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At least 127 records · Page 7

Mixed deformation styles observed on a shallow subduction thrust, Hikurangi margin, New Zealand

Geophysical observations show spatial and temporal variations in fault slip style on shallow subduction thrust faults, but geological signatures and underlying deformation processes remain poorly understood. International Ocean Discovery Program (IODP) Expeditions 372 and 375 investigated New Zealand’s Hikurangi margin in a region that has experienced both tsunami earthquakes and repeated slow-slip events. We report direct observations from cores that sampled the active Papaku splay fault at 304 m below the seafloor. This fault roots into the plate interface and comprises an 18-m-thick main fault underlain by ~30 m of less intensely deformed footwall and an ~10-m-thick subsidiary fault above undeformed footwall. Fault zone structures include breccias, folds, and asymmetric clasts within transposed and/or dismembered, relatively homogeneous, silty hemipelagic sediments. The data demonstrate that the fault has experienced both ductile and brittle deformation. As a result, this structural variation indicates that a range of local slip speeds can occur along shallow faults, and they are controlled by temporal, potentially far-field, changes in strain rate or effective stress.

58 GEOSCIENCES↗

Optimizing the shape of photometric redshift distributions with clustering cross-correlations

We present an optimization method for the assignment of photometric galaxies to a chosen set of redshift bins. This is achieved by combining simulated annealing, an optimization algorithm inspired by solid-state physics, with an unsupervised machine learning method, a self-organizing map (SOM) of the observed colours of galaxies. Starting with a sample of galaxies that is divided into redshift bins based on a photometric redshift point estimate, the simulated annealing algorithm repeatedly reassigns SOM-selected subsamples of galaxies, which are close in colour, to alternative redshift bins. We optimize the clustering cross-correlation signal between photometric galaxies and a reference sample of galaxies with well-calibrated redshifts. Depending on the effect on the clustering signal, the reassignment is either accepted or rejected. By dynamically increasing the resolution of the SOM, the algorithm eventually converges to a solution that minimizes the number of mismatched galaxies in each tomographic redshift bin and thus improves the compactness of their corresponding redshift distribution. This method is demonstrated on the synthetic Legacy Survey of Space and Time cosmoDC2 catalogue. We find a significant decrease in the fraction of catastrophic outliers in the redshift distribution in all tomographic bins, most notably in the highest redshift bin with a decrease in the outlier fraction from 57 percent to 16 percent.

79 ASTRONOMY AND ASTROPHYSICS↗

Corrosion Resistance of an AlCeMg/Stainless-Steel Reactive Bond

A major issue for metal components in many industries is corrosion as it can substantially reduce their lifetime. This issue is especially problematic for materials used in heat exchanger applications. Al–Ce–Mg alloys, which exhibit corrosion resistance and can reactively bond with other metals, may be a viable solution to this problem. This investigation studied the corrosion behavior of Al–2Ce–6Mg (atomic percent)/stainless-steel (SS) reactive bond interfaces after full immersion in nitric, sulfuric, formic, and mixed acid for 267 h. This particular Al–Ce–Mg alloy was chosen due to its good castability. The results of scanning electron microscope characterization showed that reactive bond formations repeatedly occurred throughout the length of the casting in the as-cut samples and that these formations maintained a secure bonding between the alloy and the stainless-steel tubes. Transmission electron microscopy results showed that there was a clear compositional and microstructural transition across the reactive bond. The results of the immersion tests indicated that the nitric, sulfuric, and the mixed acid did not have an observably negative effect on the reactive bond structure. As for the sample exposed to formic acid only, noticable changes were seen in both the microstructural appearance and the elemental profile across the bond, suggesting that oxide formation occurred.

Brechtl, Jamieson [ORNL] (ORCID:0000000217394283)↗

Integrated Component-Specific Measurements to Develop Emission Factors for Compressors and Gas Gathering Lines

