Quantification of Hydrogen Isotopes Utilizing Raman Spectroscopy Paired with Chemometric Analysis for Application across Multiple Systems.

Online and real-time analysis of a chemical process is a major analytical challenge that can drastically change the way the chemical industry or chemical research operates. With in situ analyses, a new and powerful understanding of chemistry can be gained; however, building robust tools for long-term monitoring faces many challenges, including compensating for instrument drift, instrument replacement, and sensor or probe replacement. Accounting for these changes by recollecting calibration data and rebuilding quantification models can be costly and time-consuming. Here, methods to overcome these challenges are demonstrated with an application of Raman spectroscopy to monitoring hydrogen isotopes with varied speciation within dynamic gas streams. Specifically, chemical data science tools such as chemometric modeling are leveraged along with several examples of calibration transfer approaches. Furthermore, the optimization of instrument and sensor cell parameters for targeted gas-phase analyses is discussed. While the particular focus on hydrogen is highly beneficial within the nuclear energy sector, mechanisms built and demonstrated here are widely applicable to optical spectroscopy monitoring in numerous other chemical systems that can be leveraged in other processes.

Iodine and Carbonate Species Monitoring in Molten NaOH-KOH Eutectic Scrubber via Dual-Phase In Situ Raman Spectroscopy.

Molten hydroxide scrubbing of off-gas vapors is a potential process to improve safety during the operation of generation IV molten salt nuclear reactors (MSRs). MSRs produce off-gases that can be vented by the reactor core and treated via off-gas scrubbers. Molten hydroxide scrubbers focus on capturing volatile iodine radionuclides, and they can also be used to capture aerosols and particulates and to neutralize acidic species. The performance of these scrubbers depends on the chemical interactions of the scrubbing medium with the off-gas species. Knowledge of the concentration and speciation of scrubbed or target species, as well as process and environmental interferents, can enable advanced operation of MSR off-gas treatment systems. Optical online monitoring is an excellent technology to provide this information in real time, while limiting the need for operators to interact with radioactive samples through hands-on interrogation. Raman spectroscopy can provide crucial chemical information on the state of the molten eutectic during treatment in the molten phase, as well as the gas phase. In this work, Raman spectroscopy is used to detect iodine species, specifically iodate, in the molten phase of a NaOH-KOH eutectic and to construct a calibration curve of the Raman signal of those species. Additionally, a carbonate interferent is followed from the gas phase to the liquid phase as a basis for reaching a Raman-aided mass balance of the molten hydroxide eutectic scrubber system.

A versatile and low-cost chip-to-world interface: Enabling ICP-MS characterization of isotachophoretically separated lanthanides on a microfluidic device.

Microfluidics offer novel and state-of-the-art pathways to process materials. Microfluidic systems drastically reduce timeframes and costs associated with traditional lab-scale efforts in the area of analytical sample preparations. The challenge arises in effectively connecting microfluidics to off-chip analysis tools to accurately characterize samples after treatment on-chip. Fabrication of a chip-to-world connection includes one end of a fused silica capillary interfaced to the outlet of a microfluidic device (MFD). The other end of the capillary is connected to a commercially available CEI-100 interface that passes samples into an inductively coupled plasma mass spectrometer (ICP-MS). This coupling creates an inexpensive and simple chip-to-world connection that enables on-chip and off-chip methods of analyzing the separation of rare earth elements. Specifically, this is demonstrated by utilizing isotachophoresis (ITP) on a microfluidic chip to separate up to 14 lanthanides from a homogenous sample into elementally pure bands. The separated analyte zones are successfully transferred across a 7 nL void volume at the microchip-capillary junction, such that separation resolution is maintained and even increased through the interface and into the ICP-MS, where the elemental composition of the sample is analyzed. Lanthanide samples of varying composition are detected using ICP-MS, demonstrating this versatile and cost-effective approach, which maintains the separation quality achieved on the MFD. This simple connection enables fast, low-cost sample preparation immediately prior to injection into an ICP-MS or other analytical instrument.

Design and optimization of a fused-silica microfluidic device for separation of trivalent lanthanides by isotachophoresis.

