Olga Borovinskaya

Capabilities of inductively coupled plasma mass spectrometry for the detection of nanoparticles carried by monodisperse microdroplets

Recently, first analyses of single sub-micrometre particles, embedded in liquid droplets, by inductively coupled plasma optical emission spectrometry (ICP-OES) with a size-equivalent detection limit of several hundred nanometres were reported. To achieve lower detection limits which might allow for the analysis of particles in the nanometre size range a more sensitive technique such as mass spectrometry (MS) is required. Various modifications of particle delivery and data acquisition systems commonly used were carried out to install a setup adequate for ICP-MS detection. These modifications enabled us to supply droplets generated by a commercial microdroplet generator (droplet size: 30–40 µm) with nearly 100% efficiency and high uniformity to the ICP. Analyses were performed using both standard solutions of dissolved metals at concentrations of 1 (Ag), 2 (Au), 5 (Au), or 10 (Cu) mg L−1 and highly diluted suspensions of gold and silver nanoparticles with sizes below 110 nm. In doing so, detection efficiencies of 10−6 counts per atom could be achieved while size-related limits of quantification were found to be 21 nm and 33 nm for gold and silver, respectively. Furthermore, the advantages of utilizing microdroplet generators vs. conventional nebulizers for nanoparticle analyses by ICP-MS are discussed.

A prototype of a new inductively coupled plasma time-of-flight mass spectrometer providing temporally resolved, multi-element detection of short signals generated by single particles and droplets

A prototype inductively coupled plasma time-of-flight mass spectrometer (ICPTOFMS) for time resolved measurements of transient signals in the microsecond regime is described in this work. Analytical figures of merit for the prototype are given for both liquid nebulization and single droplet introduction and are compared to a conventional quadrupole-based ICPMS using the same ICP source and vacuum interface. Quasi-simultaneous detection at a time resolution of 33 μs of the prototype ICPTOFMS allows multi-isotope monitoring of short signals (200–500 μs duration) generated from individual droplets and particles. The capabilities of the instrument for the analysis of single nanoparticles are studied using microdroplets consisting of a multi-element standard solution and containing 114 nm Au particles. The detection efficiencies for Ag and Au, calculated from the response of individual droplets and particles, are similar to those of the quadrupole-based instrument and amount to 1.3 × 10−6 ions per atom and 3.1 × 10−6 ions per atom, respectively. The sizes of the smallest detectable Ag, Au and U metallic nanoparticles are estimated to be 46 nm, 32 nm and 22 nm, respectively. Furthermore, time shifts of the signals of different elements within single droplets were observed. These new results demonstrate the advantage of the temporal resolution of the instrument for studying processes taking place in the plasma on the μs-time scale.

Simultaneous Mass Quantification of Nanoparticles of Different Composition in a Mixture by Microdroplet Generator-ICPTOFMS

This work investigated the potential of a high temporal resolution inductively coupled plasma time-of-flight mass spectrometer (ICPTOFMS) in combination with a microdroplet generator (MDG) for simultaneous mass quantification of different nanoparticles (NPs) in a mixture. For this purpose, a test system containing certified Au NPs, well characterized Ag NPs, and core-shell NPs composed of an Au core and an Ag shell was employed. Thanks to the full spectra coverage and rapid simultaneous detection of the TOFMS, the element composition of individual particles can be determined. The pure Ag NPs and the core-shell NPs could be differentiated despite the same mass of Ag they contain. Calibration with monodisperse droplets consisting of standard solutions allowed for the mass quantification of NPs without the use of NP certified materials. On the basis of this mass quantification, the sizes of NPs originating from the same aqueous suspension were simultaneously determined with an accuracy of 7-12%. The size-equivalent limits of detection estimated with the 3*σ criterion were 13 nm for Au and 16 nm for Ag. Estimation of the LODs using Poisson statistics resulted in 19 and 27 nm, respectively. In addition, the 30 μs temporal resolution of the ICPTOFMS allowed studying interactions of NPs with the ICP based on their transient MS signals. The results demonstrated a difference in vaporization behavior of the core-shell NPs and solutions and indicated that vaporization of the Ag shell takes place prior to the Au core.

A new microfluidics-based droplet dispenser for ICPMS

In this work, a novel droplet microfluidic sample introduction system for inductively coupled plasma mass spectrometry (ICPMS) is proposed and characterized. The cheap and disposable microfluidic chip generates droplets of an aqueous sample in a stream of perfluorohexane (PFH), which is also used to eject them as a liquid jet. The aqueous droplets remain intact during the ejection and can be transported into the ICP with >50% efficiency. The transport is realized via a custom-built system, which includes a membrane desolvator necessary for the PFH vapor removal. The introduction system presented here can generate highly monodisperse droplets in the size range of 40–60 μm at frequencies from 90 to 300 Hz. These droplets produced very stable signals with a relative standard deviation (RSD) comparable to the one achieved with a commercial droplet dispenser. Using the current system, samples with a total volume of <1 μL can be analyzed. Moreover, the capabilities of the setup for introduction and quantitative elemental analysis of single cells were described using a test system of bovine red blood cells. In the future, other modules of the modern microfludics can be integrated in the chip, such as on-chip sample pretreatment or parallel introduction of different samples.

