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At least 19 records

Quantification of SARS-CoV-2 spike protein expression from mRNA vaccines using isotope dilution mass spectrometry

The advent of mRNA vaccine technology has been vital in rapidly creating and manufacturing COVID-19 vaccines at an industrial scale. To continue to accelerate this leading vaccine technology, an accurate method is needed to quantify antigens produced by the transfection of cells with a mRNA vaccine product. This will allow monitoring of protein expression during mRNA vaccine development and provide information on how changes to vaccine components affects the expression of the desired antigen. Developing novel approaches that allow for high-throughput screening of vaccines to detect changes in antigen production in cell culture prior to in vivo studies could aid vaccine development. Here, we have developed and optimized an isotope dilution mass spectrometry method to detect and quantify the spike protein expressed after transfection of baby hamster kidney cells with expired COVID-19 mRNA vaccines. Five peptides of the spike protein are simultaneously quantified and provide assurance that protein digestion in the region of the target peptides is complete since results between the five peptides had a relative standard deviation of less than 15 %. In addition, two housekeeping proteins, actin and GAPDH, are quantified in the same analytical run to account for any variation in cell growth within the experiment. IDMS allows a precise and accurate means to quantify protein expression by mammalian cells transfected with an mRNA vaccine.

60 APPLIED LIFE SCIENCES↗

NWAL Validation Report for U Assay by Potentiometric Titration (Modified Davies and Gray Technique) and U and PU Assay by Isotope Dilution Mass Spectrometry

SRNL Sensing & Metrology, previously Analytical Laboratory, is a member of the IAEA Network of Analytical Laboratories for Nuclear Material Measurement that is qualified to provide Uranium and Plutonium isotopic analysis of nuclear materials by Thermal Ionization Mass Spectrometry. As part of the membership, SRNL participated in the 2019 Nuclear Material Round Robin to maintain the qualification to provide isotopic analysis. SRNL also participated with the additional intent to qualify Uranium Assay by Potentiometric Titration (Davies and Gray method) and Uranium and Plutonium Isotope Dilution by Thermal Ionization Mass Spectrometry as part of the International Atomic Energy Agency’s Network of Analytical Laboratories. The proficiency test exercise was conducted by the Office of Safeguards Analytical Services, Department of Safeguards.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Preparation of 241 Am/ 243 Am gravimetric mixtures and development of Am isotopic and assay measurement techniques using thermal ionization mass spectrometry

Three gravimetric mixtures with 241 Am/ 243 Am isotope ratios at nominally 1:1, 20:1, and 200:1 were prepared for calibration of the thermal ionization mass spectrometer instruments used for americium isotopic and assay measurements by isotope dilution mass spectrometry. The total evaporation analytical technique was developed for high-accuracy and precision measurements of Am isotopic ratios. The technique was also applied to Am assay measurements using isotope dilution mass spectrometry. The Am isotope ratio and assay measurement techniques were utilized to characterize batches of americium oxide separated from plutonium materials in storage at Los Alamos National Laboratory in support of commercial use of 241 AmO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uncertainty evaluation in reference material characterization by double isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS)

Double isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) is one of the most important measurement methods in the establishment of measurement standards for inorganic analysis. However, there is still no good consensus on approaches for uncertainty evaluation in double ID-ICP-MS. Particularly, approaches to treating the instrumental isotopic fractionation (IIF) phenomenon and correlation between uncertainty sources are diverse and often unclear in the literature. Here, an approach for uncertainty evaluation in double ID-ICP-MS measurements is described. Using three certified reference materials (CRMs), it is shown that the IIF effects cancel out and should not be included in the uncertainty budget. Further, a consistent way of considering correlated sources of uncertainty to prevent double counting of uncertainties is described in detail along with an example of measuring the mass fraction of magnesium in an oyster powder CRM.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A new highly enriched 233 U reference material for improved simultaneous determination of uranium amount and isotope amount ratios in trace level samples

A highly-enriched 233 U reference material (>0.99987 n( 233 U)/n(U)) has been prepared and characterized for use as an isotope dilution mass spectrometry spike. An ion exchange separation was performed on 1 g of high purity 233 U to further reduce trace amounts of contaminant Pu in the material. The purified 233 U was then prepared as a master solution which was analyzed for molality of uranium by modified Davies and Gray titration. A portion of the master solution was quantitatively diluted and dispensed for reference material units. Selected units were analyzed for verification of uranium amount and to characterize uranium isotope amount ratios by multi-collector inductively couple plasma mass spectrometry. Furthermore, modelling of spike-corrected isotopic data show that the new spike will enable simultaneous measurements of uranium amount and isotope amount ratios with resulting uncertainties that are substantially less sensitive to over spiking than widely used 233 U certified reference materials.

