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At least 19 records

$\beta $ Decays of $^{92}$Rb, $^{96\mathrm {gs}}$Y, and $^{142}$Cs Measured with the Modular Total Absorption Spectrometer and the Influence of $\gamma $ Multiplicity on Total Absorption Spectrometry Measurements

Total absorption spectroscopy is a technique that helps obtain reliable β-feeding patterns of complex decays important for nuclear structure and astrophysics modeling as well as decay heat analysis in nuclear reactors. The need for improved measurements of β-feeding patterns from fission decay products has come to the forefront of experiments that use nuclear reactors as a source of antineutrinos. Furthermore we present more detailed results, in particular the β-decay measurements of 96gs Y, and demonstrate the impact of the β-delayed γ multiplicity on the overall efficiency of Modular Total Absorption Spectrometer used at Oak Ridge National Laboratory to study the decays of fission products abundant during a nuclear fuel cycle.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The nonlinear light output of NaI(Tl) detectors in the Modular Total Absorption Spectrometer

New detector array, the Modular Total Absorption Spectrometer (MTAS),was commissioned at the Holifield Radioactive Ion Beam Facility (HRIBF) at Oak Ridge National Lab(ORNL).Total absorption gamma spectra measured with MTAS are expected to improve beta-feeding patterns and beta strength functions in fission products.MTAS is constructed out of hexagonal NaI(Tl) detectors with a unique central module surrounded by 18 identical crystals assembled in three rings. The total NaI(Tl) mass of MTAS is over1000 kg.The response of the central and other 18 MTAS modules to -radiation was simulated using the GEANT4 tool kit modified to analyze the nonlinear light output of NaI(Tl).A detailed description oftheGEANT4modifications madeisdiscussed.SimulatedenergyresolutionofMTAS modules is found to agree well with the measurements for single transitions of 662keV (137Cs) with 8.2% full width half maximum (FWHM),835keV (54Mn) with FWHM of 7.5% FWHM, and 1115keV (65Zn) with FWHM of 6.5%.Simulations of single and multiple -rays from 60Co are also discussed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Modular total absorption spectrometer

The design and performance of the Modular Total Absorption Spectrometer built and commissioned at the Oak Ridge National Laboratory is presented here. The active volume of the detector is approximately one ton of NaI(Tl), which results in very high full γ energy peak efficiency of 71% at 6 MeV and nearly flat efficiency of around 81.5% for low energy γ-rays between 300 keV and 1 MeV. In addition to the high peak efficiency, the modular construction of the detector permits the use of a γ-coincidence technique in data analysis as well as β-delayed neutron observation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Determination of arsenic species in edible periwinkles (Littorina littorea) by HPLC-ICPMS and XAS along a contamination gradient

Arsenic is naturally found in the tissues of marine animals, usually as the non-toxic arsenical arsenobetaine, but exposure to elevated arsenic concentrations in the environment may alter the arsenic species distribution within tissues of the organism. This study examined the arsenic species in the tissues of the marine periwinkle (Littorina littorea) along an arsenic concentration gradient in the sediment. The arsenicals in L. littorea were examined using the complementary analytical methods high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC–ICPMS) and X-ray absorption spectroscopy (XAS). Total arsenic concentrations in the periwinkle tissues ranged from 56 to 840 mg · kg -1 dry weight (equivalent to 13 to 190 mg · kg -1 wet weight). Inorganic arsenicals were found to be positively correlated with total arsenic concentrations (R 2 = 0.993) and reached 600 mg · kg -1 dry weight, the highest reported to date in marine organisms. These high inorganic arsenic concentrations within this low trophic organism pose a potential toxicological risk to higher trophic consumers.

Whaley-Martin, K. J.↗

Extreme Ultraviolet and Beyond Extreme Ultraviolet Lithography Using Amorphous Zeolitic Imidazolate Resists Deposited by Atomic/Molecular Layer Deposition

