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At least 901 records · Page 50
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Estimation of volume-weighted average grain size in Fe-based nanocrystalline soft magnetic materials by autocorrelation function

Highlights: • Normalized ACF of TEM images estimates the volume-weighted average grain size. • Grain size estimation by normalized ACF shows good accuracy and time efficiency. • Normalized ACF can reveal grain size difference in different areas of a TEM sample. • Normalized ACF helps modelling of grain size distributions in Fe-B nanostructures. - Abstract: The coercivity of Fe-based nanocrystalline soft magnetic materials depends critically on the grain size of bcc-Fe grains. Accurately estimating the volume-weighted mean grain size is extremely important to develop new Fe-based nanocrystalline soft magnetic materials with low coercivity. This article shows that autocorrelation analysis of dark-field transmission electron microscope (TEM) images provides a very good estimation of bcc-Fe grain size in nanocrystalline soft magnetic materials. This method can be used to efficiently estimate the volume-weighted average grain size from multiple TEM images with much less inherent bias than manual measurement techniques. The estimated grain sizes show good consistency to the grain sizes estimated by X-ray diffraction (XRD) and manual measurement. In contrast to XRD, this method can also reveal the differences in grain size from different micron-sized regions of a sample.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2012

Experimental validation of heterogeneity-corrected dose-volume prescription on respiratory-averaged CT images in stereotactic body radiotherapy for moving tumors

The purpose of this study was to experimentally assess the validity of heterogeneity-corrected dose-volume prescription on respiratory-averaged computed tomography (RACT) images in stereotactic body radiotherapy (SBRT) for moving tumors. Four-dimensional computed tomography (CT) data were acquired while a dynamic anthropomorphic thorax phantom with a solitary target moved. Motion pattern was based on cos (t) with a constant respiration period of 4.0 sec along the longitudinal axis of the CT couch. The extent of motion (A{sub 1}) was set in the range of 0.0-12.0 mm at 3.0-mm intervals. Treatment planning with the heterogeneity-corrected dose-volume prescription was designed on RACT images. A new commercially available Monte Carlo algorithm of well-commissioned 6-MV photon beam was used for dose calculation. Dosimetric effects of intrafractional tumor motion were then investigated experimentally under the same conditions as 4D CT simulation using the dynamic anthropomorphic thorax phantom, films, and an ionization chamber. The passing rate of {gamma} index was 98.18%, with the criteria of 3 mm/3%. The dose error between the planned and the measured isocenter dose in moving condition was within {+-} 0.7%. From the dose area histograms on the film, the mean {+-} standard deviation of the dose covering 100% of the cross section of the target was 102.32 {+-} 1.20% (range, 100.59-103.49%). By contrast, the irradiated areas receiving more than 95% dose for A{sub 1} = 12 mm were 1.46 and 1.33 times larger than those for A{sub 1} = 0 mm in the coronal and sagittal planes, respectively. This phantom study demonstrated that the cross section of the target received 100% dose under moving conditions in both the coronal and sagittal planes, suggesting that the heterogeneity-corrected dose-volume prescription on RACT images is acceptable in SBRT for moving tumors.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2012

Changes of the transverse diameter and volume and dosimetry before the 25th fraction during the course of intensity-modulated radiation therapy (IMRT) for patients with nasopharyngeal carcinoma

To quantify changes of the transverse diameter and volume and dosimetry, and to illustrate the inferiority of non-replanning during intensity-modulated radiotherapy (IMRT) for nasopharyngeal carcinoma (NPC) patients. Fifty-three NPC patients who received IMRT in 33 fractions were enrolled in this prospective trial. Before the 25th fraction, a new simulation computed tomography (CT) scan was acquired for all patients. The dose-volume histograms of the phantom plan were compared with the initial plan. Significant reduction of the transverse diameter of the nasopharyngeal, the neck, and 2 parotid glands volume was observed on second CT compared with the first CT (mean reduction 7.48 {+-} 4.45 mm, 6.80 {+-} 15.14 mm, 5.70 {+-} 6.26 mL, and 5.04 {+-} 5.85 mL, respectively; p < 0.01). The maximum dose and V-40 of the spinal cord, mean dose, and V30 of the left and right parotid, and V-50 of the brain stem were increased significantly in the phantom plan compared with the initial plan (mean increase 4.75 {+-} 5.55 Gy, 7.18 {+-} 10.07%, 4.51 {+-} 8.55 Gy, 6.59 {+-} 17.82%, 5.33 {+-} 8.55 Gy, 11.68 {+-} 17.11% and 1.48 {+-} 3.67%, respectively; p < 0.01). On the basis of dose constraint criterion in the RTOG0225 protocol, the dose of the normal critical structures for 52.83% (28/53) of the phantom plans were out of limit compared with 1.89% (1/53) of the initial plans (p < 0.0001). Because of the significant change in anatomy and dose before the 25th fraction during IMRT, replanning should be necessary during IMRT with NPC.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2013

