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At least 451 records · Page 25

Chemical abundances in Seyfert galaxies – Ⅸ. Helium abundance estimates

For the first time, the helium abundance relative to hydrogen (He/H), which relied on direct measurements of the electron temperature, has been derived in the narrow line regions (NLRs) from a local sample of Seyfert 2 nuclei. In view of this, optical emission line intensities [3000 < λ(Å) < 7000] of 65 local Seyfert 2 nuclei (z < 0.2), taken from Sloan Digital Sky Survey Data Release 15 and additional compilation from the literature, were considered. Here we used photoionization model grid to derive an Ionization Correction Factor (ICF) for the neutral helium. The application of this ICF indicates that the NLRs of Seyfert 2 present a neutral helium fraction of ~50 percent in relation to the total helium abundance. We find that Seyfert 2 nuclei present helium abundance ranging from 0.60 to 2.50 times the solar value, while ~85 percent of the sample present oversolar abundance values. The derived (He/H)–(O/H) abundance relation from the Seyfert 2 is stepper than that of star-forming regions (SFs) and this difference could be due to excess of helium injected into the interstellar medium by the winds of Wolf–Rayet stars. From a regression to zero metallicity, by using Seyfert 2 estimates combined with SFs estimates, we obtained a primordial helium mass fraction Y p = 0.2441 ± 0.0037, a value in good agreement with the one inferred from the temperature fluctuations of the cosmic microwave background by the Planck Collaboration, i.e. $Y_{p}^{Planck}$ =0.2471 ± 0.0003.

79 ASTRONOMY AND ASTROPHYSICS↗

No detectable redox exchange between sulfur and iron during rapid cooling of basalts

The valence states of iron and sulfur in mantle-derived melts influence and respond to the composition of the mantle as well as the subsequent evolution of those melts in Earth's crust. Characterizing the valence states of iron and sulfur in silicate melts that have quenched to form glasses is therefore critical to understanding the composition of the mantle and the magmatic processes that take place before and during volcanic eruptions. Glasses quenched from silicate melts offer the opportunity to precisely measure sulfur and iron valence states, but whether the transition from melt to glass affects the valence state of sulfur and iron is uncertain. Here, we use the glassy margins of two pillow basalts, one from a mid-ocean ridge and one from a back-arc basin, as a natural experiment to test the effect of quench rate on sulfur and iron valence states. We report micro-X-ray Absorption Near Edge Structure (XANES) measurements of S 6+ /ΣS (S 6+ /[S 6+ +S 2- ]) and Fe 3+ /ΣFe (Fe 3+ /[Fe 2+ +Fe 3+ ]) along transects from the rapidly quenched rims of the pillows down into the slowly cooled crystal-rich interiors. The range of average quench rates estimated for our selected analysis areas range from 1.2 x 10 5 °C/sec at the pillow margin to 1.1 °C/sec in the interior and span quench rates experienced by natural and experimental glasses. On average, S6+/ΣS = 0.09 ± 0.01 and Fe 3+ /ΣFe = 0.147 ± 0.002 in the mid-ocean ridge sample and S 6+ /ΣS = 0.21 ± 0.01and Fe 3+ /ΣFe = 0.153 ± 0.004 in the back-arc sample, where the quoted uncertainty is the 1σ standard deviation of n= 9-16 analyses. We find that the S 6+ /ΣS and Fe 3+ /ΣFe values along transects in each sample show no systematic changes with depth, and by proxy, no systematic changes with quench rate. In each pillow, all measured S 6+ /ΣS and Fe 3+ /ΣFe ratios are within the absolute uncertainty of each technique. We propose that these observations are consistent with either sluggish reaction kinetics between sulfur and iron, or an insignificant temperature effect on sulfur-iron redox exchange equilibria. These observations demonstrate that sulfur and iron valence states in glasses with varying quench rates can be directly compared, and that changes in sulfur and iron valence during quench are below the limits of detection with XANES.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measured CO 2 sorption isotherms with 25 Bakken Petroleum System rock samples from the Lower and Upper Shales, Middle Bakken, and Three Forks formations

