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At least 559 records · Page 31

Learning Memento archive routing with Character-based Artificial Neural Networks

This white paper describes a series of tests that were performed to determine if a neural network could learn patterns from a service that maintains a cache of routing decisions for the discovery of version information for discrete web-at-large URLs. Labeled training data was derived from a log file that records the by-archive availability of Memento availability for a given URL. Training data sets were generated from this log file on a by-archive basis (thus making it a binary classification problem). Each training data set consisted of equal numbers of hit and miss URLs, selected at random. The URLs were converted to a normalized numeric representation where each integer in a URL training vector represents a character in that URL. The corresponding label indicates whether or not Mementos were available for that URL in the selected archive. The training data matrix and the label vector became input to a neural network. A number of neural network architectures and network hyperparameters were explored, however the log entries themselves were used as-is, without any feature engineering, beyond the aforementioned normalization.

97 MATHEMATICS AND COMPUTING↗

Training Restricted Boltzmann Machines With a D-Wave Quantum Annealer

Restricted Boltzmann Machine (RBM) is an energy-based, undirected graphical model. It is commonly used for unsupervised and supervised machine learning. Typically, RBM is trained using contrastive divergence (CD). However, training with CD is slow and does not estimate the exact gradient of the log-likelihood cost function. In this work, the model expectation of gradient learning for RBM has been calculated using a quantum annealer (D-Wave 2000Q), where obtaining samples is faster than Markov chain Monte Carlo (MCMC) used in CD. Training and classification results of RBM trained using quantum annealing are compared with the CD-based method. The performance of the two approaches is compared with respect to the classification accuracies, image reconstruction, and log-likelihood results. The classification accuracy results indicate comparable performances of the two methods. Image reconstruction and log-likelihood results show improved performance of the CD-based method. It is shown that the samples obtained from quantum annealer can be used to train an RBM on a 64-bit “bars and stripes” dataset with classification performance similar to an RBM trained with CD. Though training based on CD showed improved learning performance, training using a quantum annealer could be useful as it eliminates computationally expensive MCMC steps of CD.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Archie's Saturation Exponent for Natural Gas Hydrate in Coarse-Grained Reservoirs

Accurately quantifying the amount of naturally occurring gas hydrate in marine and permafrost environments is important for assessing its resource potential and understanding the role of gas hydrate in the global carbon cycle. Electrical resistivity well logs are often used to calculate gas hydrate saturations, S h , using Archie's equation. Archie's equation, in turn, relies on an empirical saturation parameter, n . Though n = 1.9 has been measured for ice–bearing sands and is widely used within the hydrate community, it is highly questionable if this n value is appropriate for hydrate–bearing sands. In this work, we calibrate n for hydrate–bearing sands from the Canadian permafrost gas hydrate research well, Mallik 5L–38, by establishing an independent downhole S h profile based on compressional–wave velocity log data. Using the independently determined S h profile and colocated electrical resistivity and bulk density logs, Archie's saturation equation is solved for n , and uncertainty is tracked throughout the iterative process. In addition to the Mallik 5L–38 well, we also apply this method to two marine, coarse–grained reservoirs from the northern Gulf of Mexico Gas Hydrate Joint Industry Project: Walker Ridge 313–H and Green Canyon 955–H. All locations yield similar results, each suggesting n ≈ 2.5 ± 0.5. Furthermore, for the coarse–grained hydrate bearing ( S h > 0.4) of greatest interest as potential energy resources, we suggest that n = 2.5 ± 0.5 should be applied in Archie's equation for either marine or permafrost gas hydrate settings if independent estimates of n are not available.