Circumferential or sectored beam arrangements for stereotactic body radiation therapy (SBRT) of primary lung tumors: Effect on target and normal-structure dose-volume metrics

To compare 2 beam arrangements, sectored (beam entry over ipsilateral hemithorax) vs circumferential (beam entry over both ipsilateral and contralateral lungs), for static-gantry intensity-modulated radiation therapy (IMRT) and volumetric-modulated arc therapy (VMAT) delivery techniques with respect to target and organs-at-risk (OAR) dose-volume metrics, as well as treatment delivery efficiency. Data from 60 consecutive patients treated using stereotactic body radiation therapy (SBRT) for primary non–small-cell lung cancer (NSCLC) formed the basis of this study. Four treatment plans were generated per data set: IMRT/VMAT plans using sectored (-s) and circumferential (-c) configurations. The prescribed dose (PD) was 60 Gy in 5 fractions to 95% of the planning target volume (PTV) (maximum PTV dose ∼ 150% PD) for a 6-MV photon beam. Plan conformality, R{sub 50} (ratio of volume circumscribed by the 50% isodose line and the PTV), and D{sub 2} {sub cm} (D{sub max} at a distance ≥2 cm beyond the PTV) were evaluated. For lungs, mean doses (mean lung dose [MLD]) and percent V{sub 30}/V{sub 20}/V{sub 10}/V{sub 5} Gy were assessed. Spinal cord and esophagus D{sub max} and D{sub 5}/D{sub 50} were computed. Chest wall (CW) D{sub max} and absolute V{sub 30}/V{sub 20}/V{sub 10}/V{sub 5} {sub Gy} were reported. Sectored SBRT planning resulted in significant decrease in contralateral MLD and V{sub 10}/V{sub 5} {sub Gy}, as well as contralateral CW D{sub max} and V{sub 10}/V{sub 5} {sub Gy} (all p < 0.001). Nominal reductions of D{sub max} and D{sub 5}/D{sub 50} for the spinal cord with sectored planning did not reach statistical significance for static-gantry IMRT, although VMAT metrics did show a statistically significant decrease (all p < 0.001). The respective measures for esophageal doses were significantly lower with sectored planning (p < 0.001). Despite comparable dose conformality, irrespective of planning configuration, R{sub 50} significantly improved with IMRT-s/VMAT-c (p < 0.001/p = 0.008), whereas D{sub 2} {sub cm} significantly improved with VMAT-c (p < 0.001). Plan delivery efficiency improved with sectored technique (p < 0.001); mean monitor unit (MU)/cGy of PD decreased from 5.8 ± 1.9 vs 5.3 ± 1.7 (IMRT) and 2.7 ± 0.4 vs 2.4 ± 0.3 (VMAT). The sectored configuration achieves unambiguous dosimetric advantages over circumferential arrangement in terms of esophageal, contralateral CW, and contralateral lung sparing, in addition to being more efficient at delivery.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2014

A dosimetric comparison of 3D-CRT, IMRT, and static tomotherapy with an SIB for large and small breast volumes