Isotherms were measured with 25 Bakken Petroleum System (BPS) rock samples using a magnetic suspension balance at reservoir conditions of 110 °C and pressures up to 345 bar. Samples from four wells represented the Middle Bakken (MB) and Three Forks (TF) production zones, and the Upper Bakken Shale (UBS) and Lower Bakken Shale (LBS) source shales. UBS and LBS CO 2 sorption capacities at 345 bar averaged 12–14 g/kg rock compared to 1.3 to 2.5 g/kg rock for MB and TF. Increasing pressure from 150 to 345 bar resulted in only small increases in CO 2 sorption for all lithofacies. For the UBS and LBS source shales, the higher average total organic carbon (TOC) values (14.7 and 11.4 wt.%) and clay values (25 and 28 wt.%) corresponded to their higher CO 2 sorption values while for the MB and TF samples, lower TOCs (0.3 and 0.5 wt.%) and clay values (8.2 and 18.2 wt.%) corresponded to lower CO 2 sorption values. Here, when all 25 samples (from all lithofacies) were evaluated as a group, sorption capacities were highly correlated with TOC (Spearman's rho values +0.84 to +0.85), with rock density (rho values -0.75 to -0.76), and clay content (rho values +0.66). However, correlations with porosity and thermal maturity (Tmax) were weak. Measured sorption capacities and rock porosities showed that sorption accounted for about 10-times as much CO 2 storage as the available pore space for the UBS and LBS lithofacies. In contrast, the pore space dominated the storage resource of the TF and MB lithofacies.

54 ENVIRONMENTAL SCIENCES↗

Arctic Permafrost Thawing Enhances Sulfide Oxidation

Permafrost degradation is altering biogeochemical processes throughout the Arctic. Thaw-induced changes in organic matter transformations and mineral weathering reactions are impacting fluxes of inorganic carbon (IC) and alkalinity (ALK) in Arctic rivers. However, the net impact of these changing fluxes on the concentration of carbon dioxide in the atmosphere (pCO 2 ) is relatively unconstrained. Resolving this uncertainty is important as thaw-driven changes in the fluxes of IC and ALK could produce feedbacks in the global carbon cycle. Enhanced production of sulfuric acid through sulfide oxidation is particularly poorly quantified despite its potential to remove ALK from the ocean-atmosphere system and increase pCO 2 , producing a positive feedback leading to more warming and permafrost degradation. In this work, we quantified weathering in the Koyukuk River, a major tributary of the Yukon River draining discontinuous permafrost in central Alaska, based on water and sediment samples collected near the village of Huslia in summer 2018. Using measurements of major ion abundances and sulfate (SO 4 2- ) sulfur ( 34 S/ 32 S) and oxygen ( 18 O/ 16 O) isotope ratios, we employed the MEANDIR inversion model to quantify the relative importance of a suite of weathering processes and their net impact on pCO 2 . Calculations found that approximately 80% of SO 4 2- in mainstem samples derived from sulfide oxidation with the remainder from evaporite dissolution. Moreover, 34 S/ 32 S ratios, 13 C/ 12 C ratios of dissolved IC, and sulfur X-ray absorption spectra of mainstem, secondary channel, and floodplain pore fluid and sediment samples revealed modest degrees of microbial sulfate reduction within the floodplain. Weathering fluxes of ALK and IC result in lower values of pCO 2 over timescales shorter than carbonate compensation (~10 4 yr) and, for mainstem samples, higher values of pCO 2 over timescales longer than carbonate compensation but shorter than the residence time of marine (~10 7 yr). Furthermore, the absolute concentrations of and Mg 2+ in the Koyukuk River, as well as the ratios of SO 4 2- and Mg 2+ to other dissolved weathering products, have increased over the past 50 years. Through analogy to similar trends in the Yukon River, we interpret these changes as reflecting enhanced sulfide oxidation due to ongoing exposure of previously frozen sediment and changes in the contributions of shallow and deep flow paths to the active channel. Overall, these findings confirm that sulfide oxidation is a substantial outcome of permafrost degradation and that the sulfur cycle responds to permafrost thaw with a timescale-dependent feedback on warming.