58 GEOSCIENCES↗

Solvent Acts as the Referee in a Match‐Up Between Charged and Preorganized Receptors

The prevalence of anion-cation contacts in biomolecular recognition under aqueous conditions suggests that ionic interactions should dominate the binding of anions in solvents across both high and low polarities. Investigations of this idea using titrations in low polarity solvents are impaired by interferences from ion pairing that prevent a clear picture of binding. To address this limitation and test the impact of ion-ion interactions across multiple solvents, we quantified chloride binding to a cationic receptor after accounting for ion pairing. In these studies, we created a chelate receptor using aryl-triazole CH donors and a quinolinium unit that directs its cationic methyl inside the binding pocket. In low-polarity dichloromethane, the 1 : 1 complex (log K 1 : 1 ~ 7.3) is more stable than neutral chelates, but fortuitously comparable to a preorganized macrocycle (log K 1 : 1 ~ 6.9). Polar acetonitrile and DMSO diminish stabilities of the charged receptor (log K 1 : 1 ~ 3.7 and 1.9) but surprisingly 100-fold more than the macrocycle. While both receptors lose stability by dielectric screening of electrostatic stability, the cationic receptor also pays additional costs of organization. Thus even though the charged receptor has stronger binding in apolar solvents, the uncharged receptor has more anion affinity in polar solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Kimberlina synthetic multiphysics dataset for CO 2 monitoring investigations

Abstract We present a synthetic multi‐scale, multi‐physics dataset constructed from the Kimberlina 1.2 CO 2 reservoir model based on a potential CO 2 storage site in the Southern San Joaquin Basin of California. Among 300 models, one selected reservoir‐simulation scenario produces hydrologic‐state models at the onset and after 20 years of CO 2 injection. Subsequently, these models were transformed into geophysical properties, including P‐ and S‐wave seismic velocities, saturated density where the saturating fluid can be a combination of brine and supercritical CO 2 , and electrical resistivity using established empirical petrophysical relationships. From these 3D distributions of geophysical properties, we have generated synthetic time‐lapse seismic, gravity and electromagnetic responses with acquisition geometries that mimic realistic monitoring surveys and are achievable in actual field situations. We have also created a series of synthetic well logs of CO 2 saturation, acoustic velocity, density and induction resistivity in the injection well and three monitoring wells. These were constructed by combining the low‐frequency trend of the geophysical models with the high‐frequency variations of actual well logs collected at the potential storage site. In addition, to better calibrate our datasets, measurements of permeability and pore connectivity have been made on cores of Vedder Sandstone, which forms the primary reservoir unit. These measurements provide the range of scales in the otherwise synthetic dataset to be as close to a real‐world situation as possible. This dataset consisting of the reservoir models, geophysical models, simulated time‐lapse geophysical responses and well logs forms a multi‐scale, multi‐physics testbed for designing and testing geophysical CO 2 monitoring systems as well as for imaging and characterization algorithms. The suite of numerical models and data have been made publicly available for downloading on the National Energy Technology Laboratory's (NETL) Energy Data Exchange (EDX) website.

58 GEOSCIENCES↗

Quantitation of amiodarone and N-desethylamiodarone in single HepG2 cells by single-cell printing-liquid vortex capture-mass spectrometry

Quantitative measure of a drug and its associated metabolite(s) with single-cell resolution is often limited by sampling throughput or other compromises that limit broad use. Here, we demonstrate the use of single-cell printing-liquid vortex capture-mass spectrometry (SCP-LVC-MS) to quantitatively measure the intracellular concentrations of amiodarone (AMIO) and its metabolite, N-desethylamiodarone (NDEA), from thousands of single cells across several AMIO incubation concentrations ranging from 0 to 10 μM. Concentrations obtained by SCP-LVC-MS were validated through comparison with average assays and traditional measurement of cells in bulk. Average of SCP-LVC-MS measurements and aggregate vial collection assay the concentrations differed by < 5%. Both AMIO and NDEA had clear log-normal distributions with similar standard deviation of concentrations in the cell population. The mean of both AMIO and NDEA intracellular concentrations were positively correlated with AMIO incubation concentration, increasing from 0.026 to 0.520 and 0.0055 to 0.048 mM for AMIO and NDEA, respectively. The standard deviation of AMIO and NDEA log-normal distribution fits were relatively similar in value across incubation concentrations, 0.15–0.19 log 10 (mM), and exhibited a linear trend with respect to each other. The single cell-resolved conversion ratio of AMIO to NDEA increased with decreasing incubation concentration, 7 ± 2%, 18 ± 3%, and 20 ± 7% for 10.0, 1.0, and 0.1 μM AMIO incubation concentrations, respectively. Finally, association with simultaneously measured lipids had several ions with statistically significant difference in intensity but no clear correlations with AMIO intracellular content was observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A genetic meta-algorithm-assisted inversion approach: hydrogeological study for the determination of volumetric rock properties and matrix and fluid parameters in unsaturated formations