233U↗

Online collection of LC effluent as droplets for automatic injection into ICP-MS

A sample introduction technique was developed to allow for online, dropwise injection of effluent into a mass spectrometer (MS). This allowed for the coupling of chromatography systems that were not driven by pumps without altering the set-up or separation performance. This capability combined the benefits of coupling separation and measurement while also enabling accurate chromatographic evaluation that would generally be performed offline. The incorporation of a flowing rinse into the system made dropwise resolution possible for any liquid capable of forming drops under ambient conditions. The technique was demonstrated utilizing gas pressurized extraction chromatography (GPEC) and inductively coupled plasma-time-of-flight mass spectrometry (ICP-TOFMS) to illustrate the qualitative applications for rapid separation development and procedure evaluation. This method's quantitative applications were evaluated using single and double isotope dilution mass spectrometry (IDMS) with an external mass bias correction to measure analytes across entire elutions including volumes as small as single drops. In conclusion, the total neodymium values afforded by both single and double IDMS were within the uncertainty of the calculated value for evaluation of full elution peaks and for most of the single drops analyzed that reached above 10k cps Nd-144.

GPEC↗

Uranium Processing Signatures for Nuclear Forensics (NA22 End of FY23 Report)

A vacuum induction melting (VIM) furnace was used to produce an ~120 kg depleted uranium (DU) rod in November 2021 from well characterized feedstock to investigate the separation of thorium (Th) and protactinium (Pa) from uranium (U) during U metal casting and quantify the behavior of the 230 Th/ 234 U and 231 Pa/ 235 U radiochronometry systems. This work suggested that while 234 Th, measured by gamma spectrometry, appears to segregate to the top and surface of the rod, the concentration of 230 Th determined by isotope dilution mass spectrometry (IDMS) in drill turnings from multiple locations in the rod, including the hot top, is relatively consistent. To evaluate whether Th is potentially enriched at only the very outer surface of the cast DU rod relative to the bulk material in the cast rod, thin surface samples were collected from the cast DU rod. Locations sampled included the inner diameter (ID) and outer diameter (OD) of the bottom of the casting and the ID, OD, and top face of the hot top (very top of the casting). The locations are shown in Figure 1. Four samples were taken from each location at different depths in the cast material. Each cut took approximately 0.03 – 0.05” off of the casting.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

C136A and C138A Report of Analysis

In this work the isotopic ratios and weight percentages of 238 Pu, 239 Pu, 240 Pu, 241 Pu and 242 Pu were determined using Isotope Dilution Mass Spectrometry. Two samples of C136A and C138A were sent to the Analytical Research laboratories by the National Nuclear Security Administration Nuclear Reference Material Program. The four samples were dissolved in concentrated hydrochloric acid. From the parent solutions, eight aliquots were taken, diluted, spiked with 244 Pu and submitted to separations. After the samples were separated, they were analyzed using Multicollector Inductively Coupled Plasma Mass Spectrometry. Along with the samples, two C126A Quality Control Samples were analyzed each day. Mass bias standards were also analyzed at the beginning, during and at the end of the analysis. GUM Workbench Pro software Version 2.4.1.406 was used to calculate the isotopic ratios relative to 239 Pu, and total Pu mass and the correlated expanded uncertainties.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Application of HRGS for forensic characterization of uranium oxides, pure uranium metals and uranium alloys