54 ENVIRONMENTAL SCIENCES↗

The imprint of cosmic voids from the DESI Legacy Survey DR9 Luminous Red Galaxies in the Planck 2018 lensing map through spectroscopically calibrated mocks

The cross-correlation of cosmic voids with the lensing convergence (κ) map of the Cosmic Microwave Background (CMB) fluctuations provides a powerful tool to refine our understanding of the current cosmological model. However, several studies have reported a moderate tension (up to ∼2σ) between the lensing imprint of cosmic voids on the observed CMB and the ΛCDM signal predicted by simulations. To address this “lensing-is-low” tension and to obtain new, precise measurements of the signal, we exploit the large DESI Legacy Survey Luminous Red Galaxy (LRG) data set, covering approximately 19 500 deg 2 of the sky and including about 10 million LRGs at z < 1.05. Our ΛCDM template was created using the Buzzard mocks, which we specifically calibrated to match the clustering properties of the observed galaxy sample by exploiting more than one million DESI spectra. We identified our catalogs of 3D voids in the range 0.35 < z < 0.95 and cross-correlated them through a stacking methodology, dividing the sample into bins according to the redshift and λv values of the voids. For the full void sample, we report a 14σ detection of the lensing signal, with A κ = 1.016 ± 0.054, which increases to 17σ when considering the void-in-void (A κ = 0.944 ± 0.064) and the void-in-cloud (A κ = 0.975 ± 0.060) populations individually, the highest detection significance for studies of this kind. We observe a full agreement between observations and ΛCDM mocks across all redshift bins, sky regions, and void populations considered. In addition to these findings, our analysis highlights the importance of accurately matching sparseness and redshift error distributions between mocks and observations, as well as the role of λ v in enhancing the signal-to-noise ratio through void population discrimination.

79 ASTRONOMY AND ASTROPHYSICS↗

Low encounter speed comet COMA sample return missions

Comets, being considered the most primitive bodies in the solar system, command the highest priority among solar-system objects for studying solar nebula evolution and the evolution of life through biogenic elements and compounds. The study of comets, and more especially, of material from them, provides an understanding of the physical, chemical, and mineralogical processes operative in the formation and earliest development of the solar systems. These return samples will provide valuable information on comets and serve as a rosetta stone for the analytical studies conducted on interplanetary dust particles over the past two decades, and will provide much needed extraterrestrial samples for the planetary materials community since the Apollo program. Lander sample return missions require rather complex spacecraft, intricate operations, and costly propulsion systems. By contrast, it is possible to take a highly simplified approach for sample capture and return in the case of a comet. In the past, we have considered Earth free-return trajectory to the comet, in which passive collectors intercept dust and volatiles from the cometary coma. However, standard short period cometary free-return trajectories results in the comet to the spacecraft encounter speeds in the range of 10 km/s. At these speeds the kinetic energy of the capture process can render significant modification of dust structure, change of solid phase as well as the lost of volatiles components. This paper presents a class of new missions with trajectories with significant reduction of encounter speeds by incorporating gravity assists and deep space maneuvering. Low encounter speed cometary flyby sample return will enable a marked increase in the value of the return science. Acquiring thousands of samples from a known comet and thousands of images of a comet nucleus would be space firsts. Applying new approach in flight mechanics to generate a new class of low encounter speed cometary sample return trajectories opens new possibilities in science. A systematic search of trajectories for the first decade of the twenty-first century will be made. The target encounter speed is for less than 7 km/s to short period comets.

Tsou, P.↗

Simultaneous in situ electron temperature comparisons using Alouette 2 probe and plasma resonance data

The electron temperatures deduced from Alouette 2 diffuse resonance observations are compared with the temperature obtained from the Alouette 2 cylindrical electrostatic probe experiment using data from 5 mid-to-high latitude telemetry stations. The probe temperature is consistently higher than the diffuse resonance temperature. The average difference ranged from approximately 10% to 40% with the lower values occurring at the lowest altitudes sampled (near 500 km) and at high latitudes (dip latitude greater than 55 deg), and the larger values occurring at high altitudes and lower latitudes. The discrepancy appears to be of geophysical origin since it is dependent on the location of the data sample. The present observations support the view that the often observed radar backscatter - probe electron temperature discrepancy is also of geophysical origin.

Benson, R. F.↗

Simultaneous in situ electron temperature comparison of Alouette 2 probe and plasma resonance data.

The electron temperatures deduced from Alouette 2 diffuse resonance observations are compared with the temperatures obtained from the Alouette 2 cylindrical electrostatic probe experiment using data from five mid- to high-latitude telemetry stations. The probe temperature is consistently higher than the diffuse resonance temperature. The average difference ranged from approximately 10% to 40%, the lower values occurring at the lowest altitudes sampled (near 500 km) and at high latitudes (dip latitude greater than 55 deg) and the larger values occurring at higher altitudes and lower latitudes. The discrepancy appears to be of geophysical origin, since it is dependent on the location of the data sample. These observations support the view that the discrepancy often observed between radar backscatter and probe electron temperature is of geophysical origin.