An evolutionary inversion approach is suggested for the interpretation of nuclear and resistivity logs measured by direct-push tools in shallow unsaturated sediments. The efficiency of formation evaluation is improved by estimating simultaneously (1) the petrophysical properties that vary rapidly along a drill hole with depth and (2) the zone parameters that can be treated as constant, in one inversion procedure. In the workflow, the fractional volumes of water, air, matrix and clay are estimated in adjacent depths by linearized inversion, whereas the clay and matrix properties are updated using a float-encoded genetic meta-algorithm. The proposed inversion method provides an objective estimate of the zone parameters that appear in the tool response equations applied to solve the forward problem, which can significantly increase the reliability of the petrophysical model as opposed to setting these parameters arbitrarily. The global optimization meta-algorithm not only assures the best fit between the measured and calculated data but also gives a reliable solution, practically independent of the initial model, as laboratory data are unnecessary in the inversion procedure. The feasibility test uses engineering geophysical sounding logs observed in an unsaturated loessy-sandy formation in Hungary. The multi-borehole extension of the inversion technique is developed to determine the petrophysical properties and their estimation errors along a profile of drill holes. The genetic meta-algorithmic inversion method is recommended for hydrogeophysical logging applications of various kinds to automatically extract the volumetric ratios of rock and fluid constituents as well as the most important zone parameters in a reliable inversion procedure.

58 GEOSCIENCES↗

Using advanced data structures to enable responsive security monitoring

Write-optimized data structures (WODS), offer the potential to keep up with cyberstream event rates and give sub-second query response for key items like IP addresses. These data structures organize logs as the events are observed. To work in a real-world environment and not fill up the disk, WODS must efficiently expire older events. As the basis for our research into organizing security monitoring data, we implemented a tool, called Diventi, to index IP addresses in connection logs using RocksDB (a write-optimized LSM tree). In this work, we extended Diventi to automatically expire data as part of the data structures’ normal operations. We guarantee that Diventi always tracks the N most recent events and tracks no more than N + k events for a parameter k < N, while ensuring the index is opportunistically pruned. To test Diventi at scale in a controlled environment, we used anonymized traces of IP communications collected at SuperComputing 2019. We synthetically extended the 2.4 billion connection events to 100 billion events. We tested Diventi vs. Elasticsearch, a common log indexing tool. In our test environment, Elasticsearch saw an ingestion rate of at best 37,000 events/s while Diventi sustained ingestion rates greater than 171,000 events/s. Our query response times were as much as 100 times faster, typically answering queries in under 80 ms. Furthermore, we saw no noticeable degradation in Diventi from expiration. We have deployed Diventi for many months where it has performed well and supported new security analysis capabilities.

97 MATHEMATICS AND COMPUTING↗

Complexation of Plutonium(IV) with trans-1,2-Diaminocyclohexane-N,N,N',N'-tetraacetic Acid (CDTA) in Acidic Solution