Radiation therapy to the breast is a complex task, with many different techniques that can be employed to ensure adequate dose target coverage while minimizing doses to the organs at risk. This study compares the dose planning outcomes of 3 radiation treatment modalities, 3 dimensional conformal radiation therapy (3D-CRT), intensity-modulated radiation therapy (IMRT), and static tomotherapy, for left-sided whole-breast radiation treatment with a simultaneous integrated boost (SIB). Overall, 20 patients with left-sided breast cancer were separated into 2 cohorts, small and large, based on breast volume. Dose plans were produced for each patient using 3D-CRT, IMRT, and static tomotherapy. All patients were prescribed a dose of 45 Gy in 20 fractions to the breast with an SIB of 56 Gy in 20 fractions to the tumor bed and normalized so that D{sub 98%} > 95% of the prescription dose. Dosimetric comparisons were made between the 3 modalities and the interaction of patient size. All 3 modalities offered adequate planning target volume (PTV) coverage with D{sub 98%} > 95% and D{sub 2%} < 107%. Static tomotherapy offered significantly improved (p = 0.006) dose homogeneity to the PTV{sub boost} {sub eval} (0.079 ± 0.011) and breast minus the SIB volume (Breast{sub SIB}) (p < 0.001, 0.15 ± 0.03) compared with the PTV{sub boost} {sub eval} (0.085 ± 0.008, 0.088 ± 0.12) and Breast{sub SIB} (0.22 ± 0.05, 0.23 ± 0.03) for IMRT and 3D-CRT, respectively. Static tomotherapy also offered statistically significant reductions (p < 0.001) in doses to the ipsilateral lung mean dose of 6.79 ± 2.11 Gy compared with 7.75 ± 2.54 Gy and 8.29 ± 2.76 Gy for IMRT and 3D-CRT, respectively, and significantly (p < 0.001) reduced heart doses (mean = 2.83 ± 1.26 Gy) compared to both IMRT and 3D-CRT (mean = 3.70 ± 1.44 Gy and 3.91 ± 1.58 Gy). Static tomotherapy is the dosimetrically superior modality for the whole breast with an SIB compared with IMRT and 3D-CRT. IMRT is superior to 3D-CRT in both PTV dose conformity and reduction of mean doses to the ipsilateral lung.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2015

Using injectable hydrogel markers to assess resimulation for boost target volume definition in a patient undergoing whole-breast radiotherapy

Several publications have recommended that patients undergoing whole-breast radiotherapy be resimulated for boost planning. The rationale for this is that the seroma may be smaller when compared with the initial simulation. However, the decision remains whether to use the earlier or later images to define an appropriate boost target volume. A patient undergoing whole-breast radiotherapy had new, injectable, temporary hydrogel fiducial markers placed 1 to 3 cm from the seroma at the time of initial simulation. The patient was resimulated 4.5 weeks later for conformal photon boost planning. Computed tomography (CT) scans acquired at the beginning and the end of whole-breast radiotherapy showed that shrinkage of the lumpectomy cavity was not matched by a corresponding reduction in the surrounding tissue volume, as demarcated by hydrogel markers. This observation called into question the usual interpretation of cavity shrinkage for boost target definition. For this patient, it was decided to define the boost target volume on the initial planning CT instead of the new CT.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2025

Deciphering volume changes in Li-S solid-state battery components during cycling: Implication for advanced battery design

Here, in this work, we developed custom fixtures to investigate the mechanical and electrochemical behavior of all-solid-state lithium batteries during cycling under constant pressure and constant volume conditions. We successfully monitored vertical displacements during constant pressure cycling and pressure variations during constant volume cycling, allowing us decouple volume changes in the sulfur, Li 2 S cathodes, LixIn anode, and solid-state electrolyte. Scanning electron microscopy and electrochemical impedance spectroscopy confirmed that two structural changes occur during ASSLB cycling: (1) irreversible fractures in the active material particles, and (2) void formation within the electrode matrix. While the fractures in primary particles are permanent, void formation can be mitigated through stack pressure, which promotes particle rearrangement in the electrode matrix. Our findings emphasize the importance of stack pressure in maintaining the microscale integrity of all-solid-state lithium batteries, preventing void formation and enhance battery performance and durability.

Cell Design↗
DOE OSTI2025

Confocal Raman Microscopy as an In Situ Probe of Volume Change in Hydration-Sensitive Polymer Membranes

An approach is described for measuring hydration-induced volume change within ion conductive polymer membranes and thin films by adapting the technique of confocal Raman microscopy. With careful consideration of factors that affect excitation and scattering within the confocal probe volume region, material swelling and deswelling were estimated from the intensities of polymer matrix spectral features. A high numerical aperture oil-immersion objective was used to achieve tight focusing within samples and the efficient collection of Raman scattered light. The approach is demonstrated for a fluorinated cation-exchange ionomer (Nafion) and the hydrocarbon anion-exchange ionomer Sustainion. Samples were monitored while under a nitrogen atmosphere that was cycled between dry and humid (∼50% relative humidity, RH) states. The volume changes estimated from the Raman spectra were in close agreement with those derived from conventional measurements. The reported work advances understanding needed to adapt confocal Raman microscopy for quantitative in situ and operando studies of ionomers within electrochemical devices, such as polymer electrolyte membrane fuel cells and electrolyzers, and lays a foundation for broader applications in the study of hydration-induced polymer swelling and the associated molecular level water and polymer framework structural changes.