Benson, R. F.↗

Post-flight characterization of optical system samples, thermal control samples, and detectors from LDEF experiment M0003, sub-experiments 6 and 13

Flight samples and control samples of optical and thermal control coatings were measured for hemispheric reflectance and transmission. The samples were exposed directly to the orbital environment, but were on the trailing edge of the LDEF satellite. Preliminary analysis shows no significant change in the reflectance of transmission values of most of the samples. Post-flight tests of avalanche photodiodes is also discussed.

Hodgson, Randall R.↗

The oxygen stable isotope composition of CRM 125-A UO 2 standard reference material

While there is a clear need for standardized reference materials for analytical calibrations and for inter-laboratory comparisons, there are not currently any for the oxygen stable isotopic composition of uranium oxides. In this paper we summarize the results from four laboratories by seven different methods of oxygen stable isotope analyses using fluorination techniques of CRM 125-A UO 2 Standard Reference Material. We synthesize these data and methods to arrive at a consensus oxygen stable isotope composition for CRM 125-A $δ$ 18 O = -9.63‰ (±0.29‰) VSMOW. We discuss methodological differences between analytical approaches, including furnace vs laser heating, fluorination using BrF 5 or ClF 3 , as well as calibration strategies. We highlight the potential effects of calibration scale compression from single-point calibrations using reference material with $δ$ 18 O values having a large relative difference from the sample being analyzed. We demonstrate how calibration scale compression can yield differences in calibrated $δ$ 18 O values up to ~2‰ for samples with ~20‰ difference from a single reference material, if the calibration slope of different analytical systems differs by 0.1. In conclusion, we suggest the use of liquid water calibration standards sealed in silver capillary tubes for multi-point calibrations of fluorination analysis systems.

07 ISOTOPE AND RADIATION SOURCES↗

Two Polymorphs of BaZn 2 P 2 : Crystal Structures, Phase Transition, and Transport Properties

Here, the novel α-BaZn 2 P 2 structural polymorph has been synthesized and structurally characterized for the first time. Its structure, elu-cidated from single crystal X-ray diffraction, indicates that the compound crystallizes in the orthorhombic α-BaCu 2 S 2 structure type, with unit cell parameters a = 9.7567(14) Å, b = 4.1266(6) Å, and c = 10.6000(15) Å. With β-BaZn 2 P 2 being previously iden-tified as belonging to the ThCr 2 Si 2 family, and with the precedent of structural phase transitions between the α-BaCu 2 S 2 type and the ThCr 2 Si 2 type, the potential for the pattern to be extended to the two different structural forms of BaZn 2 P 2 was explored. Thermal analysis suggest that a first order phase transition occurs at ~1123 K, whereby the low-temperature orthorhombic α-phase transforms to a high-temperature tetragonal β-BaZn 2 P 2 ; the structure of which was also studied and confirmed by single-crystal X-ray diffraction. Preliminary transport properties and band structure calculations indicate that α-BaZn 2 P 2 is a p-type, narrow-gap semiconductor with a direct bandgap (Eg) of 0.5 eV. The Seebeck coefficient, S(T), for the material increases steadily from the room temperature value of 119 µV/K to 184 µV/K at 600 K. The electrical resistivity of α-BaZn 2 P 2 is relatively high, on the order of 40 mΩ·cm, and the ρ(T) dependence shows gradual decrease upon heating. Such behavior is comparable to those of the typical semimetals or degenerate semiconductors. Although the observed values of the as-synthesized samples are not optimal, the carrier concentration can apparently be tuned to fall between the values of metals and semiconductors, thus providing an open window for optimizing this phase towards achieving an enhanced thermoelectric figure of merit zT. The calculated indirect band gap for the β-BaZn 2 P 2 phase is Eg = 0.03 eV which is about an order of magnitude lower than that of α-BaZn 2 P 2 . It is expected that the cage-like structural motif and layered structure possessed by α-BaZn 2 P 2 and β-BaZn 2 P 2 phases, respectively, would promote the realiza-tion of a low thermal conductivity in both compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of a Layered Morphology on Drip Suppression in Burning Polymers

