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As a result of their unique physical, chemical and/or biological properties, the use of engineered nanoparticles (ENPs) is growing very rapidly. Iron oxide nanoparticles (IONPs) are of particular interest owing to their magnetic properties, and thus the development of suitable methods for their characterization is essential. Inductively coupled plasma-mass spectrometry (ICP-MS) operated in single-particle (SP) mode provides different types of relevant information, such as size distribution and particle number and mass concentrations. However, the use of SP-ICP-MS becomes less straightforward when the analyte signal is subject to spectral overlap. In the case of IONPs, characterization by means of SP-ICP-MS is hindered by the occurrence of ArO+ polyatomic ions with the same nominal mass-to-charge (m/z) ratio as the most abundant Fe isotope. In this work, different approaches relying on either chemical or physical (mass) resolution, to avoid this spectral interference otherwise jeopardizing accurate results, were assessed. In the case of chemical resolution, the performance of on-mass and mass-shift approaches was evaluated using different types of quadrupole-based ICP-MS instrumentation, including single-quadrupole (SQ) and tandem ICP-MS (ICP-MS/MS) units. Physical resolution was accomplished using a new generation of sector field (SF) ICP-MS instrumentation, capable of dealing with transient signals of extremely short duration (10–100 μs dwell time), even when operated at higher mass resolution (pseudo-resolution mode). Based on the figures-of-merit obtained for the different approaches evaluated, an on-mass approach using NH3 as the reaction gas in SQ-ICP-MS, an on-mass approach using H2 as the collision/reaction gas in ICP-MS/MS and pseudo-medium resolution in SF-ICP-MS were found to be the best-suited approaches for fast interference-free monitoring of the ion signals generated by IONPs in SP mode. While the use of chemical (H2/on-mass) and physical (pseudo-medium) resolutions also provided accurate and precise results for custom-made Fe3O4 (magnetite) NPs of ≈50 nm, the use of NH3 was less successful, as it leads to an extension of the SP pulse profile and a lower signal-to-background ratio. Finally, SF-ICP-MS operated in pseudo-medium resolution mode was used for the characterization of Fe3O4 NPs synthesized electrochemically (batch and continuous operation mode).

The occurrence of microplastics in many, if not all environmental compartments is a matter of increasing concern and deserves proper attention. However, there is still a lack of analytical tools for straightforward monitoring of these tiny plastic particles at environmentally relevant levels in water. Inductively coupled plasma-mass spectrometry (ICP-MS) operated in single-particle mode (SP-ICP-MS) was demonstrated to be a powerful technique for the characterization of metallic nanoparticles, but to the best of the authors' knowledge, SP-ICP-MS has not yet been evaluated for the purpose of detection of microplastics and their quantitative determination (particle number density). In this work, spherical polystyrene microspheres of 1 and 2.5 μm – to mimic microplastics coming from plastic waste – have been detected using ICP-MS. The approach developed relies on the ultra-fast monitoring of transient signals (with a dwell time of 100 μs) when using a quadrupole-based ICP-MS unit in the so-called single-event mode and registering the signal spikes produced by individual microparticles by monitoring the signal intensity at a mass-to-charge ratio (m/z) of 13 (13C+). The accuracy of the number-based concentration results (particle number densities) has been assessed by comparing the number of events detected when monitoring 13C+ to those detected when monitoring 165Ho+ for 2.5 μm lanthanide-doped polystyrene beads. Additionally, the results obtained for both polystyrene microspheres in terms of size (most frequently occurring intensity of the signal distribution) compare well with the size as determined using electron microscopy. ICP-MS operated in single-event mode thus allows information on both the size distribution and mass concentration of microplastics to be obtained. As this approach makes use of instrumentation already available in many routine labs analyzing environmental samples, it can enable these labs to analyze microplastics by using their instrument in single-event mode.

