CO2 laser heating system for in situ radial x-ray absorption at 16-BM-D at the Advanced Photon Source.

We present a portable CO2 laser heating system for in situ x-ray absorption spectroscopy (XAS) studies at 16-BM-D (High Pressure Collaborative Access Team, Advanced Photon Source, Argonne National Laboratory). Back scattering optical measurements are made possible by the implementation of a Ge beamsplitter. Optical pyrometry is conducted in the near-infrared, and our temperature measurements are free of chromatic aberration due to the implementation of the peak-scaling method [A. Kavner and W. R. Panero, Phys. Earth Planet. Inter. 143-144, 527-539 (2004) and A. Kavner and C. Nugent, Rev. Sci. Instrum. 79, 024902 (2008)] and mode scrambling of the input signal. Laser power stabilization is established using electronic feedback, providing a steady power over second timescales [Childs et al., Rev. Sci. Instrum. 91, 103003 (2020)]-crucial for longer XAS collections. Examples of in situ high pressure-temperature extended x-ray absorption fine structure measurements of ZrO2 are presented to demonstrate this new capability.

Pressure-induced metallization and 3d-like behavior in TcS2.

TcS2 undergoes a charge transfer insulator to metal transition above 28 GPa. Laser annealing reveals a kinetically hindered high pressure arsenopyrite phase that is recoverable to ambient. The new phase is similar to the Mn-dichalcogenides rather than the expected Re-dichalcogenides and involves the formation of S-S and Tc-Tc bonds.

Synthesis and chemical stability of technetium nitrides.

We demonstrate the synthesis and phase stability of TcN, Tc2N, and a substoichiometric TcNx from 0 to 50 GPa and to 2500 K in a laser-heated diamond anvil cell. At least potential recoverability is demonstrated for each compound. TcN adopts a previously unpredicted structure identified via crystal structure prediction.

Phosphorus Dimerization in Gallium Phosphide at High Pressure.

Using combined experimental and computational approaches, we show that at 43 GPa and 1300 K gallium phosphide adopts the super- Cmcm structure, here indicated with its Pearson notation oS24. First-principles enthalpy calculations demonstrate that this structure is more thermodynamically stable above ∼20 GPa than previously proposed polymorphs. In contrast to other polymorphs, the oS24 phase shows a strong bonding differentiation and distorted fivefold coordination geometries of both P atoms. The shortest bond of the phase is a single covalent P-P bond measuring 2.171(11) Šat synthesis pressure. Phosphorus dimerization in GaP sheds light on the nature of the super- Cmcm phase and provides critical new insights into the high-pressure polymorphism of octet semiconductors. Bond directionality and anisotropy explain the relatively low symmetry of this high-pressure phase.

Detection and Quantification of Silver Nanoparticles at Environmentally Relevant Concentrations Using Asymmetric Flow Field-Flow Fractionation Online with Single Particle Inductively Coupled Plasma Mass Spectrometry.

The presence of silver nanoparticles (AgNPs) in aquatic environments could potentially cause adverse impacts on ecosystems and human health. However, current understanding of the environmental fate and transport of AgNPs is still limited because their properties in complex environmental samples cannot be accurately determined. In this study, the feasibility of using asymmetric flow field-flow fractionation (AF4) connected online with single particle inductively coupled plasma mass spectrometry (spICPMS) to detect and quantify AgNPs at environmentally relevant concentrations was investigated. The AF4 channel had a thickness of 350 µm and its accumulation wall was a 10 kDa regenerated cellulose membrane. A 0.02% FL-70 surfactant solution was used as an AF4 carrier. With 1.2 mL/min AF4 cross-flow rate, 1.5 mL/min AF4 channel flow rate, and 5 ms spICPMS dwell time, the AF4-spICPMS can detect and quantify 40-80 nm AgNPs, as well as Ag-SiO2 core-shell nanoparticles (51.0 nm diameter Ag core and 21.6 nm SiO2 shell), with good recovery within 30 min. This system was not only effective in differentiating and quantifying different types of AgNPs with similar hydrodynamic diameters, such as in mixtures containing Ag-SiO2 core-shell nanoparticles and 40-80 nm AgNPs, but also suitable for differentiating between 40 nm AgNPs and elevated Ag(+) content. The study results indicate that AF4-spICPMS is capable of detecting and quantifying AgNPs and other engineered metal nanomaterials in environmental samples. Nevertheless, further studies are needed before AF4-spICPMS can become a routine analytical technique.

Separation and measurement of silver nanoparticles and silver ions using magnetic particles.

The recent surge in consumer products and applications using metallic nanoparticles has increased the possibility of human or ecosystem exposure due to unintentional release into the environment. To protect consumer health and the environment, there is an urgent need to develop tools that can characterize and quantify these materials at low concentrations and in complex matrices. In this study, magnetic nanoparticles coated with either dopamine or glutathione were used to develop a new, simple and reliable method for the separation/pre-concentration of trace amounts of silver nanoparticles followed by their quantification using inductively coupled plasma mass spectrometry (ICP-MS). The structurally modified magnetic particles were able to capture trace amounts of silver nanoparticles (~2 ppb) and concentrate (up to 250 times) the particles for analysis with ICP-MS. Under laboratory conditions, recovery of silver nanoparticles was >99%. More importantly, the magnetic particles selectively captured silver nanoparticles in a mixture containing both nano-particulate and ionic silver. This unique feature addresses the challenges of separation and quantification of silver nanoparticles in addition to the total silver in environmental samples. Spiking experiments showed recoveries higher than 97% for tap water and both fresh and saline surface water.