Fire safety in polymers is critically important with products such as textiles and consumer goods, as well as materials used in construction, aerospace, transportation, and furniture. Additives used as anti-dripping and flame-retardant agents impose acute human health issues and have negative environmental impacts. With a focus on developing additive-free solutions, here we used multilayer coextrusion to fabricate layered polyethylene/polypropylene (PE/PP) films and investigated the effect of a layered morphology on dripping and burning rates. The experimental results for multilayered PE/PP samples were compared to control groups of melt blended PE/PP samples. The multilayer configuration provides two significant advantages: 154% delay in the time to the first drip and up to 87% reduction in the number of drips compared to the value for the melt blended samples with no additives. PE/PP blends with up to 2 wt % polytetrafluoroethylene, a commonly used anti-dripping agent in the industry, showed only 85% delay in the time to the first drip and about 60% reduction in the number of drips. We discovered a linear relationship between film thickness and burning rate, which allows for the use of the volumetric burning rate to normalize the effect of film thickness. No benefit in the burning rate was observed when comparing multilayered structures and conventional melt blended architectures or blends with PTFE. Annealing studies and transmission electron microscopy at areas close to the combustion zones confirmed that higher extensional viscosities induced by the layered structures and morphological changes due to the layer breakup play an important role in reducing dripping. By combining the first drip time and overall drip numbers, a parameter, “dripping index”, was defined to establish a fire safety map to simplify material comparisons. This study demonstrates that a multilayer film geometry can provide an additive-free solution to yield control over fire safety parameters in polymers.

36 MATERIALS SCIENCE↗

Surface emissivity of a reinforced carbon composite material with an oxidation-inhibiting coating

Total effective emissivity and spectral emissivity over the wavelength range of 0.65 to 6.3 microns were determined for temperatures from 1300 t0 2250 deg K. A multi channel radiometer was used in the arcjet and laboratory tests. The black-body-hole method was used to independently check radiometer results. The results show the silicon-carbide coated reinforced carbon composite material is a nongray radiator. The total effective emissivity and the spectral emissivity at 0.65 micron both decreased with increasing temperature, respectively, from approximately 0.8 to 0.6, and from 0.4 to 0.25, over the temperature range. The emissivity values were the same when the sample was viewed normal to the surface or at a 45 deg angle. Recommended emissivity values are presented.

Wakefield, R. M.↗

The effects of terrestrial weathering on samarium-neodymium isotopic composition of ordinary chondrites

Following their fall to Earth, meteorites experience weathering. In this systematic study, we evaluate the trace element composition of ordinary chondrites from the Antarctic cold desert, and Atacama (Chile) and Lut (Iran) hot deserts, with an emphasis on rare earth elements (REE). Our data confirms that terrestrial weathering of meteorites in hot deserts changes their trace element (Sr, Ba, REE, Hf, Th, and U) concentrations. However, weathering effects in majority of Antarctic samples are limited to slight Ba, REE, Hf, and Th depletions and in some case to U enrichment. In comparison to the Antarctic meteorites, hot desert samples show greater disturbances and REE fractionation relative to the average fall values. We measured the Sm-Nd isotopic composition of the hot desert meteorites that have heavily affected REE compositions. Our Sm-Nd isotopic data show a significant effect of terrestrial weathering evidenced by non-CHUR (147)Sm/(144)Nd and (143)Nd/(144)Nd ratios. Measurements show a higher variation and lower values of (147)Sm/(144)Nd for the Atacama samples than those from the Lut Desert. Deviations from CHUR (147)Sm/(144)Nd value are in positive accordance with the degree of La/Lu fractionation caused by weathering. The ɛNd values of Atacama and Lut deserts meteorites range from −2.20 to +1.61, which is wider than the −1.07 to +0.64 range for falls. We suggest that disturbance of primary Sm/Nd ratios resulting from mixing with terrestrial components originating from soil during weathering is responsible for lower (147)Sm/(144)Nd ratio in these meteorites. The majority of the Atacama meteorites regardless of their weathering degrees have their REE compositions and ɛNd affected by terrestrial contamination. Both (147)Sm/(144)Nd ratio and ɛNd values show no straightforward relationship with weathering degree. However, in both cases the samples with the highest negative isotopic disturbances are H chondrites from the Atacama and Lut deserts. In addition, Ba concentration shows a negative correlation with (147)Sm/(144)Nd ratio. Care must be taken into account while dealing with samples collected from hot deserts, even fresh-looking ones.