Elemental analysis of rare earth elements is essential in a variety of fields including environmental monitoring and nuclear safeguards; however, current techniques are often labor intensive, time consuming, and/or costly to perform. The difficulty arises in preparing samples, which requires separating the chemically and physically similar lanthanides. However, by transitioning these separations to the microscale, the speed, cost, and simplicity of sample preparation can be drastically improved. Here, all fourteen non-radioactive lanthanides (lanthanum through lutetium minus promethium) are separated by ITP for the first time in a serpentine fused-silica microchannel (70 µm wide × 70 µm tall × 33 cm long) in <10 min at voltages ≤8 kV with limits of detection on the order of picomoles. This time includes the 2 min electrokinetic injection time at 2 kV to load sample into the microchannel. The final leading electrolyte consisted of 10 mM ammonium acetate, 7 mM α-hydroxyisobutyric acid, 1% polyvinylpyrrolidone, and the final terminating electrolyte consisted of 10 mM acetic acid, 7 mM α-hydroxyisobutyric acid, and 1% polyvinylpyrrolidone. Electrophoretic electrodes are embedded in the microchip reservoirs so that voltages can be quickly applied and switched during operation. The limits of detection are quantified using a commercial capacitively coupled contactless conductivity detector (C4 D) to calculate ITP zone lengths in combination with ITP theory. Optimization of experimental procedures and reproducibility based on statistical analysis of subsequent experimental results are addressed. Percent error values in band length and conductivity are ≤8.1 and 0.37%, respectively.

In Situ Spectroscopic Analysis and Quantification of [Tc(CO)3]+ in Hanford Tank Waste.

The quantitative conversion of nonpertechnetate [Tc(CO)3]+ species in nuclear waste storage tank 241-AN-102 at the Hanford Site is demonstrated. A waste sample containing the [Tc(CO)3]+ species is added to a developer solution that rapidly converts the nonemissive species into a luminescent complex, which is detected spectroscopically. This method was first demonstrated using a [Tc(CO)3]+ sample of nonwaste containing matrix to determine a detection limit (LOD), resulting in a [Tc(CO)3]+ LOD of 2.20 × 10-7 M, very near the LOD of the independently synthesized standard (2.10 × 10-7 M). The method was then used to detect [Tc(CO)3]+ in a simulated waste using the standard addition method, resulting in a [Tc(CO)3]+ concentration of 1.89 × 10-5 M (within 27.7% of the concentration determined by ß liquid scintillation counting). Three samples from 241-AN-102 were tested by the standard addition method: (1) a 5 M Na adjusted fraction, (2) a fraction depleted of 137Cs, and (3) an acid-stripped eluate. The concentrations of [Tc(CO)3]+ in these fractions were determined to be 9.90 × 10-6 M (1), 0 M (2), and 2.46 × 10-6 M (3), respectively. The concentration of [Tc(CO)3]+ in the as-received AN-102 tank waste supernatant was determined to be 1.84 × 10-5 M.

In Situ Quantification of [Re(CO)3]+ by Fluorescence Spectroscopy in Simulated Hanford Tank Waste.

A pretreatment protocol is presented that allows for the quantitative conversion and subsequent in situ spectroscopic analysis of [Re(CO)3]+ species in simulated Hanford tank waste. In this test case, the nonradioactive metal rhenium is substituted for technetium (Tc-99), a weak beta emitter, to demonstrate proof of concept for a method to measure a nonpertechnetate form of technetium in Hanford tank waste. The protocol encompasses adding a simulated waste sample containing the nonemissive [Re(CO)3]+ species to a developer solution that enables the rapid, quantitative conversion of the nonemissive species to a luminescent species which can then be detected spectroscopically. The [Re(CO)3]+ species concentration in an alkaline, simulated Hanford tank waste supernatant can be quantified by the standard addition method. In a test case, the [Re(CO)3]+ species was measured to be at a concentration of 38.9 µM, which was a difference of 2.01% from the actual concentration of 39.7 µM.

Optically Transparent Thin-Film Electrode Chip for Spectroelectrochemical Sensing.

A novel microfabricated optically transparent thin-film electrode chip for fluorescence and absorption spectroelectrochemistry has been developed. The working electrode was composed of indium tin oxide (ITO); the quasi-reference and auxiliary electrodes were composed of platinum. The stability of the platinum quasi-reference electrode was improved by coating it with a planar, solid state Ag/AgCl layer. The Ag/AgCl reference was characterized with scanning electron microscopy and energy-dispersive X-ray spectroscopy. Cyclic voltammetry measurements showed that the electrode chip was comparable to a standard electrochemical cell. Randles-Sevcik analysis of 10 mM K3[Fe(CN)6] in 0.1 M KCl using the electrode chip gave a diffusion coefficient of 1.59 × 10-6 cm2/s, in comparison to the value of 2.38 × 10-6 cm2/s using a standard electrochemical cell. By using the electrode chip in an optically transparent thin-layer electrode (OTTLE), the absorption based spectroelectrochemical modulation of [Fe(CN)6]3-/4- was demonstrated, as well as the fluorescence based modulation of [Ru(bpy)3]2+/3+. For the fluorescence spectroelectrochemical determination of [Ru(bpy)3]2+, a detection limit of 36 nM was observed.

GOx signaling triggered by aptamer-based ATP detection.

Aptamer based ATP binding leads to the release of the co-factor FAD, which acts as a trigger to 'turn-on' the activity of apo-GOx and thus generates a measurable response.