Development of analytical methods for the characterization (particle size determination, chemical identification, and quantification) of the low µm-range microplastic (MPs; 1-10 µm) and nanoscale plastic (NPs; 1-1000 nm) debris in environmental matrices is a quickly emerging scientific field and has gained considerable attention, not only within the scientific community, but also on the part of policy makers and the general public. However, due to the limited sensitivity of the current state of the art monitoring techniques, detection of MPs and NPs in water is one of the biggest challenges for their monitoring, source identification and, ultimately, risk assessment.As it is evident that no single method will provide all the information required for a complete characterization of MPs and NPs in water, the present work is aimed to give an overview of different complementary analytical methodologies showing considerable promise for the particle size determination, chemical identification, and quantification of MPs and NPs [1]. In addition, results of three case studies will be included to adequately address the smallest fractions in plastic debris size determination, making such approaches worthwhile to be further explored.The first case study offers a novel method based on the use of inductively coupled plasma-mass spectrometry operated in single-event mode and relies on our previous work where for the first time ever single particle inductively coupled plasma-mass spectrometry based on carbon monitoring was successfully used for the detection, particle size characterization and particle number concentration of polystyrene MPs [2]. The second case study further explore light scattering methods, including nanoparticle tracking analysis or dynamic light scattering, for MPs and NPs particle size distribution and particle number in water. Finally, the capabilities of size exclusion chromatography in combination with online detection techniques such as UV-visible absorption spectrometry will be presented for the particle size determination of smallest fraction of NPs (1-100 nm). M.V. is a senior postdoctoral fellow of the Research Foundation – Flanders (FWO 12ZD120N). References[1] Velimirovic M., Tirez K., Voorspoels S., Vanhaecke F. (2020) Recent developments in mass spectrometry for the characterization of micro- and nanoscale plastic debris in the environment, Analytical and Bioanalytical Chemistry, 1-9.[2] Bolea-Fernandez E., Rua-Ibarz A., Velimirovic M., Tirez K., and Vanhaecke F. (2020) Detection of microplastics using inductively coupled plasma-mass spectrometry (ICP-MS) operated in single-event mode. Journal of Analytical Atomic Spectrometry 35, 455-460.

The use of an internal standard to correct for potential matrix effects and instrument instability is common practice in ICP-MS. However, with the introduction of a new generation of ICP-MS instrumentation with a tandem mass spectrometry configuration (ICP-MS/MS), the use of chemical resolution in a mass-shift approach has become much more popular, suggesting that the appropriate selection of an internal standard needs revision. In this particular case, it needs to be decided whether the internal standard should also be subjected to a mass-shift or can simply be monitored on-mass ("to shift, or not to shift"). In this work, 17 elements covering a wide range of masses (24-205 amu) and ionization energies (3.89-9.39 eV) were measured via on-mass and/or mass-shift strategies, and the corresponding atomic ions and reaction product ions were monitored during various systematic experiments. For mass-shifting, an NH3/He gas mixture was used to obtain NH3-based reaction product ions (cluster formation). Product ion scanning (PIS) was used for assessing the differences in reactivity between the different analytes and for the identification of the best suited reaction product ions. It was found that the use of chemical resolution can significantly affect the short-term signal stability and that ion signals measured on-mass are not affected in the same way as those measured mass-shifted. Variations affecting the signal intensities of both atomic and reaction product ions can be attributed to the ion-molecule chemistry occurring within the collision/reaction cell and were found to be related with some degree of initial instability in the cell and differences in reactivity. The use of a sufficiently long stabilization time, however, avoids or at least mitigates such differences in the behavior between signals monitored on-mass and after mass-shifting, respectively. Furthermore, the introduction of cell disturbances, such as those generated after quickly switching between different sets of operating conditions in a multi-tune method, revealed significant differences in signal behavior between atomic and reaction product ions, potentially hampering the use of an internal standard monitored on-mass when the analysis is based on an analyte monitored after mass-shifting. However, the use of a reasonable waiting time again greatly mitigates such differences, with the duration of this stabilization time depending on the magnitude of the cell disturbances (e.g., switch between vented and pressurized mode or only between pressurized modes using different gas flow rates). In addition, also the effect of varying different instrument settings (plasma power, torch position, and gas and liquid flow rates) was evaluated, but no remarkable differences were found between signals monitored on-mass and those mass-shifted. Interestingly, a statistical evaluation of the influence of the different settings on the signal intensities of all ions monitored did not reveal the a priori important role of some properties traditionally suggested for adequate selection of analyte/internal standard pairs, such as mass number or ionization energy, as also suggested in other recent studies. © The Royal Society of Chemistry.