Absorption↗
DOE OSTI2025

Reaction-Induced Fracturing of Porous Carbonate Rocks during Volume-Increasing Replacement by Witherite

Volume-increasing replacement reactions can lead either to fracturing of the parent phase or to the formation of cohesive layers that passivate further reaction, but the factors that drive one outcome or the other are not understood. In this experimental study, we investigated the volume-increasing replacement of carbonate rocks (consisting of CaCO 3 and CaMg(CO 3 ) 2 ) of different porosity by witherite (BaCO 3 ). Samples were characterized using scanning electron microscopy, Raman spectroscopy, small-angle neutron/X-ray scattering, X-ray tomography, and scanning transmission electron microscopy. We observed the formation of a witherite reaction layer and witherite formation within pores and along grain boundaries. Despite this being a volume-increasing replacement reaction, newly formed witherite was porous, potentially allowing further replacement. Filled fractures were observed in the low-porosity carbonates, whereas witherite formed within pores in high-porosity carbonates. We conclude that fracturing of the parent phase versus passivation is contingent on the initial microstructure of the parent with an optimal degree of porosity required for fracturing.

Calcite↗
DOE OSTI2022

Understanding Relationships between Free Volume and Oxygen Absorption in Ionic Liquids

In this report understanding the factors that govern gas absorption in ionic liquids is critical to the development of high-capacity solvents for catalysis, electrochemistry, and gas separations. Here, we report experimental probes of liquid structure that provide insights into how free volume impacts the O 2 absorption properties of ionic liquids. Specifically, we establish that isothermal compressibility - measured rapidly and accurately through small-angle X-ray scattering - reports on the size distribution of transient voids within a representative series of ionic liquids and is correlated with O 2 absorption capacity. Additionally, O 2 absorption capacities are correlated with thermal expansion coefficients, reflecting the beneficial effect of weak intermolecular interactions in ionic liquids on free volume and gas absorption capacity. Molecular dynamics simulations show that the void size distribution - in particular, the probability of forming larger voids within an ionic liquid - has a greater impact on O 2 absorption than the total free volume. These results establish relationships between the ionic liquid structure and gas absorption properties that offer design strategies for ionic liquids with high gas solubilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

A Quasielastic Neutron Scattering Study of Water Diffusion in Model Anion Exchange Membranes over Localized and Extended Volume Increments

Anion exchange membranes provide the basis for potentially more cost-effective fuel cells, electrochemical energy conversion, and energy storage. The membranes consist of a polymer domain with tethered cationic side groups and a pervading aqueous domain that conducts water and anions. Water diffusion is investigated through temperature-dependent quasielastic neutron scattering (QENS) at application relevant water contents, employing the BASIS spectrometer at ORNL. The spectrometer resolves two distinct quasielastic components corresponding to localized water diffusion (on length scales lower than the water domain thickness) and to extended water diffusion (on length scales approaching the water domain thickness). Water diffusion coefficients in membranes are time and length scale dependent and water exchanges between diffusion on a localized and extended volume increment. An exchange model for QENS is developed to describe the exchange of water between the two volume increments. In conclusion, the populations and lifetimes of water in each volume are discussed in terms of their connection to long-range water transport and membrane nanomorphology.

Diffusion↗
DOE OSTI2023

Structure, Dynamics, and Hydrogen Transport in Amorphous Polymers: An Analysis of the Interplay between Free Volume Element Distribution and Local Segmental Dynamics from Molecular Dynamics Simulations