A nondestructive iterative method for uranium-bearing material characterization with HRGS developed earlier in (J. appl. Rad. Isotopes, 166 (2020) 109433) is applied to determine matrix densities and uranium isotope masses of a variety of uranium materials, namely uranium ore, UO 2 and U 3 O 8 powders, fuel elements in the form of UO2 microspheres, uranium metal and uranium alloys. It is shown that U 3 O 8 powders with uranium mass fraction of about 84% can be distinguished from the powders of UO 2 with uranium mass fraction of about 87%; uranium products in the form of liquid or loose powder with matrix density of 0.5-2.0 g/cm 3 can be distinguished from uranium products in the form of compacted fuel elements with matrix density of 6.0-10.0 g/cm 3 and from pure metal uranium and uranium alloys with matrix density of 14.0- 19.0 g/cm 3 . In fuel microspheres based on UO2 the uranium mass fraction 88.02% measured by HRGS is consistent, within the measurement uncertainties, with the results of isotope dilution mass spectrometry 87.76±0.64 % and also is confirmed by X-ray diffraction technique. The uranium mass fraction of the uranium ore estimated as 0.08% by HRGS is consistent, within the measurement uncertainties, with the value 0.09±0.01% determined with WDXRF. Densities of two different uranium metal samples, estimated as 18.42 g/cm 3 and 19.33 g/cm 3 by HRGS are consistent with values 18.24±0.55 g/cm 3 and 18.86±0.59 g/cm 3 , respectively, obtained by the gas pycnometry technique.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

New Capability at ORNL: High Precision Uranium Titration

Destructive analytical measurements establish a nuclear facility’s nuclear material inventory and inventory differences for Nuclear Material Accountancy and Control. A nuclear laboratory’s ability to perform accurate high-precision analytical measurements is key for tracking large inventories within a facility’s material balance areas and during production to track material movement through dynamic processes. For uranium, these measurements are made by using several established high-precision measurement protocols. These include isotope dilution mass spectrometry, gravimetry, and potentiometric titrations. Whatever measurement technique a nuclear lab chooses to use, reference materials (RMs) with certified attributes and accompanying uncertainties are used to calibrate measurement systems, and are the cornerstone for accurate results. In addition to calibration, RMs provide for metrological traceability, are used for method development and validation, and thus provide critical evaluations of the appropriateness and performance of analytical processes used. Evaluations may include validation that a method is fit-for-purpose, quantification of systematic and random biases, and the evaluation of long-term and short-term performance metrics. High-precision measurement techniques require that measured attributes be certified to a high degree of precision in the RMs used—ultimately, to a higher degree than that of the measurement technique itself. The US authority on the production of special nuclear material Certified Reference Materials is the NBL Program Office (NBLPO), formally known as New Brunswick Laboratory (NBL). The NBLPO is responsible for the sales and distribution of existing NBL certified reference materials (CRMs) and for the production of the next generation of nuclear RMs. To accomplish its mission, NBLPO is establishing key base capabilities within the DOE laboratory complex that formerly existed at the NBL laboratory. The Nuclear Analytical Chemistry (NAC) section within the Chemical Sciences Division (CSD) at Oak Ridge National Laboratory (ORNL) is currently working with NBLPO to set up laboratory and measurement capabilities to provide measurements and capabilities for production and/or recertification of existing and future CRMs for uranium assay. The NBL-developed high-precision titration (HPT) method is a critically-evaluated, extremely precise and accurate primary method utilized for the determination of uranium content in a variety of uranium materials. The HPT method, combined with detailed balance weighing protocols, provides for an analytical methodology that is unsurpassed in precision and one in which all sources of error have been evaluated, a requirement of CRM certification. HPT capability within the United States was lost with the closure of the labs at NBL. The NAC has been collaborating with NBLPO to stand up and demonstrate the capability to perform uranium assay via HPT at ORNL. HPT can produce results with an expanded uncertainty of approximately 0.01% for pure uranium compounds, with typical precisions of <0.006%. The major tasks required to stand up the method at ORNL were the refurbishment of a dedicated lab and equipment setup, procedure development, analyst training, establishing method-specific quality assurance, and qualification of an analyst to perform the method. This report summarizes these tasks, outlines the documents drafted, and gives the outcome of the qualification titrations.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Destructive Analysis of TRISO Particles: Crush/Burn/Leach Followed by Davies-Gray Titration and IDMS