Whales accumulate mercury (Hg), but do not seem to show immediate evidence of toxic effects. Analysis of different tissues (liver, kidney, muscle) and biofluids (blood, milk) from a pod of stranded long-finned pilot whales (Globicephala melas) showed accumulation of Hg as a function of age, with a significant decrease in the MeHg fraction. Isotopic analysis revealed remarkable differences between juvenile and adult whales. During the first period of life, Hg in the liver became isotopically lighter (δ202Hg decreased) with a strongly decreasing methylmercury (MeHg) fraction. We suggest this is due to preferential demethylation of MeHg with the lighter Hg isotopes and transport of MeHg to less sensitive organs, such as the muscles. Also changes in diet, with high MeHg intake in utero and during lactation, followed by increasing consumption of solid food contribute to this behavior. Interestingly, this trend in δ202Hg is reversed for livers of adult whales (increasing δ202Hg value), accompanied by a progressive decrease of δ202Hg in muscle at older ages. These total Hg (THg) isotopic trends suggest changes in the Hg metabolism of the long-finned pilot whales, development of (a) detoxification mechanism(s) (e.g., though the formation of HgSe particles), and Hg redistribution across the different organs.

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The increase in the use of SiO2 nanoparticles (NPs) is raising concern about their environmental and health effects, thus necessitating the development of novel methods for their straightforward detection and characterization. Single particle ICP-mass spectrometry (SP-ICP-MS) is able to provide information on the size of NPs, their particle number density and mass concentration. However, the determination of Si via ICP-MS is strongly hampered by the occurrence of spectral overlap from polyatomic species (e.g., CO+ and N2+). The use of tandem ICP-MS (ICP-MS/MS) enables interference-free conditions to be obtained, even in the most demanding applications. Upon testing several gases, the use of CH3F (monitoring of SiF+, mass-shift approach) and of H2 (monitoring of Si+, on-mass approach) were demonstrated to be the most suitable to overcome the spectral interference affecting ultra-trace Si determination (LoD 100 nm, it was possible to provide accurate results in a straightforward way, as the signals they give rise to are well resolved from those of the background. In the case of 80 and 100 nm NPs, the use of a simple deconvolution approach following a Gaussian model was needed to characterize SiO2 NPs apparently showing incomplete distributions as a result of the presence of the background signal. Overall, the methods developed using SP-ICP-MS/MS are sensitive and selective enough for the interference-free determination of Si at ultra-trace levels, also in the form of SiO2 NPs.

Hg pollution released from the U-864 submarine sunk during WWII and potential introduction of that Hg into the marine food chain have been studied by a combination of quantitative Hg and MeHg determination and Hg isotopic analysis via cold vapor generation multicollector inductively coupled plasma-mass spectrometry (CVG-MC-ICP-MS) in sediment and Cancer pagurus samples. The sediment pollution could be unequivocally linked with the metallic Hg present in the wreck. Crabs were collected at the wreck location and 4 nmi north and south, and their brown and claw meat were analyzed separately. For brown meat, the δ202Hg values of the individuals from the wreck location were shifted toward the isotopic signature of the sediment and, thus, the submarine Hg. Such differences were not found for claw meat. The isotope ratio results suggest direct ingestion of metallic Hg by C. pagurus but do not offer any proof for any other introduction of the submarine Hg into the marine food chain.