The Department of Energy (DOE) National Energy Technology Laboratory (NETL) and other critical stakeholders (e.g., U.S. Environmental Protection Agency (USEPA), state regulators, and industry) seek to more accurately characterize and quantify methane emissions from compressors and gathering lines within the Gathering and Boosting (G&B) segment of the natural gas system network. These efforts will reduce uncertainties in emissions estimates in USEPA’s current Green House Gas Inventory (GHGI) under their Greenhouse Gas Reporting Program (GHGRP). For this study, four G&B stations in the Gulf Coast Area were visited four times over the course of one year. Components were classified according to equipment and component type and emissions from select components were measured using multiple measurement technologies. The following major equipment types were considered: i) compressors, ii) separators, iii) dehydrators, iv) coalescers, v) slug catchers, vi) yard piping, vii) tanks, and viii) gathering lines. Individual components on each equipment type were further divided into the following main categories: i) connectors, ii) valves, iii) pressure relief valves (PRV), iv) meters, v) gauges, vi) regulators, vii) pneumatic device vents, and viii) compressor vents (e.g., distance piece vents [DPVs] and rod packing vents [RPVs]). Components were screened for the presence of leaks and venting emissions with an optical gas imaging (OGI) camera, and methane emission rates were measured using a microdilution high volume sampler. Downwind emissions were measured using an Open Path Fourier Transform Infrared (OP-FTIR) Spectrometer. Data were evaluated to assess correlation with site, equipment, time, and operational variables. Key findings and recommendations from the study include: A) Different counting methodologies can result in vastly different component counts, thus influencing total emissions calculations using Subpart W population EFs. A standard methodology should be adopted for classifying and counting components in order to minimize inconsistencies across studies and instruct stakeholders responsible for GHGI reporting. B) Results support current component subcategories listed in USEPA Subpart W, including the subdivision of connectors (flanged and “other”) and pneumatic device vents (intermittent, continuous low bleed, and continuous high bleed). C) Emission rates vary across sites and a relationship between higher emissions and compressor age was observed for some components. D) Component emission rates varied between field campaigns. The type of components contributing to overall measured emissions also varied among field campaigns. However, the emission rate variability was larger between different components (of the same category) than the variability in one component over the four field campaigns. Therefore, when calculating emission factors, it is not necessary to take repeat measurements to capture component variability. E) Measuring the emission rate of a sample for an extended period of time is not necessary to capture the average component emission rate. F) For reporting purposes, excluding liquid lines from site-wide screening may have a negligible effect on component-related emissions. However, from a site management perspective, malfunctioning components were not uncommon on liquid lines and contributed substantially to fugitive emissions at some sites. G) Population EFs, whether including or excluding liquid lines, were a conservative estimate of fugitive emissions. Leaker EFs consistently underestimated emissions at the field sites. Measurements at more sites, particularity sites in other areas of the country, need to be completed before determining the accuracy of EFs.

03 NATURAL GAS↗

Assessment of human nuclear and mitochondrial DNA qPCR assays for quantification accuracy utilizing NIST SRM 2372a

In forensic DNA casework, a highly accurate real-time quantitative polymerase chain reaction (qPCR) assay is recommended per the Scientific Working Group on DNA Analysis Methods (SWGDAM) (SWGDAM Validation Guidelines for DNA Analysis Methods [1]) to determine whether a DNA sample is of sufficient quantity and robust quality to move forward with downstream short tandem repeats (STR) or sequencing analyses. Most of these assays rely on a standard curve, referred to herein and traditionally as absolute qPCR, in which an unknown is compared, relative to that curve. However, one fundamental issue with absolute qPCR is the quantifiable concentration of commercial assay standards can vary depending on (1) origin, i.e., whether from a cell line or a human subject, (2) supplier, (3) lot number, (4) shipping method, etc. In 2018, the National Institute for Standards and Technology (NIST) released a human DNA standard reference material for evaluating qPCR quantification standards, Standard Reference Material (SRM) 2372a, Romsos et al. (2018) [2] which contains three well-characterized human genomic DNA samples: Component A) a single male1 donor, Component B) a single female 1 donor, and Component C) a 1:3 male 2 :female 2 donor, each with certification data for nDNA and informational mitochondrial DNA(mtDNA)/nuclear DNA (nDNA) ratio data. The SRM 2372a was used to assess four qPCR assays: (1) Quantifiler Trio (Thermo Fisher Scientific, Waltham, MA) for nDNA quantification, (2) NovaQUANT (EMD Millipore Corporation, San Diego, CA) for nDNA and mtDNA quantification, (3) a custom duplex mtDNA assay, and (4) a custom triplex mtDNA assay. Additionally, extracts from eighteen (18) skeletal remains were tested with the latter three assays for concordance of DNA concentration and with assays (2) and (3), for the degradation state. Our assessment revealed that an accurate, efficient, and reproducible qPCR assay is dependent on (1) the quality and reliability of the DNA standard, (2) the qPCR chemistry, and (3) the specific primers, and probes (if applicable), used in an assay. Finally, our findings indicate qPCR assays may not always quantify as expected and that performance of each lot should be verified using a well-characterized DNA standard such as the NIST SRM 2372a and adjusted if warranted.