Understanding the interaction of Pu(IV) with complexing agents present in the nuclear fuel cycle is important for predicting the performance of used nuclear fuel separations. The complexation of Pu(IV) with trans -1,2-diaminocyclohexane-N,N,N’,N’-tetraacetic acid (CDTA) was studied in acidic solutions of 0.10 0.50 mol∙L -1 HClO 4 with 1.00 mol∙L -1 (Na,H)ClO 4 total ionic strength by a liquid&ndash;liquid extraction method using tracer quantities of 238 Pu. The acid dissociation constants of CDTA and the autoprotolysis constant of water were determined via potentiometric titrations in 0.10&ndash;2.00 mol∙L -1 NaClO 4 and 25.0 ± 0.1 °C. The variation of the dissociation constants with ionic strength was modeled with the Specific ion Interaction Theory (SIT) and the associated SIT parameters were obtained. The thermodynamic dissociation 23 constants at zero ionic strength for water and CDTA were determined from this analysis as PK$^o_w$ = 14.00 ± 0.03, PK$^o_{a2}$ = 1.52 ± 0.04, PK$^o_{a3}$ = 2.78 ± 0.05, PK$^o_{a4}$ = 4.17 ± 0.04, PK$^o_{a5}$ = 6.75 ± 0.02, and PK$^o_{a6}$ = 10.64 ± 0.04 at 25.0 ± 0.1 °C. The results of the liquid–liquid extraction experiments indicated the formation of a 1:0:1 complex, PuCDTA o , and the presence of additional protonated species, Pu(HCDTA) + and Pu(H 2 CDTA )2+ , at these acidities. The corresponding stability constants in 1.00 mol·L -1 (Na,H)ClO 4 and 23 ± 1 °C were determined to be log 10 β 101 =24.2 ± 0.3, log 10 β 111 =25.4 ± 0.2, and log 10 β 121 = 25.8 ± 0.1.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Design of a wideband microstrip nanoantenna array

This paper presents the design of a logarithmic array of microstrip nano-antennas at terahertz frequencies. For applications in which small antennas are required, microstrip antennas are preferred. However, they have a narrow bandwidth. To overcome this problem in microstrip antennas, a log-periodic nanoantenna design is presented which exhibits a wide bandwidth and ultra-compact design. This antenna is smaller in size compared to log-periodic antennas in microwave bands and comparable and better radiation characteristics. The proposed Log-periodic microstrip nanoantenna array consists of seven patch elements on a dielectric layer and are fed directly by a feed line through the branch lines connected to each of the elements. Scaling factor, τ = 0.95 is considered for this design and inset feed is used. In this structure, the substrate has a relative dielectric constant of ε{sub r} = 4.4 and a thickness of h = 800 nm. For good performance at high frequencies, gold is used for the design of the antenna. The considered operating frequency is 3.3 THz corresponding to a wavelength of 91 µm. Good impedance matching and a wide bandwidth of 800 GHz is obtained.

42 ENGINEERING↗

Insights of Boundary Layer Turbulence Over the Complex Terrain of Central Himalaya from GVAX Field Campaign

Limited observations hinder understanding of turbulent characteristics in mountainous terrain resulting from heating or cooling of slopes, wind, vertical motions, and heat or moisture advection, which disperse aerosols and other pollutants over the region. In this study, the 1290 MHz radar wind profiler data are utilized to compute the boundary layer height (BLH), the refractive index structure constant (C n 2 ), and the energy dissipation rate (ε) over the central Himalayan site for the period of November 2011 to March 2012, from the intense Ganges Valley Aerosol Experiment (GVAX) field measurements. The radar wind profiler (RWP) based estimation of BLH and ε is validated against the radiosonde, representing the effectiveness of the datasets for further investigation. The strong seasonal variation of log C n 2 and log ε, with average values of ≈ -12 m -2/3 and -2 m 2 s -3 , respectively, is associated with the mountain-induced local circulations and stability in the atmospheric boundary layer. The weak stratification during weak flow is found to be responsible for deep mixing, particularly in the nocturnal boundary layer in spring. Furthermore, the level of cloud cover significantly impacts the strength of turbulence, with the highest cloud cover resulting in a substantial increase in log C n 2 (approximately -11 m -2/3 ) due to intense updraft and downdraft motions compared to clear skies. Additionally, the distribution of aerosol loading across the site, coupled with the behavior of BLH, atmospheric stability, and orographic-induced circulations, implies distinctive seasonal mechanisms for transporting aerosols toward the mountains. This study offers valuable insights into the diurnal and seasonal patterns of turbulent mixing and the mechanisms behind the transport of pollutants through boundary layer processes over the region.