Isotope geochemistry↗

Correlation function distributions for O ( N ) lattice field theories in the disordered phase

Numerical computations in strongly interacting quantum field theories are often performed using Monte Carlo sampling methods. A key task in these calculations is to estimate the value of a given physical quantity from the distribution of stochastic samples that are generated using the Monte Carlo method. Typically, the sample mean and sample variance are used to define the expectation values and uncertainties of computed quantities. However, the Monte Carlo sample distribution contains more information than these basic properties, and it is useful to investigate it more generally. In this work, the exact form of the probability distributions of two-point correlation functions at zero momentum in O ( N ) lattice field theories in the disordered phase and in infinite volume are determined. These distributions allow for a robust investigation of the efficacy of the Monte Carlo sampling procedure and are shown also to allow for improved estimators of the target physical quantity to be constructed. The theoretical expectations are shown to agree with numerical calculations in the O ( 2 ) model. Published by the American Physical Society 2024

Astronomy & Astrophysics↗

DSP Implementation of a Novel Recurrent Neural Network Controller into a TI Solar Microinverter

Single-phase grid-tied inverters are widely used to integrate small-scale renewable energy sources and distributed generations to the utility grid. A novel Recurrent Neural Network (RNN) current controller is introduced to solve the resonant problem associated with LCL based inverters. The well-trained RNN controller was validated through a Texas Instruments (TI) LCL filter based solar microinverter kit that contains a C2000 TI microcontroller. The inverter closed current loop test without the grid connection was conducted in a laboratory setup to verify the RNN contoller functionality. The laboratory waveform results verified that the RNN current controller produced the strong tracking of the measured inverter AC current to its reference value even at a low sampling frequency of 5KHz. The proposed RNN current controller also proved to perform better than the built-in three-pole-three-zero (3P3Z) current controller provided by TI and produce lower values of Total Harmonic Distortion (THD).

digital signal processor↗

A Comparison of Groundwater Sampling Technologies, Including Passive Diffusion Sampling, for Radionuclide Contamination - 20205

Using traditional high-flow purge methods for long-term water quality monitoring of deep groundwater wells can be expensive, affect contaminant migration, and produce excessive volumes of discharge water that can be difficult to manage. The use of low-flow pumping methods and depth discrete bailers (DDBs) can reduce the cost of sampling deep groundwater wells. In general, using different pumping methods to obtain reproducible and representative groundwater can be challenging. Passive diffusion samplers (PDSs) have successfully been used in long-term monitoring for volatile organic compounds, major ions, and trace-elements, but application has been limited for stable and radioactive isotopes. Beginning in 2018, the United States Geological Survey (USGS) conducted three sampling events to test the ability of PDSs and DDBs to obtain reproducible and representative groundwater samples. The sampled well is completed in a regional, permeable carbonate aquifer and is one in a set of wells that have historically been used for tritium tracer testing. All samples were obtained at 180 m (590 ft) below land surface (bls) in a 13.97 cm (5.5 inch) uncased well that has a total depth of 202 m (662 ft) bls. The first sampling event deployed a regenerated cellulose dialysis membrane (RCDM) PDS for 14 days with deionized water as the blank. The second sampling event deployed a RCDM for 27 days also with deionized water as the blank. The third sampling event deployed a Dual Membrane (DM) PDS for 65 days using a blank of tritium-dead carbonate water. The DM PDS was used to assess the effect of longer term deployment on tritium concentrations and address whether or not the PDSs reached equilibrium with ambient groundwater. The day after each of the three passive samplers were retrieved a DDB was used to obtain discrete non-integrated groundwater samples. For each DDB sampling day, the bailer was lowered into the well 10 consecutive times to determine if the water chemistry changed from the first to the last bailed sample. Quality assurance samples including blanks and duplicates were obtained during all three sampling events. All blank waters had tritium concentrations less than 21±33 pCi/L. Major ion (e.g. calcium, chloride, sodium, and sulfate) results were compared between all samples obtained with RCDM and DDB. Major ion concentrations showed a coefficient of variation of less than 6% between all RCDM and DDB samples; however, the coefficient of variation between the different deployment times and the two different methods for trace-element concentrations was much larger, particularly for manganese (82%), lead (41%), and zinc (33%). Stable isotope values were compared between the RCDM and DDB samples. The DDB sample results all fell within analytical uncertainty and were considered representative of the formation groundwater. The stable isotope values from the RCDM samples indicated that a longer deployment time was necessary to gain equilibrium and to obtain representative groundwater samples. Tritium results from groundwater samples obtained from the RCDM, DM, and DDB indicate that groundwaters obtained with PDSs produced tritium concentrations 2 to 3 times higher (between 1,426 and 3,060±87 pCi/L) than groundwaters obtained with a DDB (479 to 1,219±51 pCi/L). The longer the passive diffusion samplers were deployed, the higher the tritium concentration, suggesting that equilibrium with tritium was not reached within a 27-day deployment. DDB samples showed tritium results declining from the first to the last bailed sample for all three sampling events. This research suggests that tritium results from groundwater samples obtained from PDSs are more reproducible than samples obtained from DDBs. Also, PDSs likely do not accumulate isotopes of water but rather equilibrate with the ambient groundwater. On the other hand, both PDSs and DDBs were able to provide representative groundwater samples for major ions and have the potential to produce representative groundwater samples for stable isotopes of water (δD and δ{sup 18}O). Utilizing the most effective method for sampling groundwater is important for long-term groundwater monitoring. Quantifying the ability of passive diffusion groundwater samplers to obtain representative radioactive chemistry samples will help determine if these methods can be a useful alternative to pumping and purging wells for long-term monitoring. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Salt Vessel-Sample Generator Interface