59 BASIC BIOLOGICAL SCIENCES↗

Finding simplicity: unsupervised discovery of features, patterns, and order parameters via shift-invariant variational autoencoders *

Abstract Recent advances in scanning tunneling and transmission electron microscopies (STM and STEM) have allowed routine generation of large volumes of imaging data containing information on the structure and functionality of materials. The experimental data sets contain signatures of long-range phenomena such as physical order parameter fields, polarization, and strain gradients in STEM, or standing electronic waves and carrier-mediated exchange interactions in STM, all superimposed onto scanning system distortions and gradual changes of contrast due to drift and/or mis-tilt effects. Correspondingly, while the human eye can readily identify certain patterns in the images such as lattice periodicities, repeating structural elements, or microstructures, their automatic extraction and classification are highly non-trivial and universal pathways to accomplish such analyses are absent. We pose that the most distinctive elements of the patterns observed in STM and (S)TEM images are similarity and (almost-) periodicity, behaviors stemming directly from the parsimony of elementary atomic structures, superimposed on the gradual changes reflective of order parameter distributions. However, the discovery of these elements via global Fourier methods is non-trivial due to variability and lack of ideal discrete translation symmetry. To address this problem, we explore the shift-invariant variational autoencoders (shift-VAEs) that allow disentangling characteristic repeating features in the images, their variations, and shifts that inevitably occur when randomly sampling the image space. Shift-VAEs balance the uncertainty in the position of the object of interest with the uncertainty in shape reconstruction. This approach is illustrated for model 1D data, and further extended to synthetic and experimental STM and STEM 2D data. We further introduce an approach for training shift-VAEs that allows finding the latent variables that comport to known physical behavior. In this specific case, the condition is that the latent variable maps should be smooth on the length scale of the atomic lattice (as expected for physical order parameters), but other conditions can be imposed. The opportunities and limitations of the shift VAE analysis for pattern discovery are elucidated.

97 MATHEMATICS AND COMPUTING↗

Laser Confocal Microscopy Uncertainty Quantification Study

At Los Alamos National Laboratory (LANL), the Storage Safety and Engineering (SSE) team completes annual surveillance on a subset of in-use interim nuclear material storage containers in fulfilment of requirements outlined in DOE Manual M 441.1-1. The containers are selected through several methods, such as subject matter expert judgement, random selection, and trending items. Following these selections, the SSE team has the capacity to complete surveillance on 15-20 containers each fiscal year, composed of a combination of SAVY-4000 and Hagan storage containers. Through previous work, the stainless-steel components of the containers have been identified as life limiting components, with an emphasis on the thin-walled bodies. The team is focused on understanding the extent of general and pitting corrosion, due to observations of extensive corrosion from stored contents and bag-out-bag degradation. Quantifying corrosion effects on the thin-walled stainless steel container bodies, and understanding potential impacts to the respective design release rates and design qualification release rates is paramount to the team. To date, destructive examination (DE) has proven to be the most insightful method for developing an understanding on the extent of corrosion on used containers. To standardize this process, the SSE team developed a destructive examination guide for analyzing stainless steel components of the containers. Corroded containers of interest are identified during surveillance activities and set aside for sectioning and characterization. Following sectioning, a major step in the DE workflow is the utilization of laser confocal microscopy for scanning corroded samples of interest and extracting data on pits, such as count, depth, and equivalent diameter. Adhering to the techniques outlined in the DE guide, analysis has been completed on two Hagans and one SAVY-4000 container, with the maximum pit depth recorded as 139.1 ± 22.82 μm on a 17.5 year old Hagan. The findings from the completed destructive examinations will be utilized to support lifetime extension efforts of the SAVY-4000 as the team can better estimate corrosion rates and effects over time based on stored contents and age. Due to the implications of observing extreme pit depths that approach the nominal container body thickness of .0299 inches (0.759 mm) or minimum container thickness of 0.236” (0.6 mm), high confidence in the LCM measurements is desired. Through testing outlined in, it was concluded that the total error ascribed to the 20x objective when conducting large image mapping on the Keyence VK-X3050 laser confocal microscope (LCM) relative to a 50x objective (reference) is 16.4% (± 8.73%). For shallow features on the order of pristine SAVY surface defects (i.e. 5 μm), this uncertainty is appropriate. However, this conservative estimate of total error poses a fundamental concern for pit depths that approach the thickness of the measured samples. That is, with the measurement uncertainty currently employed on all measurements, the LCM would be unable to resolve if a pit with a depth of 515 μm is through wall. Standard step height samples were procured and used in the present study to assess the resolution and repeatability of height measurements. Understanding the resolution and repeatability of height measurements was the first focus of the team as it relates directly to pit depth, which is of primary concern. Calibration gratings were procured to evaluate the resolution and repeatability of measurements in the X and Y axes of the LCM stage. The results of the depth uncertainty study were conducted first and presented in the subsequent sections. The planar uncertainty study is appended to the depth study with conclusions from both summarized at the end of the report.