Amorphous zinc-imidazolate (aZnMIm) resists show potential to meet the demands for next-generation high-numerical aperture (high-NA) metal-containing extreme ultraviolet (EUV) resist materials, given their ease of deposition by atomic/molecular layer deposition (ALD/MLD) at thicknesses of 20 nm and below. Here, this study demonstrates that aZnMIm thin films, previously identified as high-resolution electron beam resists, can also function as negative-tone EUV photoresists. Water development achieves high sensitivity (5 mJ/cm 2 ) but leaves significant residue, while acetic acid development results in poor contrast. A hybrid approach─water followed by acetic acid─enables residue-free development with a sensitivity of 181 mJ/cm 2 . Dry development using 1,1,1,5,5,5-hexafluoroacetylacetone (hfacH) is also possible but shows lower sensitivity (375 mJ/cm 2 ) compared to wet development methods. EUV photoelectron spectroscopy (PES), reflectometry/EUV absorption, total electron yield (TEY), residual gas analysis (RGA), and time-of-flight secondary ion mass spectrometry (TOF-SIMS) were used to investigate the effects of EUV irradiation on aZnMIm resists. Reflectometry experiments reveal an aZnMIm EUV absorption coefficient of 6.2 μm –1 , while PES and TEY analyses show that, compared to poly(4-hydroxystyrene) (PHS), a polymer-based reference resist, aZnMIm emits more primary and secondary electrons but generates fewer slow electrons relative to its primary electron emission; its total electron yield is similar to that of poly(methyl methacrylate) (PMMA) resists. When exposed to EUV, aZnMIm predominantly outgasses H 2 , as determined by RGA. TOF-SIMS measurements demonstrate that high-dose EUV exposure only partially fragments the 2-methylimidazole (2MIm) organic linkers, unlike high-dose electron beam exposure, which is known to completely degrade them. Additionally, aZnMIm resists show promise for potential beyond EUV lithography (BEUVL) due to the presence of Zn, which provides higher sensitivity at a wavelength of 6.7 nm compared to other metal ions, such as Sn, that are currently used in the best-performing EUV metal–organic resists. TEY measurements demonstrate that aZnMIm emits nearly twice as many electrons as PHS at 6.7 nm. The BEUV TEY of aZnMIm also surpasses that of PMMA, poly(pentafluorostyrene), and poly(4-iodostyrene), with the latter two being known for their high EUV TEYs. This work provides insight into zeolitic imidazolate framework (ZIF)-based EUV and BEUV resists and highlights their potential for both wet and dry development.

lithography↗

Modular multi-interface nanocrystals for enhanced ethanol oxidation electrocatalysis

Electrochemical processes that utilize biomass-derived ethanol as a source of electrons and protons offer a sustainable energy strategy, yet their practical implementation is limited by sluggish ethanol oxidation reaction (EOR) kinetics and catalyst poisoning. Here, in this study, we report a modular multi-interface nanocrystal catalyst comprising core/shell Co 2 P/Pd and Pd-Au heterostructured interfaces that exhibit complementary functions for the enhanced EOR catalysis. The Co 2 P/Pd interface boosts Pd atom utilization and lowers the kinetic barriers for ethanol-to-acetate conversion, while the Pd-Au interface effectively alleviates CO poisoning caused by C–C bond cleavage of ethanol. In-depth analyses using in situ attenuated total reflectance-surface-enhanced infrared absorption spectroscopy, differential electrochemical mass spectrometry, and density functional theory calculations elucidate the mechanistic roles of these interfaces. The optimized Co 2 P/Pd-Au 0.08 nanorods achieve an excellent mass activity, underscoring the potential of modular, multi-interface nanocrystals for advancing EOR catalysis and offering a generalizable strategy for broader catalytic innovations.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Exposure to mercury among Spanish preschool children: Trend from birth to age four

The purpose of this study is to describe the total hair mercury concentrations and their determinants in preschool Spanish children, as well as to explore the trend in mercury exposure from birth to the age four. This evolution has been scarcely studied in other birth cohort studies. The study population was 580 four year old children participating in the INMA (i.e. Childhood and Environment) birth cohort study in Valencia (2008–2009). Total mercury concentration at age four was measured in hair samples by atomic absorption spectrometry. Fish consumption and other covariates were obtained by questionnaire. Multivariate linear regression models were conducted in order to explore the association between mercury exposure and fish consumption, socio-demographic characteristics and prenatal exposure to mercury. The geometric mean was 1.10 µg/g (95%CI: 1.02, 1.19). Nineteen percent of children had mercury concentrations above the equivalent to the Provisional Tolerable Weekly Intake proposed by WHO. Mercury concentration was associated with increasing maternal age, fish consumption and cord blood mercury levels, as well as decreasing parity. Children whose mothers worked had higher mercury levels than those with non working mothers. Swordfish, lean fish and canned fish were the fish categories most associated with hair mercury concentrations. We observed a decreasing trend in mercury concentrations between birth and age four. In conclusion, the children participating in this study had high hair mercury concentrations compared to reported studies on children from other European countries and similar to other countries with high fish consumption. The INMA study design allows the evaluation of the exposure to mercury longitudinally and enables this information to be used for biomonitoring purposes and dietary recommendations. - Highlights: • The geometric mean of hair Hg concentrations was 1.10 µg/g. • 19% of children had Hg concentrations above the RfD proposed by the WHO. • Hair Hg concentrations in children increased as a function of total fish intake. • Swordfish, lean fish and canned fish were the most related to Hg concentrations. • There was a decrease in Hg concentrations from birth to age four.