The goal of the salt sampling program at Argonne is to develop and deploy automated molten salt sampling approaches for interfacing relevant unit operations with salt analysis to improve the timeliness and accuracy of sampling-based accountancy measurements. One technology under development is a vacuum sampler loop module. In this system, molten salt is drawn from a process vessel through a heated sampling line and into a charge vessel. Next, one or more samples are split from the volume in the charge vessel and the remaining salt is returned to the process. The vacuum sampler loop module is being developed to interface with other sample processing and analysis modules to enable rapid at-line sample characterization. The main purpose of the vacuum sampling loop module is to enable the collection of samples that are more representative of the bulk salt by replacing traditional point samplers (i.e., dip probes) with a sampling approach that captures a larger cross section of salt. Additionally, the vacuum sampling approach eliminates the risk of dross contamination of samples and avoids the use of moving parts in the salt. Two methods of interfacing the vacuum sampling loop with a precision pneumatic sample generator were investigated in FY21. This report covers the testing of fluidic coupling between the two modules. Two iterations of the fluidically coupled modules were tested. The first iteration system coupled the two modules using a freeze valve to seal the vacuum sampler during filling and to control flow into the pneumatic sample generator. While this integrated system functioned as intended, some changes were implemented to make the system more robust and better suited to remote deployment. Specifically, the system was made to be more modular and active control of the vacuum filling operation was replaced with a passive control mechanism. For passive filling, the salt charge vessel was vented to a small gas tank that was at negative pressure, causing salt to be drawn into the vessel until the force of the fluid head was in equilibrium with the gas pressure. The passive control system performed well and will be used in future iterations. Another change in the second system was a newly configured pneumatic sample generator in which sample ejection occurred through a hole in the reservoir’s stainless-steel side wall instead of through a non-wetted sapphire orifice on the bottom. This alternate configuration may be better suited for near-process deployment because it enables on-line orifice maintenance and an orifice bypass drain back to the process. A third change in the second iteration system was the transition to a two-chamber charge vessel which split off a fraction of the sampled salt as a liquid aliquot. The goal was to create a buffer mechanism that would allow reproducible aliquoting of samples, independently of variability in the charge vessel fill height. While the two-chamber design was functional, the sample size reproducibility was below target values. To improve reproducibility and overcome many of the impediments to remote deployment of the vacuum sampling loop module, separate work was conducted to replace the two-chamber liquid aliquoting mechanism with aliquoting into single-use sample tubes. Solid salt transfer in the sample tubes will replace fluidic coupling for integrating the vacuum sampler with downstream modules. Because the proposed operations can all be executed with simple overhead actuation mechanisms or other existing hot-cell technology, there will be no need for large investments in novel hot cell sample handling technologies using this alternate approach. As such, near-term deployment of the vacuum sampling technology will be achievable. This new approach for automated coupling of sample tubes with down-stream modules is covered in a separate FY21 report, and a remotely operated version of the vacuum sampler loop module with the tube aliquoting feature is planned for FY22.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