36 MATERIALS SCIENCE↗

DeepClimGAN: A High-Resolution Climate Data Generator

Earth system models (ESMs), which simulate the physics and chemistry of the global atmosphere, land, and ocean, are often used to generate future projections of climate change scenarios. These models are far too computationally inten- sive to run repeatedly, but limited sets of runs are insufficient for some important applications, like adequately sampling distribution tails to characterize extreme events. As a com- promise, emulators are substantially less expensive but may not have all of the complexity of an ESM. Here we demon- strate the use of a conditional generative adversarial network (GAN) to act as an ESM emulator. In doing so, we gain the ability to produce daily weather data that is consistent with what ESM might output over any chosen scenario. In particular, the GAN is aimed at representing a joint proba- bility distribution over space, time, and climate variables, enabling the study of correlated extreme events, such as floods, droughts, or heatwaves.

Extreme events, Machine Learning, deep learning↗

Towards Low-Temperature CVD Synthesis and Characterization of Mono- or Few-Layer Molybdenum Disulfide

Molybdenum disulfide (MoS 2 ) transistors are a promising alternative for the semiconductor industry due to their large on/off current ratio (>10 10 ), immunity to short-channel effects, and unique switching characteristics. MoS 2 has drawn considerable interest due to its intriguing electrical, optical, sensing, and catalytic properties. Monolayer MoS 2 is a semiconducting material with a direct band gap of ~1.9 eV, which can be tuned. Commercially, the aim of synthesizing a novel material is to grow high-quality samples over a large area and at a low cost. Although chemical vapor deposition (CVD) growth techniques are associated with a low-cost pathway and large-area material growth, a drawback concerns meeting the high crystalline quality required for nanoelectronic and optoelectronic applications. This research presents a lower-temperature CVD for the repeatable synthesis of large-size mono- or few-layer MoS 2 using the direct vapor phase sulfurization of MoO 3 . The samples grown on Si/SiO 2 substrates demonstrate a uniform single-crystalline quality in Raman spectroscopy, photoluminescence (PL), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and scanning transmission electron microscopy. These characterization techniques were targeted to confirm the uniform thickness, stoichiometry, and lattice spacing of the MoS 2 layers. The MoS 2 crystals were deposited over the entire surface of the sample substrate. With a detailed discussion of the CVD setup and an explanation of the process parameters that influence nucleation and growth, this work opens a new platform for the repeatable synthesis of highly crystalline mono- or few-layer MoS 2 suitable for optoelectronic application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

PMK 1000 cone-socket ventilator fittings force testing to ISO 5356-1:2015 Standard

This memo summarizes the results of verification tests on a cone-socket fitting to the ISO 5356-1:2015 standard, annexes B and F. The components were found to meet requirements holding 50N tensile force and more than 35 N-cm of torque for 10 seconds without separating at 35°C with a fresh socket. Humidity control was unavailable; consequently, humidity was significantly lower than the values in the ISO standard. Several repeat tests of the fitting with force, torque, and time excursions give us confidence that the fittings perform suitably to the ISO standard. Force overload tests suggest that the samples will disengage under tension at around 69 N, while torque overload tests under a force of 50 N will fail at 79 N-cm of torque. If repeated tests are performed on the same component, the socket can deform and lead to the connection failing the standard requirements. However, such failures only occur with repeated testing, and the gripping of such units can be modified so that they pass the standard. This observation demonstrates that socket gripping is responsible for those failures and would not be a problem in application.