54 ENVIRONMENTAL SCIENCES↗

Towards a mechanistic understanding of the sol–gel syntheses of ternary carbides

Sol–gel chemistry, while being extremely established, is to this day not fully understood, and much of the underlying chemistry and mechanisms are yet to be unraveled. Here, in this work, we elaborate on the sol–gel chemistry of Cr 2 GaC, the first layered ternary carbide belonging to the MAX phase family to ever be synthesized using this wet chemical approach. Leveraging a variety of both in- and ex situ characterization techniques, including X-ray and neutron powder diffraction, X-ray absorption fine structure analyses, total scattering analyses, and differential scanning calorimetry coupled with mass spectrometry, in-depth analyses of the local structures and reaction pathways are elucidated. While the metals first form tetrahedrally and octahedrally coordinated oxidic structures, that subsequently grow and crystallize into oxides, the carbon source citric acid sits on a separate reaction pathway, that does not merge with the metals until the very end. In fact, after decomposing it remains nanostructured and disordered graphite until the temperature allows for the reduction of the metal oxides into the layered carbide. Based on this, we hypothesize that the method is mostly applicable to systems where the needed metals are reducible by graphite around the formation temperature of the target phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rate constant for the reaction NH2 + NO from 216 to 480 K

The absolute rate constant was measured by the technique of flash photolysis-laser induced fluorescence (FP-LIF). NH2 radicals were produced by the flash photolysis of ammonia and the fluorescent NH2 photons were measured by multiscaling techniques. At each temperature, the results were independent of variations in total pressure, and flash intensity. The results are compared with previous determinations using the techniques of mass spectrometry, absorption spectroscopy, laser absorption spectroscopy, and laser induced fluorescence. The implications of the results are discussed with regard to combustion, post combustion, and atmospheric chemistry. The results are also discussed theoretically.

Stief, L. J.↗

A comparative review of optical surface contamination assessment techniques

This paper will review the relative sensitivities and practicalities of the common surface analytical methods that are used to detect and identify unwelcome adsorbants on optical surfaces. The compared methods include visual inspection, simple reflectometry and transmissiometry, ellipsometry, infrared absorption and attenuated total reflectance spectroscopy (ATR), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS), and mass accretion determined by quartz crystal microbalance (QCM). The discussion is biased toward those methods that apply optical thin film analytical techniques to spacecraft optical contamination problems. Examples are cited from both ground based and in-orbit experiments.

Heaney, James B.↗

Copper and zinc levels in soil, water, wheat, and hair of inhabitants of three areas of the Orenburg region, Russia

Highlights: • Soil, water, wheat and hair levels of Zn and Cu in Orenburg region were studied. • Both Zn and Cu levels in the samples were higher in the eastern area. • Higher levels of Zn and Cu in the eastern area may occur due to industrial activities. • Water Zn levels were associated with hair Zn levels. The objective of the present study was to assess the level of zinc and copper in soil, water, wheat and hair of inhabitants of the western, central, and eastern areas of the Orenburg region. A total of 525 water, soil, and wheat samples, as well as 420 hair samples were assessed using atomic absorption spectrometry (water, soil, wheat) and inductively-coupled plasma mass spectrometry (hair). The highest levels of Zn and Cu in water (4.9(4.2–5.1) and 1.0(0.9–1.1) mg/l), soil (23.8(20.7–27.0) and 2.6(1.9–3.1) mg/kg), and wheat (24.7(20.5–31.0) and 4.8(4.2–5.5) mg/kg) were observed in the eastern area (p < 0.001). Hair zinc levels in inhabitants of the western (184(165–198) µg/g) and eastern (224(211–253) µg/g) areas of the region exceeded the respective values from the central area by 32% and 61% (p < 0.001). In turn, hair Cu levels in the central (16.4(14.3–17.8) µg/g) and eastern (17.9(16.4–19.0) µg/g) areas exceeded the values from the western area by 10% and 20%, respectively. Correlation analysis demonstrated that hair Zn levels were positively correlated with water and soil content, whereas wheat Zn levels were associated with soil and water content. For copper significant direct correlation was observed only between soil and water Cu content. In multiple regression models, only water zinc level was significantly associated with hair Zn content, although the general model accounted for 55% of variability of hair Zn content. Higher zinc and copper exposure in the eastern area is presumably associated with higher activity of metal-processing industry.