Polymers are attractive membrane materials owing to their mechanical robustness and relatively inexpensive fabrication. An important indicator of membrane performance are free volume elements (FVE): microporous void spaces created by the inefficient packing of bulky groups along the polymer chain. FVEs tend to degrade over time, as polymer chains reorganize irreversibly. While it is widely accepted that polymer flexibility has an impact on membrane transport properties, the molecular nature of this impact is still not well understood. By the establishment of a correlation between local chain dynamics and the distribution of free volume elements (FVEs), penetrant transport can be regulated more efficiently in amorphous polymer membranes. In this work, we implement all-atom molecular dynamics (MD) simulations to explore the relationship between chain dynamics and free volume in three polymers with different levels of backbone flexibility: polymethylpentene (PMP), polystyrene (PS), and HAB-6FDA thermally rearranged polymer (TRP). We construct these polymers at different temperatures and examine how temperature impacts the FVE distribution and segmental mobility. Our analysis shows that chain segments near FVEs have higher mobility compared with the atoms in the bulk; the extent of this difference increases with chain flexibility. Increasing the chain flexibility by increasing the temperature results in a broader FVE distribution. Rigid polymers such as TRP show the most robust FVE distribution and are not significantly affected by the temperature change. To capture penetrant diffusion through the polymer matrix, hydrogen is inserted and the diffusion is measured at different temperatures; hydrogen mobility is influenced by the FVE structure and overall mobility of polymer chains. Lastly, at low temperatures, hydrogen mobility is influenced by void distribution, while at high temperatures, polymer dynamics dictate hydrogen transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Gyroid Structures at Highly Asymmetric Volume Fractions by Blending of ABC Triblock Terpolymer and AB Diblock Copolymer

Here, we investigated, via small angle X-ray scattering and transmission electron microscopy, the morphologies of binary blend of polyisoprene- b -polystyrene- b -poly(2-vinylpyridine) (ISP) triblock terpolymer and polyisoprene-b-polystyrene (IS) diblock copolymer. An asymmetric ISP with volume fractions ( f ) of 0.12, 0.75, and 0.13 for PI, PS, and P2VP blocks, respectively, showed a new morphology: Coexistence of spheres and cylinders with tetragonal packing. Asymmetric IS with f I = 0.11 and f S =0.89 showed conventional body-centered cubic spherical microdomains. Very interestingly, a binary blend of ISP and IS with overall volume fractions of f I = 0.12, f S = 0.79, and f P = 0.09 exhibited core-shell double gyroid (CSG: Q 230 space group), where PI consists of thin core and PS forms thick shell, while P2VP becomes thin matrix. It is very unusual to form highly asymmetric CSG with the matrix having very small volume fraction (0.09).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Using X-ray Microscopy To Understand How Nanoporous Materials Can Be Used To Reduce the Large Volume Change in Alloy Anodes

Tin metal is an attractive negative electrode material to replace graphite in Li-ion batteries due to its high energy density. However, tin undergoes a large volume change upon alloying with Li, which pulverizes the particles, and ultimately leads to short cycling lifetimes. Nevertheless, nanoporous materials have been shown to extend battery life well past what is observed in nonporous material. Despite the exciting potential of porous alloying anodes to significantly increase the energy density in Li-ion batteries, the fundamental physics of how nanoscale architectures accommodate the electrochemically induced volume changes are poorly understood. Here, operando transmission X-ray microscopy has been used to develop an understanding of the mechanisms that govern the enhanced cycling stability in nanoporous tin. We found that in comparison to dense tin, nanoporous tin undergoes a 6-fold smaller areal expansion after lithiation, as a result of the internal porosity and unique nanoscale architecture. The expansion is also more gradual in nanoporous tin compared to the dense material. The nanoscale resolution of the microscope used in this study is ~30 nm, which allowed us to directly observe the pore structure during lithiation and delithiation. We found that nanoporous tin remains porous during the first insertion and desinsertion cycle. This observation is key, as fully closed pores could lead to mechanical instability, electrolyte inaccessibility, and short lifetimes. Here, while tin was chosen for this study because of its high X-ray contrast, the results of this work should be general to other alloy-type systems, such as Si, that also suffer from volume change based cycling degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Increasing Volume in Conjugated Polymers to Facilitate Electrical Doping with Phosphomolybdic Acid

Molecular p-type electrical dopants have been proven useful to fine-tune the optoelectronic properties of bulk organic semiconductors and their interfaces. In this work, the volume in polymer films and its role in solution-based electrical p-type doping using phosphomolybdic acid (PMA) are studied. The polymer film volume was controlled using two approaches. One is based on heating both the PMA solution and the film prior to immersion. The second is based on coating the polymer film with a liquid blend that contains the PMA solution and a swelling solvent. 31 P NMR and FTIR experiments indicate that the Keggin structure appears to be preserved throughout the doping process. Results show that increasing the polymer volume facilitates the infiltration of the PMA Keggin structure, which results in an increased electrical p-type doping level.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Hierarchically Porous Graphitic Carbon with Simultaneously High Surface Area and Colossal Pore Volume Engineered via Ice Templating

