature. Leachate temperature and composition, such as the DOC, as well as the used particle coating determined the mechanistic route of clearance of sedimentation versus degradation. Our study shows, that mechanistic investigations are necessary to determine the persistence of nanoparticles depending on their coatings in waste matrices which can be further used to assess hazardous risks of such nanowastes.

A methodological approach for the on-site quantification of food losses in primary production: Austrian and German case studies using the example of potato harvest.

In the last decade, in many European Countries more and more measures have been initiated aiming at the prevention of food losses and wastes along the entire value chain. In order to evaluate or monitor such important measures it is crucial to obtain quantitative information on generated food waste amounts, subsequently enabling the quantitative evaluation of the measure's outcomes and efficiency. Currently there is a paucity of quantitative information, particularly on food losses that are directly generated during harvesting processes. Up to date, no method is available or standardised aiming at the in-situ or on-site quantification of food losses during harvest. Using the example of the potato harvest, this study presents a practical approach for determining potato losses. To test the applicability of the developed method, on-site measurements were conducted directly on the field at five different locations in Austria and Germany. Our method enables the quantification of food losses based on defined areas along the harvested potato rows, where the analyser manually collects potatoes during their harvest. Hereby, two types of potato losses needs to be considered: non-harvested, under-sized potatoes that remain under the earth and the harvested ones, which are rejected on-site because of quality requirements regarding their size, shape, and state of health. Our study shows that between 1 and 9% of field losses (based on yield potential) can be generated during the potato harvest. In future, this method may be the basis for standardised protocols in order to be able to derive cultivar-specific benchmarks and, consequently, to develop measures for preventing food losses. In general, more case studies and evidence-based ground-up measurements on other cultivars and for other regions are needed focusing on the on-site quantification of post-harvest losses.

A review of the fate of engineered nanomaterials in municipal solid waste streams.

Significant knowledge and data gaps associated with the fate of product-embedded engineered nanomaterials (ENMs) in waste management processes exist that limit our current ability to develop appropriate end-of-life management strategies. This review paper was developed as part of the activities of the IWWG ENMs in Waste Task Group. The specific objectives of this review paper are to assess the current knowledge associated with the fate of ENMs in commonly used waste management processes, including key processes and mechanisms associated with ENM fate and transport in each waste management process, and to use that information to identify the data gaps and research needs in this area. Literature associated with the fate of ENMs in wastes was reviewed and summarized. Overall, results from this literature review indicate a need for continued research in this area. No work has been conducted to quantify ENMs present in discarded materials and an understanding of ENM release from consumer products under conditions representative of those found in relevant waste management process is needed. Results also indicate that significant knowledge gaps associated with ENM behaviour exist for each waste management process investigated. There is a need for additional research investigating the fate of different types of ENMs at larger concentration ranges with different surface chemistries. Understanding how changes in treatment process operation may influence ENM fate is also needed. A series of specific research questions associated with the fate of ENMs during the management of ENM-containing wastes have been identified and used to direct future research in this area.

Modeling the fate and end-of-life phase of engineered nanomaterials in the Japanese construction sector.

To date construction materials that contain engineered nanomaterials (ENMs) are available at the markets, but at the same time very little is known about their environmental fate. Therefore, this study aimed at modeling the potential fate of ENMs by using the example of the Japanese construction sector and by conducting a dynamic material flow analysis. Expert interviews and national reports revealed that about 3920-4660 tons of ENMs are annually used for construction materials in Japan. Nanoscale TiO2, SiO2, Al2O3 and carbon black have already been applied for decades to wall paints, road markings or concrete. The dynamic material flow model indicates that in 2016 about 95% of ENMs, which have been used since their year of market penetration, remained in buildings, whereas only 5% ended up in the Japanese waste management system or were diffusely released into the environment. Considering the current Japanese waste management system, ENMs were predicted to end up in recycled materials (40-47%) or in landfills (36-41%). It was estimated that only a small proportion was used in agriculture (5-7%, as ENM-containing sewage sludges) or was diffusely released into soils, surface waters or the atmosphere (5-19%). The results indicate that ENM release predominantly depend on their specific applications and characteristics. The model also highlights the importance of adequate collection and treatment of ENM-containing wastes. In future, similar dynamic flow models for other countries should consider, inasmuch as available, historical data on ENM production (e.g. like declaration reports that are annually published by relevant public authorities or associations), as such input data is very important regarding data reliability in order to decrease uncertainties and to continuously improve model accuracy. In addition, more environmental monitoring studies that aim at the quantification of ENM release and inadvertent transfer, particularly triggered by waste treatment processes, would be needed in order to validate such models.