H2O2 was demonstrated to narrow the size distribution and decrease the size of CuO and hydrous FeOOH (2-line ferrihydrite) nanoparticles under conditions of high supersaturation. We introduce oxidation-assisted alkaline precipitation (Ox-AP) and compare it to traditional alkaline precipitation (AP). While for AP, a metal salt solution (e.g., CuCl2) is mixed with an alkali (e.g., NaOH), for Ox-AP, the more reduced form of that metal salt solution (e.g., CuCl) is simultaneously mixed with that alkali and an oxidant (e.g., H2O2). The resulting precipitates were characterized with SEM, XRD, DLS and single particle ICP-MS and shown to be nanoparticles (NPs). Ox-AP CuO NPs were up to 3 times smaller than AP NPs. Ox-AP FeOOH NPs were up to 22.5% smaller than AP NPs. We discuss and propose a possible mechanism of Ox-AP through careful consideration of the known reaction chemistry of iron and copper. We propose that an increased monomer formation rate enhances the nucleation rate, which ultimately results in smaller particles with a more narrow distribution. The more distinct effect of Ox-AP on copper, was attributed to the fast formation of the stable CuO monomer, compared to AP, where the Cu(OH)2 and/or Cu2(OH)3Cl monomers are more likely formed. Although, the exact mechanism of Ox-AP needs experimental confirmation, our results nicely demonstrate the potential of using Ox-AP to produce smaller NPs with a more narrow distribution in comparison to using AP. ispartof: RSC ADVANCES vol:9 issue:51 pages:29902-29908 ispartof: location:England status: published

Liver and muscle tissue of tusks (Brosme brosme) have been analyzed for their THg and MeHg concentrations and Hg isotopic signatures for tracing Hg pollution along the Norwegian coast. Clear differences between tissue types and locations were established. At five of the eight locations, the Hg concentration in muscle exceeded the maximum allowable level of 0.5 mg kg(-1) wet weight. delta Hg-202 values in both tissue types indicated that Hg speciation affects the bulk Hg isotopic signature. Tusk liver seems to be more sensitive to immediate changes and to anthropogenic inorganic Hg, while the muscle rather reflects the Hg accumulated over a longer period of exposure. The delta Hg-202 values of liver and muscle also enabled different sources of Hg and exposure pathways to be distinguished. delta Hg-202(muscle)-delta Hg-202(liver) showed a clear correlation with the % MeHg in tusk liver for the coastal waters, but not for the fjords. The absence of significant differences in Delta Hg-199 values between both tissues of tusk from the same location suggests that in vivo metabolic processes are the underlying reason for the differences in Hg speciation and in delta Hg-202 values. This work highlights the importance of selecting different tissues of marine fish in future Hg monitoring programs.

This work uses the tandem ICP-MS (ICPMS/MS) for obtaining interference-freeconditions to characterize SiO2 nanoparticles ranging between 80 and 400nm. These NPs have been detected and accurately characterized. For SiO2 NPs >100 nm, it was possible to provide accurateresults in a straightforward way, as theirsignal distributions are well resolved fromthat of the background.

The increase in the use of SiO2 nanoparticles (NPs) is raising concern about their environmental and health effects, thus necessitating the development of novel methods for their straightforward detection and characterization. Single particle ICP-mass spectrometry (SP-ICP-MS) is able to provide information on the size of NPs, their particle number density and mass concentration. However, the determination of Si via ICP-MS is strongly hampered by the occurrence of spectral overlap from polyatomic species (e.g., CO+ and N2+). The use of tandem ICP-MS (ICP-MS/MS) enables interference-free conditions to be obtained, even in the most demanding applications. Upon testing several gases, the use of CH3F (monitoring of SiF+, mass-shift approach) and of H2 (monitoring of Si+, on-mass approach) were demonstrated to be the most suitable to overcome the spectral interference affecting ultra-trace Si determination (LoD < 15 ng L-1). By using these approaches, SiO2 NPs (ranging between 80 and 400 nm) can be detected and characterized. For SiO2 NPs > 100 nm, it was possible to provide accurate results in a straightforward way, as the signals they give rise to are well resolved from those of the background. In the case of 80 and 100 nm NPs, the use of a simple deconvolution approach following a Gaussian model was needed to characterize SiO2 NPs apparently showing incomplete distributions as a result of the presence of the background signal. Overall, the methods developed using SP-ICP-MS/MS are sensitive and selective enough for the interference-free determination of Si at ultra-trace levels, also in the form of SiO2 NPs.

Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision ≤0.006% relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the latest generations of some biological RMs.