The accurate accounting of nuclear materials is a cornerstone of international nuclear safeguards. One emerging challenge in this domain is the fabrication of TRIstructural ISOtropic (TRISO) particle fuels. Although these innovative fuel forms are critical for advanced reactor applications, their robust refractory ceramics and coating compositions present significant obstacles to destructive analysis (DA) methods. Ensuring full and quantitative recovery from these particles is essential for accurate mass accountancy. The current study was initiated to address these challenges, first by validating a previously established destructive method developed by Oak Ridge National Laboratory (ORNL) for the quantitative recovery of uranium from TRISO particles and then following that process with uranium content determination through isotope dilution mass spectrometry (IDMS) and Davies-Gray titration. This study expands on the scope of a digestive method that was developed under the Advanced Gas Reactor Fuel Development and Qualification program and is currently implemented in both the Coated Particle Fuel Development Laboratory and Irradiated Fuels Examination Laboratory at ORNL. The success of the previous Advanced Gas Reactor work relied on developing a DA method to evaluate the fabrication process and reactor experiments. The methodology described in this report was designed to rigorously investigate the efficacy of the crush/burn/leach sample preparation of TRISO particles; it aims to quantify uranium recovery while also assessing the effects of TRISO constituents (e.g., silicon and zirconium) on analytical precision and accuracy. By comparing the results from the titration method and IDMS, we sought to determine whether existing analytical procedures accepted by the International Atomic Energy Agency (IAEA) could be effectively translated to TRISO fuel forms. The team employed an approach that involved processing replicate TRISO samples, optimizing the milling (i.e., crushing) step and performing serial leaches. The elemental composition of the analytical samples was examined to prepare for interference studies in the second year of this project. The integration of gamma spectrometry to verify residual uranium activity further strengthened the validation. Statistical methods were applied to the collected data to evaluate the uncertainties arising from sampling, sample preparation and uranium quantification. These uncertainties were then compared to the IAEA’s international target values (ITVs). Additional data collected in upcoming project work will strengthen the uncertainty estimates. Ultimately, it is hoped that this project will contribute materially to the body of work related to characterization of TRISO based fuels for the purpose of material accountancy and its applications to international safeguards.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Helium concentration in the earth's lower atmosphere

A helium content of 5.222 + or - 0.017 ppm by volume has been established by measurements during 1981 of the earth's lower atmosphere, using isotope dilution mass spectrometry. This compares well with the currently accepted value of 5.239 + or - 0.004 ppm determined by Gluekhauf (1946) on the basis of measurements conducted in the 1930s. While processes that could have altered helium concentrations since the 1930s imply a significant increase in concentration, due to helium release during natural gas production, possible net helium losses from the atmosphere are not easily quantifiable.

Oliver, B. M.↗

U-238-U-234-Th-230-Th-232 systematics and the precise measurement of time over the past 500,000 years

A method is presented for the high-precision measurement of the Th-230 abundance in corals by isotope-dilution mass spectrometry using techniques developed by Chen and Wasserburg (1980, 1981) and Chen et al. (1986). It is shown that 6 x 10 to the 8th atoms of Th-230 can be measured to + or - 30 percent (2 sigma) and 2 x 10 to the 10th atoms of Th-230 to + or - 2 percent. The time over which useful age data on corals can be obtained ranges from a few years to about 500 ky, with the uncertainty in age ranging from 5 y for a 180-y-old coral, to 44 y for a 8294-y-old coral, to 1.1 ky for a 123.1-ky-old coral. Ages were determined with high analytical precision for several corals that grew during high sea-level stands about 120 ky ago, supporting the view that the dominant cause of Pleistocene climate change was Milankovitch forcing.

Edwards, R. Lawrence↗

RAPID UNSEPARATED RARE EARTH ELEMENT ANALYSES BY ISOTOPE DILUTION MULTICOLLECTOR INDUCTIVELY COUPLED MASS SPECTROMETRY (ID-MC-ICP-MS)

We present a method for analyzing rare earth elements (REEs) by isotope dilution without separation of individual elements. Utilizing a Nu Plasma 2 multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) equipped with an Aridus II desolvation nebulizer, sample introduction tuning parameters (torch position, gas flows) were investigated and used to minimize oxide formation (e.g., NdO/Nd <0.05%) and remove the need to analyze the REEs as separated “cuts.” Ratios for spike/sample isotopes in mixed synthetic standards containing varying amounts of Ce, Nd, Sm, Eu, Gd, Dy, Er, and Yb were measured accurately within 1% of IUPAC values. La and Lu in the standards were more than 2% off from expected values due to more demanding interference corrections. A USGS BCR-2 rock standard was also processed with flux fusion, iron coprecipitation and a single column pass bulk separation followed by analysis. The concentrations for Ce, Nd, Sm, Eu, Dy, Er, and Yb fell within 2% of consensus values. A United States Geological Survey (USGS) BIR-1A rock standard was also processed in triplicate by hydrofluoric and nitric acid digestion, yielding rare earth concentrations within 3% of consensus values with 0.3% relative standard deviation (n=3). This demonstrates the ability to produce high quality REE patterns of comparable quality to traditional methods involving labor and time intensive REE separation, with sample preparation and analytical times that are comparable to analyses against isotope dilution by single-collector ICP-MS.

