Characterization of silver nanoparticle products using asymmetric flow field flow fractionation with a multidetector approach--a comparison to transmission electron microscopy and batch dynamic light scattering.

Due to the already prevalent and increasing use of silver-nanoparticle (Ag-NP) products and the raised concerns in particular for the aquatic environment, analytical techniques for the characterization of such products are of need. However, because Ag-NP products are of different compositions and polydispersities, analysis especially of the size distribution is challenging. In this work, an asymmetric flow field flow fractionation (A4F) multidetector system (UV/vis, light scattering, inductively coupled plasma mass spectrometry - ICPMS), in combination with a method to distinguish and quantify the particle and dissolved Ag fractions (ICPMS after ultracentrifugation), for the characterization of Ag-NP products with different degrees of polydispersities is presented. For validation and to outline benefits and limitations, results obtained from batch dynamic light scattering (batch-DLS) and transmission electron microscopy (TEM) were compared. With the developed method a comprehensive understanding in terms of dissolved Ag and Ag-NP concentration as well as an element selective, mass- and number particle size distribution (PSD) was obtained. In relation to batch-DLS, the reliability of the data was improved significantly. In comparison to TEM, faster measurement times and the ability to determine the samples directly in dispersions are clearly advantageous. The proposed setup shows potential for a rapid- and reliable characterization method of virtually any polydisperse metallic NP dispersion, many of them available on the market already.

Testing the bioaccumulation potential of manufactured nanomaterials in the freshwater amphipod Hyalella azteca.

Standardized experimental approaches for the quantification of the bioaccumulation potential of nanomaterials in general and in (benthic) invertebrates in particular are currently lacking. We examined the suitability of the benthic freshwater amphipod Hyalella azteca for the examination of the bioaccumulation potential of nanomaterials. A flow-through test system that allows the generation of bioconcentration and biomagnification factors was applied. The feasibility of the system was confirmed in a 2-lab comparison study. By carrying out bioconcentration and biomagnification studies with gold, titanium dioxide and silver nanoparticles as well as dissolved silver (AgNO3) we were able to assess the bioaccumulation potential of different types of nanomaterials and their exposure pathways. For this, the animals were examined for their total metal body burden using inductively coupled mass spectroscopy (ICP-MS) and for the presence of nanoparticulate burdens using single-particle ICP-MS. The role of released ions was highlighted as being very important for the bioavailability and bioaccumulation of metals from nanoparticles for both examined uptake paths examined (bioconcentration and biomagnification). In 2018 a tiered testing strategy for engineered nanomaterials was proposed by Handy et al. that may allow a waiver of bioaccumulation fish studies using inter alia invertebrates. Data gained in studies carried out with invertebrates like the developed Hyalella azteca test may be included in this proposed tiered testing strategy.

Size, number and chemical composition of nanosized particles in drinking water determined by analytical microscopy and LIBD.

In this paper we comprehensively characterized particles in drinking water originating from a lake water source. We focused on particles smaller than a few hundred nm. Several analytical techniques were applied to obtain information on number concentration, size distribution, morphology and chemical composition of the particles. Morphological information was obtained by atomic force microscopy (AFM) analysis. Two types of particles, spherical aggregates up to a few tens of nm and elongated fibers were identified. Similar structures were also observed in transmission electron microscope (TEM) images. A size distribution of the particles was obtained by applying image analysis (IA) tools on the TEM images. IA results showed an exponential increase of the particle number concentration down to 40 nm, which is the lower detection limit of our setup. The total number of particles down to 10 nm and the average particle diameter were determined with the laser-induced breakdown detection (LIBD) method. The results were in good agreement with the TEM-IA data and showed a total number concentration of roughly 10(8) particles/mL in the purified water. The carbon of the particles was investigated with scanning transmission X-ray microscopy (STXM), which revealed that most particles were organic matter; the C-1s spectra were typical for dissolved organic matter. The methods were applied to characterize the particles from two different drinking waters treated with different methods (conventional vs. ultrafiltration (cut-off 100 kDa)). The results showed that the particle number density following ultrafiltration was lower by a factor of 5-10, compared to conventional treatment. However, the average particle diameter in the finished water of both treatment trains was roughly the same.

On source identification and alteration of single diesel and wood smoke soot particles in the atmosphere; an X-ray microspectroscopy study.

Diesel and wood combustion are major sources of carbonaceous particles in the atmosphere. It is very hard to distinguish between the two sources by looking at soot particle morphology, but clear differences in the chemical structure of single particles are revealed by C(1s) NEXAFS (near edge X-ray absorption fine structure) microspectroscopy. Soot from diesel combustion has a dominant spectral signature at approximately 285 eV from aromatic pi-bonds, whereas soot from wood combustion has the strongest signature at approximately 287 eV from phenolic carbon bonds. To investigate if it is possible to use these signatures for source apportionment purposes, we collected atmospheric samples with either diesel or wood combustion as a dominant particle source. No spectra obtained from the atmospheric particles completely matched the emission spectra. Especially particles from the wood dominated location underwent large modifications; the phenolic spectral signature at approximately 287 eV is greatly suppressed and surpassed by the peak attributed to the aromatic carbon groups at approximately 285 eV. Comparison with spectra from diesel soot samples experimentally aged with ozone show that very fast modification of the carbon structure of soot particles occurs as soon as they enter the atmosphere. Source attribution of single soot particles with microspectroscopy is thus hardly possible, but NEXAFS remains a powerful tool to study aging effects.

Synthetic TiO2 nanoparticle emission from exterior facades into the aquatic environment.

We present direct evidence of the release of synthetic nanoparticles from urban applications into the aquatic environment. We investigated TiO(2) particles as these particles are used in large quantities in exterior paints as whitening pigments and are to some extent also present in the nano-size range. TiO(2) particles were traced from exterior facade paints to the discharge into surface waters. We used a centrifugation based sample preparation which recovers TiO(2) particles between roughly 20 and 300nm. Analytical electron microscopy revealed that TiO(2) particles are detached from new and aged facade paints by natural weather conditions and are then transported by facade runoff and are discharged into natural, receiving waters. Microscopic investigations are confirmed by bulk chemical analysis. By combining results from microscopic investigations with bulk chemical analysis we calculated the number densities of synthetic TiO(2) particles in the runoff.

Application of the focused ion beam technique in aerosol science: detailed investigation of selected, airborne particles.

The focused ion beam technique was used to fabricate transmission electron microscope lamellas of selected, micrometre-sized airborne particles. Particles were sampled from ambient air on Nuclepore polycarbonate filters and analysed with an environmental scanning electron microscope. A large number of particles between 0.6 and 10 microm in diameter (projected optical equivalent diameter) were detected and analysed using computer-controlled scanning electron microscopy. From the resulting dataset, where the chemistry, morphology and position of each individual particle are stored, two particles were selected for a more detailed investigation. For that purpose, the particle-loaded filter was transferred from the environmental scanning electron microscope to the focused ion beam, where lamellas of the selected particles were fabricated. The definition of a custom coordinate system enabled the relocation of the particles after the transfer. The lamellas were finally analysed with an analytical transmission electron microscope. Internal structure and elemental distribution maps of the interior of the particles provided additional information about the particles, which helped to assign the particles to their sources. The combination of computer-controlled scanning electron microscopy, focused ion beam and transmission electron microscopy offers new possibilities for characterizing airborne particles in great detail, eventually enabling a detailed source apportionment of specific particles. The particle of interest can be selected from a large dataset (e.g. based on chemistry and/or morphology) and then investigated in more detail in the transmission electron microscope.