42 ENGINEERING↗

Measurement and interpretation of Mueller matrices of barley leaves

We report the results of measuring Mueller matrices for three groups of leaf samples of common barley (Hordeum vulgare): Chlorina mutant, Chlorina etiolated mutant and Cesaer varieties. The repeatability of the measurement results of Mueller matrices of such a complex and highly depolarising object as a plant leaf is demonstrated. It is shown that the barley leaves of these three groups can be reliably identified both at forward scattering and backward scattering modes; the best results are obtained in the case of forward scattering. In both cases, the most informative matrix elements are identified. It is also shown that at backward scattering mode linear dichroism comes out, the magnitude of which increases with decreasing observation angle. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Early-life atomic-bomb irradiation accelerates immunological aging and elevates immune-related intracellular reactive oxygen species

Reactive oxygen species (ROS) play an important role in immune responses; however, their excessive production and accumulation increases the risk of inflammation-related diseases. Although irradiation is known to accelerate immunological aging, the underlying mechanism is still unclear. To determine the possible involvement of ROS in this mechanism, we examined 10,023 samples obtained from 3752 atomic-bomb survivors in Hiroshima and Nagasaki, who participated in repeated biennial examinations from 2008 to 2016, for the effects of aging and radiation exposure on intracellular ROS (H 2 O 2 and O 2 •- ) levels, percentages of T-cell subsets, and the effects of radiation exposure on the relationship between cell percentages and intracellular ROS levels in T-cell subsets. The cell percentages and intracellular ROS levels in T-cell subsets were measured using flow cytometry, with both fluorescently labeled antibodies and the fluorescent reagents, carboxy-DCFDA and hydroethidine. The percentages of naïve CD4 + and CD8 + T cells decreased with increasing age and radiation dose, while the intracellular O 2 •- levels in central and effector memory CD8 + T cells increased. Additionally, when divided into three groups based on the percentages of naïve CD4 + T cells, intracellular O 2 •- levels of central and effector memory CD8 + T cells were significantly elevated with the lowest radiation dose group in the naïve CD4 + T cells. Thus, the radiation exposure-induced decrease in the naïve CD4 + T cell pool size may reflect decreased immune function, resulting in increased intracellular ROS levels in central and effector memory CD8 + T cells, and increased intracellular oxidative stress.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Flexible positioning of a large area detector using an industrial robot

The DIAD beamline for Dual Imaging and Diffraction at Diamond Light Source has opted to use an industrial robot to position its Dectris Pilatus 2M CdTe diffraction detector. This setup was chosen to enable flexible positioning of the detector in a quarter-sphere around the sample position whilst reliably holding the large weight of 139 kg of detector, detector mount and cabling in a stable position. Metrology measurements showed that the detector can be positioned with a linear repeatability of <19.7 µm and a rotational repeatability of <16.3 µrad. The detector position stays stable for a 12 h period with <10.1 µm of movement for linear displacement and <3.8 µrad for rotational displacement. X-ray diffraction from calibration samples confirmed that the robot is sufficiently stable to resolve lattice d-spacings within the instrumental broadening given by detector position and beam divergence.

36 MATERIALS SCIENCE↗

Report for the Corrosion Testing of Solutions to Aid in the Removal of 241-AP-106 Waste: Dilution Series Testing

Corrosion analyses were conducted at the 222-S Laboratory in support of proposed liquid waste removal from tank 241-AP-106 (AP-106) in preparation for its use in direct feed low activity waste treatment. The work reported here builds upon previous corrosion testing performed at the 222-S Laboratory that used a high-density caustic and an AP-106 tank waste sample. In this current study, a second liquid grab sample from AP-106 was diluted, 50:50 vol%, with raw water, and this dilution was repeated for a total of 5 dilutions steps. Following each dilution step, the resulting solution was tested for pitting corrosion using linear polarization resistance followed by cyclic potentiodynamic polarization.

241-AP-106↗

Radiological Characterisation of VLLW Produced at High-Energy Particle Accelerators - 19118

In this paper we describe the characterisation method of very-low-level radioactive waste (VLLW) produced at the European Organization for Nuclear Research (CERN). The method is based on the calculation of a preliminary radionuclide inventory using either analytical or Monte Carlo codes, on the measurement of γ-emitters and on the quantification of pure-α, pure-β and low-energy X-ray emitters, called difficult-to-measure (DTM) radionuclides, using the so-called scaling factor (SF) technique. The first stage of the characterisation process is the calculation of the radionuclide inventory, which is a list of radionuclides that can potentially be produced via the interaction of primary and secondary particles with the surrounding media. Once the preliminary radionuclide inventory is obtained, the γ-emitting radionuclides are measured via γ-ray spectrometry on each package of the waste population. The major γemitter, called key nuclide (KN), is also identified. The scaling factor method estimates the activity of DTM radionuclides by checking for a consistent and repeated relationship between the key nuclide and the activity of the difficult to measure radionuclides from samples. Between 2016 and 2018, several hundred samples were collected at CERN and over 1000 radiochemical analyses were performed to estimate robust statistics to quantify scaling factors for the most common DTM radionuclides, such as H-3, Fe-55 and Ni-63. This paper illustrates the sample collection strategy, the tests performed to choose the most appropriate statistical models describing the behaviour of scaling factors and a complete quantification of the uncertainties associated with the characterisation process. Finally, we present the results obtained during the characterisation of over 2000 m{sup 3} radioactive metals and cables disposed of at the French National repository for VLLW. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Investigating Soil Organic Matter Complexation using Spectral Induced Polarization