54 ENVIRONMENTAL SCIENCES↗

Solubility of U(VI) in chloride solutions. II. The stable oxides/hydroxides in alkaline KCl solutions: Thermodynamic description and relevance in cementitious systems

In this study, the solubility of U(VI) is investigated from undersaturation conditions in 0.1, 0.51, 1.03, 3.31 and 4.58 m KCl–KOH solutions at pHm = 7.5–14.6 (with pH m = –log [H + ] in molal units). All experiments were performed under Ar atmosphere at T = (22 ± 2)°C. XRD, quantitative chemical analysis, SEM–EDS and TG–DTA confirm that K 2 U 2 O 7 ·1.5H 2 O(cr) is the solid phase controlling the solubility in all evaluated systems at pH m ≥ 9.5. Below this pH m and with decreasing KCl concentration, the formation of sub-stoichiometric phases with K:U < 1 is indicated by XRD and solubility data. The concentration of uranium in equilibrium with K 2 U 2 O 7 ·1.5H 2 O(cr) shows a pH-independent behaviour up to pH m ≈ 11 regardless of ionic strength, whereas an increase of the solubility with a well–defined slope of +1 (log [U] vs. pH m ) is observed at pH m ≥11. These results are consistent with the predominance of UO 2 (OH) 3 – and UO 2 (OH) 4 2- species as previously reported in the literature. The combination of solubility data obtained in the present study with K 2 U 2 O 7 ·1.5H 2 O(cr) and the U(VI) hydrolysis scheme reported in Altmaier et al. (2017) yields a solubility product of log *K° s ,0{0.5K 2 U 2 O 7 ·1.5H 2 O(cr)} = (12.0 ± 0.2). SIT ion interaction coefficients for UO 2 (OH) 3 – and UO 2 (OH) 4 2- with K + are derived based on the newly generated experimental data in dilute to concentrated KCl systems and analogy with NaCl systems. This work extends the thermodynamic database available for U(VI) and allows more accurate source term calculations in the context of nuclear waste disposal under boundary conditions where significant K concentrations may be present and redox conditions lie in the stability field of U(VI). Finally, the K 2 U 2 O 7 ·1.5H 2 O(cr) solid phase can be considered to control the solubility of U(VI) in the degradation phase I of cement and cementitious materials.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Maternal body burden of cadmium and offspring size at birth

Increasing evidence suggests an inverse association between cadmium (Cd) and size at birth, potentially greatest among female neonates. We evaluated whether greater maternal body burden of Cd is associated with reduced neonatal anthropometry (birthweight, birth length, head circumference, and ponderal index) and assessed whether these associations differ by infant sex. The analytic sample for the present study (n=396) was derived from a subcohort of 750 women randomly drawn from among all participants (N=4344) in the Omega Study, a prospective pregnancy cohort. Creatinine-corrected Cd in maternal clean-catch spot urine samples (U-Cd) was quantified by inductively coupled plasma mass spectrometry. Continuous log{sub 2}-transformed Cd (log{sub 2}-Cd) and U-Cd tertiles (low<0.29 μg/g creatinine, middle 0.29–0.42 μg/g creatinine, high≥0.43 μg/g creatinine) were used in multivariable linear regression models. Females had reduced birth length with greater U-Cd tertile, whereas males birth length marginally increased [β(95% CI) females: low=reference, middle=−0.59 cm (−1.37, 0.19), high=−0.83 cm (−1.69, 0.02), p-trend=0.08; males: low=reference, middle=0.18 cm (−0.59, 0.95), high=0.78 cm (–0.04, 1.60), p-trend=0.07; p for interaction=0.03]. The log{sub 2}-Cd by infant sex interaction was statistically significant for ponderal index [p=0.003; β(95% CI): female=0.25 kg/m{sup 3} (−0.20, 0.70); male=−0.63 kg/m{sup 3} (−1.01, −0.24)] and birth length [p<0.001; β(95% CI): female=−0.47 cm (−0.74, −0.20), male=0.32 cm (0.00, 0.65)]. Our findings suggest potential sex-specific reversal of Cd’s associations on birth length and contribute to the evidence suggesting Cd impairs fetal growth. - Highlights: • Cadmium levels in the general population potentially adversely affect size at birth. • Maternal urinary cadmium was inversely related to birth length among female infants. • For male infants, maternal cadmium was positively associated with birth length. • Maternal cadmium was also inversely related to ponderal index among male infants.