Developing hierarchical porous carbon (HPC) materials with competing textural characteristics such as surface area and pore volume in one material is difficult to accomplish—particulalry for an atomically ordered (graphitic) carbon. Herein we describe a synthesis strategy to engineer tunable hierarchically porous carbon (HPC) materials across micro- meso- and macroporous length scales, allowing the fabrication of a graphitic HPC with both very high surface area (> 2500 m2/g) and pore volume (>10 cm3/g), the combination of which has not been seen previously. The mesopore volume alone for these materials is up to 7.91 cm3/g, the highest ever reported. The unique material was explored for use as a supercapaictor electrode and for oil adsorption; two applications that require textural properties that are typicaly exclusive to one another. This design scheme for HPCs can be utilized in broad applications, including electrochemical systems such as batteries and supercapacitors, sorbents, and catalyst supports.

Estevez, Luis↗
DOE OSTI2017

Colossal Volume Contraction in Strong Polar Perovskites of Pb(Ti,V)O 3

The unique physical property of negative thermal expansion (NTE) is not only interesting for scientific research but also important for practical applications. Chemical modification generally tends to weaken NTE. It remains a challenge to obtain enhanced NTE from currently available materials. Herein, we successfully achieve enhanced NTE in Pb(Ti 1-x V x )O 3 by improving its ferroelectricity. With the chemical substitution of vanadium, lattice tetragonality (c/a) is highly promoted, which is attributed to strong spontaneous polarization, evidenced by the enhanced covalent interaction in the V/Ti-O and Pb-O2 bonds from first principles calculations. As a consequence, Pb(Ti 0.9 V 0.1 )O 3 exhibits a nonlinear and much stronger NTE over a wide temperature range with a volumetric coefficient of thermal expansion α v = -3.76 X 10 -5 /ºC (25-550 ºC). Interestingly, an intrinsic giant volume contraction (~3.7%) was obtained at the composition of Pb(Ti 0.7 V 0.3 )O 3 during the ferroelectric-to-paraelectric phase transition, which represents the highest value ever reported. Such volume contraction is well correlated to the effect of spontaneous volume ferroelectrostriction. This study extends the scope of the NTE family and provides an effective approach to explore new materials with large NTE, such as through adjusting the NTE-related ferroelectric property in the family of ferroelectrics.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Characterization of the intragranular water regime within subsurface sediments: Pore volume, surface area, and mass transfer limitations

Although 'intragranular' pore space within grain aggregates, grain fractures, and mineral 24 surface coatings may contain a relatively small fraction of the total porosity within a porous 25 medium, it often contains a significant fraction of the reactive surface area, and can thus strongly 26 affect the transport of sorbing solutes. In this work, we demonstrate a batch experiment 27 procedure using tritium and bromide as high-resolution diffusive tracers to characterize the 28 intragranular pore space. The method was tested using uranium-contaminated sediments from 29 the vadose and capillary fringe zones beneath the former 300A process ponds at the Hanford site 30 (Washington State, USA). Sediments were contacted with tracers in artificial groundwater, 31 followed by replacement of bulk solution with tracer-free groundwater and monitoring of tracer 32 release. From these data, intragranular pore volumes were calculated and mass transfer rates 33 were quantified using a multirate first-order mass transfer model. Tritium-hydrogen exchange 34 on surface hydroxyls was accounted for by conducting additional tracer experiments on sediment 35 that was vacuum dried after reaction. The complementary ('wet' and 'dry') techniques allowed 36 for the simultaneous determination of intragranular porosity and surface area using tritium. The 37 Hanford 300A samples exhibited intragranular pore volumes of {approx}1% of the solid volume and 38 intragranular surface areas of {approx}20-30% of the total surface area. Comparison with N2 gas 39 adsorption suggests that this pore space includes both 'micropores' (< 2 nm diameter) and 40 'mesopores' (> 2 nm). Intragranular porosity estimates obtained using bromide were 41 significantly smaller, likely due to anion exclusion of Br- from pores with negatively charged 42 surfaces.

300A↗