Spectral induced polarization (SIP) laboratory experiments were conducted to determine the sensitivity of this method to the formation of soil organic matter (SOM) complexes, with a long-term goal of field-scale monitoring. There are few SIP experiments that have explored this topic, yet understanding the dynamic behavior and interactions of SOM at the field scale could provide insight into soil fertility and health which influences crop yields, microorganisms that degrade organic pollutants, and carbon stabilization. We present the results of three experiments where the iron oxide, ferrihydrite (Fhy), was used to coat different media, and then the OM compound pentaglycine (PG) was pulse injected to form SOM complexes. SIP data was collected during these injections to capture any surface complexation changes. These experiments were performed in 1) a fluidic cell containing a micromodel, 2) a column containing Fhy coated ceramic beads and 3) a column containing Fhy coated Accusand®. Our results show a higher frequency response (defined here as > 1 Hz) in all three experiments, with the largest amplitude response after the first PG injection (Figure S.1). The repeatability of this response is encouraging and supporting data collected on the Accusand® experiment provides preliminary insight into the mechanisms controlling the SIP signatures. Sampling of fluid conductivity $σ_w$ and pH may indicate deprotonation of SOM occurring or rapid adsorption and release of protons from the Fhy sites. However additional experiments are needed to identify and confirm the primary and secondary reactions impacting the SIP response. We are looking towards other opportunities to continue this work, particularly to repeat experiments while collecting supporting datasets.

58 GEOSCIENCES↗

UNESE Argon-39 Measurement Techniques: Developing an above-ground Argon-39 Measurement Capability

The Underground Nuclear Explosion Signatures Experiment (UNESE) sought to use 37 Ar as a tracer for measuring noble-gas migration in the soil surrounding historic Underground Nuclear Explosions (UNE). One unexpected observation was the presence of the much longer-lived isotope 39 Ar from historic UNEs. Quantifying the activity of 39 Ar proved difficult due to the lack of capability to measure significantly-above-background levels of 39 Ar and a general discomfort to repeatedly expose Ultra-Low-Background Proportional Counters (ULBPCs) to significant radioactivity. Because the whole-air samples collected for the 37 Ar tracer measurement were already being measured on the above-ground argon capability, it was decided to expand that capability to include 39 Ar. This document describes the efforts required to achieve quantitative reporting of the 39 Ar backgrounds measured during experiments at the sites of the historic Barnwell and Disko Elm UNEs.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Analysis of liquid petroleum using a laser-induced breakdown spectroscopy instrument

Here, a prototype analyzer for the direct LIBS analysis of nebulized liquid samples was developed and tested, particularly for the analysis of petroleum, organic solvents and aqueous solutions. The LIBS analyzer requires about 750 µl of liquid sample, 1 liter of N 2 gas, and 10 s of the analysis time to record 100 spectra. The limits of detection in oil and solvent are as low as 0.01–0.04 ppm for Li, Mg, and Cu. They increase for the difficult elements, such as Pb and Hg (7-10 ppm), Cl (250 ppm), and S (~0.7%). The relative standard deviation of measuring 100 ppm vanadium in oil and solvent was 1.5%. The LIBS detection limits and repeatability are better than required by the standard method ASTM D5185 for the analysis of lubricating oils in ICP-OES. Several petroleum samples were analyzed by LIBS and the quantitative results for V, Ni, and Fe compared to the ICP-OES data. Light crude oils can be nebulized and analyzed directly. Medium crude oils require minimal dilution at least 1:1, otherwise errors of determination become large. Presumably, utilization of the internal standard and chemometrics can be useful to correct for the matrix effects. In addition to the trace element analysis, the LIBS prototype demonstrated ability to measure the hydrogen-to-carbon ratio in organic liquid samples. Several unidentified features were observed in the carbon spectrum. Their possible origin is discussed.

02 PETROLEUM↗