54 ENVIRONMENTAL SCIENCES↗

Use of a silver-based sanitizer to accelerate Escherichia coli die-off on fresh-cut lettuce and maintain produce quality during cold storage: Laboratory and pilot-plant scale tests

Outbreaks and product recalls involving romaine and iceberg lettuce are frequently reported in the United States. Novel technologies are needed to inactivate pathogens without compromising product quality and shelf life. In this study, the effects of a process aid composed of silver dihydrogen citrate, glycerin, and lactic acid (SGL) on Escherichia coli and Listeria monocytogenes concentrations on lettuce immediately after washing and during cold storage were evaluated. Sensory and quality attributes of fresh-cut iceberg lettuce were also evaluated. Laboratory results indicated that application of SGL solution for 30 s as a first step in the washing process resulted in a 3.15 log reduction in E. coli O157:H7 immediately after washing. For E. coli O157:H7 a significant difference between SGL treatment and all other treatments was maintained until day 7. On day zero, SGL led to a 2.94 log reduction of L. monocytogenes. However, there was no significant difference between treatments with or without SGL regardless of storage time. Pilot-plant results showed that samples receiving SGL spray followed by chlorinated flume wash exhibited a greater reduction (1.48 log) in nonpathogenic E. coli populations at the end of shelf life than other treatments (p < 0.05). Additional pilot plant tests were conducted to investigate the hypothesis that SGL residues could continue to impact microbial survival on the final washed lettuce. Results show that pathogens introduced subsequent to flume washing of lettuce pretreated with SGL solution were not affected by antimicrobial residues. Here, the final quality and shelf life of flume washed lettuce were also unaffected by pretreatment with SGL. In conclusion, the results of this study demonstrate that this new technology has the potential to accelerate E. coli die-off on fresh-cut lettuce during cold storage and improve product safety, while not affecting quality throughout the shelf life of the finished products.

59 BASIC BIOLOGICAL SCIENCES↗

National forest timber bids and export price interlinkages in the USA: The bounds testing approach

We examine the interrelationships of national forest timber bid and log export prices for Douglas-fir (Region 6) in 2003–2021 and loblolly pine (Region 8) using time-series stationarity and bounds-testing approaches. The analysis shows the difference in time series properties across different geographies and time scales. Bid prices for these dominant species of timber in each of two Forest Service regions are found to be stationary, while log export prices for those same species appear to be non-stationary. Bounds testing conducted with autoregressive distributed lag modeling methods provides strong evidence for a cointegrating relationship between timber bid prices and log export prices in Forest Service Region 6. In Region 8, evidence for a cointegrating relationship was weak. Here, the share of salvage wood in national forest timber sales is a statistically significant control variable in all models estimated.

54 ENVIRONMENTAL SCIENCES↗

SoK: What does it Mean to Benchmark Database Forensics?

Relational Database Management Systems are the backbone of modern enterprises and public-sector services, and are thus frequent targets of security incidents, insider threats, and thorough regulatory audits. Consequently, databases have become key sources of digital evidence, requiring investigators to reconstruct past activity from audit logs, transaction logs, and backups. Although benchmarking frameworks such as those developed by the Transaction Processing Performance Council (TPC) are widely used to evaluate database performance, they do not capture forensic requirements such as evidentiary completeness, tamper-evidence, chain of custody, or regulatory compliance under GDPR and CCPA. This survey examines the emerging domain of forensic database benchmarking. We gathered prior research on database forensics, secure logging, and tamper-evident data structures; we analyze modern forensic-ready features in commercial and open-source systems (SQL Server Ledger, Oracle Blockchain Tables, PostgreSQL pgAudit, Db2 Audit, Aurora Database Activity Streams, Oracle Real Application Security and IBM Guardium) and assess why existing benchmarks are insufficient. We propose forensic workloads, metrics, and methodologies that incorporate adversarial stressors, deleted-record recovery, and backup analysis. We also identify open research problems and call for a community-driven forensic benchmark suite. The result is an idea for evaluating not only database performance but also forensic soundness, bridging the gap between system engineering, compliance, and digital investigations.