Atomistic Description of Thiostannate-Capped CdSe Nanocrystals: Retention of Four-Coordinate SnS4 Motif and Preservation of Cd-Rich Stoichiometry

Colloidal semiconductor nanocrystals (NCs) are widely studied as building blocks for novel solid-state materials. Inorganic surface functionalization, used to displace native organic capping ligands from NC surfaces, has been a major enabler of electronic solid-state devices based on colloidal NCs. At the same time, very little is known about the atomistic details of the organic-to-inorganic ligand exchange and binding motifs at the NC surface, severely limiting further progress in designing all-inorganic NCs and NC solids. Taking thiostannates (K4SnS4, K4Sn2S6, K6Sn2S7) as typical examples of chalcogenidometallate ligands and oleate-capped CdSe NCs as a model NC system, in this study we address these questions through the combined application of solution 1H NMR spectroscopy, solution and solid-state 119Sn NMR spectroscopy, far-infrared and X-ray absorption spectroscopies, elemental analysis, and by DFT modeling. We show that through the X-type oleate-to-thiostannate ligand exchange, CdSe NCs retain their Cd-rich stoichiometry, with a stoichiometric CdSe core and surface Cd adatoms serving as binding sites for terminal S atoms of the thiostannates ligands, leading to all-inorganic (CdSe)core[Cdm(Sn2S7)yK(6y-2m)]shell (taking Sn2S76– ligand as an example). Thiostannates SnS44– and Sn2S76– retain (distorted) tetrahedral SnS4 geometry upon binding to NC surface. At the same time, experiments and simulations point to lower stability of Sn2S64– (and SnS32–) in most solvents and its lower adaptability to the NC surface caused by rigid Sn2S2 rings.

Diffusion- and velocity-driven spatial separation of analytes from single droplets entering an ICP off-axis

The reproducible temporal separation of ion signals generated from a single multi-element droplet, observed in previous studies, was investigated in detail in this work using an ICPTOFMS with high temporal resolution. It was shown that the signal peak intensities of individual elements temporally shift relative to each other only for droplets moving through the plasma off-axis. The magnitude of these shifts correlated with the vaporization temperatures of the analytes and depended on the radial position of the droplets as well as on the thermal properties and velocity profiles of the carrier gases of the ICP. The occurrence of the signal shifting was explained by a spatial separation of analytes already present in the vapor phase in the ICP from a yet unvaporized residue of the droplet. This separation is most likely driven by anisotropic diffusion of vaporized analytes towards the plasma axis and a radial velocity gradient. The proposed explanation is supported by modeling of the gas velocities inside the ICP and imaging of the atomic and ionic emissions produced from single droplets, whose patterns were sloping towards the center of the torch. The effects observed in these studies are important not only for the fundamental understanding of analyte–plasma interactions but have also a direct impact on the signal intensities and stability.

Capabilities of sequential and quasi-simultaneous LA-ICPMS for the multi-element analysis of small quantity of liquids (pl to nl): insights from fluid inclusion analysis

Three configurations of inductively coupled plasma mass spectrometers (ICPMS), namely: a quadrupole (QMS) and a sector-field (SFMS), both equipped with a standard cylindrical ablation cell, and an orthogonal time-of-flight (TOFMS), equipped with a fast washout ablation cell, were coupled with the same 193 nm Excimer laser ablation system in order to evaluate their capabilities for measurement of multiple minor and trace elements in small quantities of liquids (pl to nl), such as fluid inclusions. Analyses were performed with different objects: (i) multi-element solutions sealed in silica capillaries of internal diameter of 20 μm serving as synthetic analogues of natural fluid inclusions; (ii) natural two-phase (liquid + vapour) fluid inclusions with low salinity (ca. 4.8 wt% NaCl eq.) and homogeneous compositions, trapped in quartz crystals from the Alps; (iii) natural multi-phase (liquid + vapour + multiple solids) fluid inclusions with high salinity (ca. 13–15 wt% NaCl eq.) and homogeneous compositions, trapped in quartz crystals from the Zambian Copperbelt. This study demonstrates that the SFMS and TOFMS provide improvements, particularly in term of limits of detection (LODs) and precision, compared to the QMS traditionally used for the measurement of fluid inclusions. SFMS leads on average to lower LODs within one order of magnitude compared to QMS and TOFMS, but precision and accuracy are lower due to longer acquisition cycle times. TOFMS presents both advantages of having rapid and quasi-simultaneous acquisition for all isotopes from 6Li to 238U in a very short cycle time down to 30 μs, with higher precisions and lower LODs than for QMS for isotopes with m/Q > 11. Its use, coupled to a fast washout cell, leads to (i) the improvement in the analysis of small-size (<10 μm) and multi-phase fluid inclusions and (ii) detection of higher number of isotopes compared to QMS and SFMS, which are both limited by the number of measured isotopes from short transient signals of fluid inclusions. Consequently, the tested TOFMS, coupled with a fast washout ablation cell, appears to be a promising instrument for the analysis of natural fluid inclusions by LA-ICPMS, especially for small, multi-phase and/or low salinity fluid inclusions.