54 ENVIRONMENTAL SCIENCES↗

Templates of expected measurement uncertainties for neutron-induced capture and charged-particle production cross section observables

This paper provides a template of expected uncertainties and correlations for measurements of neutron-induced capture and charged-particle production cross sections. Measurements performed in-beam include total absorption spectroscopy, total energy detection, γ -ray spectroscopy, and direct charged-particle detection. Offline measurements include activation analysis and accelerator mass spectrometry. The information needed for proper use of the datasets in resonance region and high energy region evaluations is described, and recommended uncertainties are provided when specific values are not available for a dataset.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The determination of the global average OH concentration using a deuteroethane tracer

It is proposed to measure the decreasing global concentration of an OH reactive isotopic tracer, G sub 2 D sub 6, after its introduction into the troposphere in a manner to facilitate uniform global mixing. Analyses at the level of 2 x 10 to the -19th power fraction, corresponding to one kg uniformly distributed globally, should be possible by a combination of cryogenic absorption techniques to separate ethane from air and high sensitivity isotopic analysis of ethane by mass spectrometry. Aliquots of C sub 2 D sub 6 totaling one kg would be introduced to numerous southern and northern latitudes over a 10 day period in order to achieve a uniform global concentration within 3 to 6 months by the normal atmospheric circulation. Then samples of air of 1000 l (STP) would be collected periodically at a tropical and temperate zone location in each hemisphere and spiked with a known amount of another isotopic species of ethane, C-13 sub 2 H sub 6, at the level of 10 to the -11th power mole fraction. After separation of the ethanes from air, the absolute concentration of C sub 2 D sub 6 would be analyzed using the Argonne 100-inch radius mass spectrometer.

Stevens, Charles M.↗

Molecular Characterization of Water-Soluble Brown Carbon Chromophores in Snowpack from Northern Xinjiang, China

This study reports molecular-level characterization of brown carbon (BrC) attributed to water-soluble organic carbon in six snowpack samples collected from northern Xinjiang, China. Here, the molecular composition and light-absorbing properties of BrC chromophores were unraveled by application of high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector and high-resolution mass spectrometry. The chromophores were classified into five major types, that is, (1) phenolic/lignin-derived compounds, (2) flavonoids, (3) nitroaromatics, (4) oxygenated aromatics, and (5) other chromophores. Identified chromophores account for ~23–64% of the total light absorption measured by the PDA detector in the wavelength range of 300–370 nm. In the representative samples from urban and remote areas, oxygenated aromatics and nitroaromatics dominate the absorption in the wavelengths below and above 320 nm, respectively. The highly polluted urban sample shows the most complex HPLC-PDA chromatogram, and more other chromophores contribute to the bulk absorption. Phenolic/ lignin-derived compounds are the most light-absorbing species in the soil-influenced sample. Chromophores in two remote samples exhibit ultraviolet–visible features distinct from other samples, which are attributed to flavonoids. Identification of individual chromophores and quantitative analysis of their optical properties are helpful for elucidating the roles of BrC in snow radiative balance and photochemistry.

54 ENVIRONMENTAL SCIENCES↗

Biochemical Characterization of the Influences of Pump-and-Treat Remediation on Aquifer Conditions on the Central Plateau of the Hanford Site

The aim of this research was to quantify and characterize the organic carbon present in the subsurface on the Hanford site, specifically where groundwater pump-and-treat (P&T) operations are currently taking place. The primary purpose of P&T is to remediate groundwater contaminants, however water treatment can alter subsurface conditions by introducing a low, but consistent supply of organic carbon to the subsurface. These inputs have not been characterized and the consequences therein have not been considered prior. Approximately 40 L of groundwater from the P&T facility was processed by stepwise ultra-filtration for carbon characterization. Groundwater was first filtered to remove particulate organic carbon (POC) and colloids (operationally defined as > 0.2 µm) and subsequently, two size fractions of dissolved organic carbon (DOC, operationally defined as <0.2 µm), the > 10 kDa fraction and the >5 kDa fraction. POC was analyzed via X-Ray powder Diffraction (XRD) for structural and phase characterization of groundwater particulates. Dissolved organic carbon (10 kDa fraction) was quantified using a total carbon analyzer (NPOC, non-particulate organic carbon) and the chemical character of this carbon further defined by specific UV absorption and Fourier-Transform Ion Cyclotron Resonance - Mass Spectrometry (FTICR-MS). This detailed analysis of groundwater carbon reveals how P&T operations are affecting subsurface nutrient dynamics, which in turn could have a positive feedback on natural attenuation pathways in the 200W contaminant plume at the Hanford Site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