Traceability of fluorescent engineered nanomaterials and their fate in complex liquid waste matrices.

The number of products containing engineered nanomaterials (ENMs) has increased due to their high industrial relevance as well as their use in diverse consumer products. At the end of their life cycle ENMs might be released to the environment and therefore concerns arise regarding their environmental impact. In order to track their fate upon disposal, it is crucial to establish methods to trace ENMs in complex environmental samples and to differentiate them from naturally-occurring nanoparticles. The goal of this study was to distinctively trace ENMs by (non-invasive) detection methods. For this, fluorescent ENMs, namely quantum dots (QDs), were distinctively traced in complex aqueous matrices, and were still detectable after a period of two months using fluorescence spectroscopy. In particular, two water-dispersible QD-species, namely CdTe/CdS QDs with N-acetyl-l-cysteine as capping agent (NAC-QDs) and surfactant-stabilized CdSe/ZnS QDs (Brij(®)58-QDs), were synthesized to examine their environmental fate during disposal as well as their potential interaction with naturally-occurring substances present in landfill leachates. When QDs were spiked into a leachate from an old landfill site, alteration processes, such as sorption, aggregation, agglomeration, and interactions with dissolved organic carbon (DOC), led to modifications of the optical properties of QDs. The spectral signatures of NAC-QDs deteriorated depending on residence time and storage temperature, while Brij(®)58-QDs retained their photoluminescence fingerprints, indicating their high colloidal stability. The observed change in photoluminescence intensity was mainly caused by DOC-interaction and association with complexing agents, such as fulvic or humic acids, typically present in mature landfill leachates. For both QD-species, the results also indicated that pH of the leachate had no significant impact on their optical properties. As a result, the unique spectroscopic fingerprints of QDs, specifically surfactant-stabilized QDs, allowed distinctive tracing in complex aqueous waste matrices in order to study their long-term behavior and ultimate fate.

Current limitations and challenges in nanowaste detection, characterisation and monitoring.

Engineered nanomaterials (ENMs) are already extensively used in diverse consumer products. Along the life cycle of a nano-enabled product, ENMs can be released and subsequently accumulate in the environment. Material flow models also indicate that a variety of ENMs may accumulate in waste streams. Therefore, a new type of waste, so-called nanowaste, is generated when end-of-life ENMs and nano-enabled products are disposed of. In terms of the precautionary principle, environmental monitoring of end-of-life ENMs is crucial to allow assessment of the potential impact of nanowaste on our ecosystem. Trace analysis and quantification of nanoparticulate species is very challenging because of the variety of ENM types that are used in products and low concentrations of nanowaste expected in complex environmental media. In the framework of this paper, challenges in nanowaste characterisation and appropriate analytical techniques which can be applied to nanowaste analysis are summarised. Recent case studies focussing on the characterisation of ENMs in waste streams are discussed. Most studies aim to investigate the fate of nanowaste during incineration, particularly considering aerosol measurements; whereas, detailed studies focusing on the potential release of nanowaste during waste recycling processes are currently not available. In terms of suitable analytical methods, separation techniques coupled to spectrometry-based methods are promising tools to detect nanowaste and determine particle size distribution in liquid waste samples. Standardised leaching protocols can be applied to generate soluble fractions stemming from solid wastes, while micro- and ultrafiltration can be used to enrich nanoparticulate species. Imaging techniques combined with X-ray-based methods are powerful tools for determining particle size, morphology and screening elemental composition. However, quantification of nanowaste is currently hampered due to the problem to differentiate engineered from naturally-occurring nanoparticles. A promising approach to face these challenges in nanowaste characterisation might be the application of nanotracers with unique optical properties, elemental or isotopic fingerprints. At present, there is also a need to develop and standardise analytical protocols regarding nanowaste sampling, separation and quantification. In general, more experimental studies are needed to examine the fate and transport of ENMs in waste streams and to deduce transfer coefficients, respectively to develop reliable material flow models.