Three-Dimensional Reconstruction of the Tissue-Specific Multielemental Distribution within Ceriodaphnia dubia via Multimodal Registration Using Laser Ablation ICP-Mass Spectrometry and X-ray Spectroscopic Techniques

In this work, the three-dimensional elemental distribution profile within the freshwater crustacean Ceriodaphnia dubia was constructed at a spatial resolution down to 5 μm via a data fusion approach employing state-of-the-art laser ablation-inductively coupled plasma-time-of-flight mass spectrometry (LA-ICP-TOFMS) and laboratory-based absorption microcomputed tomography (μ-CT). C. dubia was exposed to elevated Cu, Ni, and Zn concentrations, chemically fixed, dehydrated, stained, and embedded, prior to μ-CT analysis. Subsequently, the sample was cut into 5 μm thin sections that were subjected to LA-ICP-TOFMS imaging. Multimodal image registration was performed to spatially align the 2D LA-ICP-TOFMS images relative to the corresponding slices of the 3D μ-CT reconstruction. Mass channels corresponding to the isotopes of a single element were merged to improve the signal-to-noise ratios within the elemental images. In order to aid the visual interpretation of the data, LA-ICP-TOFMS data were projected onto the μ-CT voxels representing tissue. Additionally, the image resolution and elemental sensitivity were compared to those obtained with synchrotron radiation based 3D confocal μ-X-ray fluorescence imaging upon a chemically fixed and air-dried C. dubia specimen.

Element analysis of small and even smaller objects by ICPMS and LA-ICPMS.

Inductively coupled plasma mass spectrometry is increasingly used for non-traditional applications such as the analysis of solids at high spatial resolution when combined with laser ablation or the analysis of engineered nanoparticles. This report highlights recent projects and discusses the potentials and limitations these techniques offer. High-resolution laser ablation instrumentation allows element imaging at the μm-scale and can, therefore, be applied to, e.g., the mapping of metal isotope-labeled antibodies in biological tissues. Despite these advancements, the quantitative analysis of laser-produced aerosols is still a major concern. Here, the accuracy of analysis was found to strongly depend on particle size distribution but also on the morphology and composition of particles. In order to achieve a controlled supply of nanoparticles for analysis by inductively coupled plasma mass spectrometry, a dedicated microdroplet injection system was developed and characterized. This system allows a reproducible injection of single nanoparticles together with internal standards to determine their mass and composition.

Multi-element analysis of single nanoparticles by ICP-MS using quadrupole and time-of-flight technologies

Determining composition, shape, and size of nanoparticles dispersed in a complex matrix is necessary in the assessment of toxicity, for regulatory actions, and environmental monitoring. Many types of nanoparticles that are currently used in consumer products contain more than one metal which are often not uniformly distributed (e.g., core–shell nanoparticles). This compositional and structural complexity makes their characterization difficult. In this study, we investigate the capability of single particle inductively coupled plasma mass spectrometry (spICP-MS) using time-of-flight (TOF) and quadrupole (Q) mass analyzers to determine the composition, size distribution, and concentration of a series of nanoparticles that are used in a variety of industrial applications: BiVO4, (Bi0.5Na0.5)TiO3 and steel (which contains Fe, Cr, Ni, Mo) nanoparticles. In addition, we tested both types of mass analyzers with Au-core/Ag-shell nanoparticles, which are well-characterized and have already been used for assessment of multi-element capabilities of spICP-MS. The results confirm that both types of mass analyzers produce accurate estimations of the size of Au-core/Ag-shell particles. For other multi-element nanoparticles, spICP-MS provided the size of aggregates and/or agglomerates in the prepared suspensions. In general, particle size detection limits (dLOD) of spICP-TOFMS instruments with values of 29 nm for Ti, 14 nm for Mo, and 7 nm for Au, are smaller than those obtained for the quadrupole instruments. This study finds that only spICP-TOFMS can accurately assess the elemental composition of nano-steel particles. By contrast, spICP-QMS is limited to the detection of 2 elements in an individual particle and the elemental composition of nano-steel particles is less accurate. In general, spICP-TOFMS was able to quantify multiple elements with high precision and that currently makes it the first choice for multi-element detection of unknown nanoparticles.