Shen, Steve D.↗

Determination of Mercury Content in a Shallow Firn Core from Summit, Greenland by Isotope Dilution Inductively Coupled Plasma Mass Spectrometry

The total mercury Hg content was determined in 6 cm sections of a near-surface 7 m firn core and in surrounding surface snow from Summit, Greenland (elevation: 3238 m, 72.58 N, 38.53 W) in May 2001 by isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICP-MS). The focus of this research was to evaluate the capability of the ID-CV-ICPMS technique for measuring trace levels of Hg typical of polar snow and firn. Highly enriched Hg-201 isotopic spike is added to approximately 10 ml melted core and thoroughly mixed. The Hg(+2) in the sample is reduced on line with tin (II) chloride (SnCl2) and the elemental Hg (Hg(0)) vapor pre-concentrated on to gold gauze using a commercial amalgam system. The Hg is then thermally desorbed and introduced into a quadrupole ICP-MS. The blank corrected Hg concentrations determined for all samples ranged from 0.25 ng/L to 1.74 ng/L (ppt) (average 0.59 ng/L plus or minus 0.28 ng/L) and fall within the range of those previously determined by Boutron et al., 1998 (less than or equal to 0.05 ng/L to 2.0 ng/L) for the Summit site. The average blank value was 0.19 ng/L plus or minus 0.045 ng/L (n=6). The Hg values specifically for the firn core range from 0.25 ng/L to 0.87 ng/L (average 0.51 ng/L plus or minus 0.13 ng/L) and show both values declining with time and larger variability in concentration in the top 1.8 m.

Mann, Jacqueline L.↗

Determination of 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and -furans at the part per trillion level in United States beef fat using high-resolution gas chromatography/high-resolution mass spectrometry

As part of the U.S. EPA Dioxin Reassessment Program, the 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and furans were measured at part per trillion (ppt) levels in beef fat collected from slaughter facilities in the United States. This is the first statistically designed national survey of these compounds in the U.S. beef supply. Analyte concentrations were determined by high-resolution gas chromatography/high-resolution mass spectrometry, using isotope dilution methodology. Method limits of detection on a whole weight basis were 0.05 ppt for TCDD and 0.10 ppt for TCDF, 0.50 ppt for the pentas (PeCDDs/PeCDFs)/hexas (HxCDDs/HxCDFs)/heptas (HpCDDs/HpCDFs), and 3.00 ppt for the octas (OCDD/OCDF). Method detection and quantitation limits were established on the basis of demonstrated performance criteria utilizing fortified samples rather than by conventional signal-to-noise or variability of response methods. The background subtraction procedures developed for this study minimized the likelihood of false positives and increased the confidence associated with reported values near the detection limits. Mean and median values for each of the 2,3,7,8-Cl-substituted dioxins and furans are reported, along with the supporting information required for their interpretation. The mean toxic equivalence values for the samples are 0.35 ppt (nondetects = 0) and 0.89 ppt (nondetects = 1/2 LOD).

Benzofurans/analysis↗

A highly-enriched 244 Pu reference material for nuclear safeguards and nuclear forensics measurements

A highly-enriched 244 Pu isotope dilution reference material has been prepared and characterized for metrologically traceable measurements of very small quantities of plutonium. The amount of plutonium in samples associated with nuclear safeguards and nuclear forensic measurements can be significantly less than 1 ng. Accordingly, the ability to quantify the amount and isotopic composition of plutonium from a single mass-spectrometric analysis is particularly desirable. The highly-enriched 244 Pu reference material, described here, will minimize the magnitude of spike corrections necessary to obtain accurate information on plutonium isotopic composition from isotope dilution measurements.

07 ISOTOPE AND RADIATION SOURCES↗