Lenard, Ben↗

Dissolution of nontronite in chloride brines and implications for the aqueous history of Mars

Increasing evidence suggests the presence of recent liquid water, including brines, on Mars. Brines have therefore likely impacted clay minerals such as the Fe-rich mineral nontronite found in martian ancient terrains. So to interpret these interactions, we conducted batch experiments to measure the apparent dissolution rate constant of nontronite at 25.0 °C at activities of water (aH 2 O) of 1.00 (0.01 M CaCl 2 or NaCl), 0.75 (saturated NaCl or 3.00 mol kg -1 CaCl 2 ), and 0.50 (5.00 mol kg -1 CaCl 2 ). Experiments at aH 2 O = 1.00 (0.01 M CaCl 2 ) were also conducted at 4.0 °C, 25.0 °C, and 45.0 °C to measure an apparent activation energy for the dissolution of nontronite. Apparent dissolution rate constants at 25.0 °C in CaCl 2 -containing solutions decrease with decreasing activity of water as follows: 1.18 × 10 -12 ± 9 × 10 -14 mol mineral m -2 s -1 (aH 2 O = 1.00) > 2.36 × 10 -13 ± 3.1 × 10 -14 mol mineral m -2 s -1 (aH 2 O = 0.75) > 2.05 × 10 -14 ± 2.9 × 10 -15 mol mineral m -2 s -1 (aH 2 O = 0.50). Similar results were observed at 25.0 °C in NaCl-containing solutions: 1.89 × 10 -12 ± 1 × 10 -13 mol mineral m -2 s -1 (aH 2 O = 1.00) > 1.98 × 10 -13 ± 2.3 × 10 -14 mol mineral m -2 s -1 (aH 2 O = 0.75). This decrease in apparent dissolution rate constants with decreasing activity of water follows a relationship of the form: log k diss = 3.70 ± 0.20 × aH 2 O - 15.49, where k diss is the apparent dissolution rate constant, and aH 2 O is the activity of water. The slope of this relationship (3.70 ± 0.20) is within uncertainty of that of other minerals where the relationship between dissolution rates and activity of water has been tested, including forsteritic olivine (log R = 3.27 ± 0.91 × aH 2 O - 11.00) and jarosite (log R = 3.85 ± 0.43 × aH 2 O - 12.84), where R is the mineral dissolution rate. This result allows prediction of mineral dissolution as a function of activity of water and suggests that with decreasing activity of water, mineral dissolution will decrease due to the role of water as a ligand in the reaction. Apparent dissolution rate constants in the dilute NaCl solution (1.89 × 10 -12 ± 1 × 10 -13 mol mineral m -2 s -1 ) are slightly greater than those in the dilute CaCl 2 solutions (1.18 × 10 -12 ± 9 × 10 -14 mol mineral m -2 s -1 ). We attribute this effect to the exchange of Na with Ca in the nontronite interlayer. An apparent activation energy of 54.6 ± 1.0 kJ/mol was calculated from apparent dissolution rate constants in dilute CaCl 2 -containing solutions at temperatures of 4.0 °C, 25.0 °C, and 45.0 °C: 2.33 × 10 -13 ± 1.3 × 10 -14 mol mineral m -2 s -1 (4.0 °C), 1.18 × 10 -12 ± 9 × 10 -14 mol mineral m -2 s -1 (25.0 °C), and 4.98 × 10 -12 ± 3.8 × 10 -13 mol mineral m -2 s -1 (45.0 °C). The greatly decreased dissolution of nontronite in brines and at low temperatures suggests that any martian nontronite found to be perceptibly weathered may have experienced very long periods of water–rock interaction with brines at the low temperatures prevalent on Mars, with important implications for the paleoclimate and long-term potential habitability of Mars.

58 GEOSCIENCES↗