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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

A Nonlinear Viscoelastic Model for Ceramics at High Temperatures

High-temperature creep behavior of ceramics is characterized by nonlinear time-dependent responses, asymmetric behavior in tension and compression, and nucleation and coalescence of voids leading to creep rupture. Moreover, creep rupture experiments show considerable scatter or randomness in fatigue lives of nominally equal specimens. To capture the nonlinear, asymmetric time-dependent behavior, the standard linear viscoelastic solid model is modified. Nonlinearity and asymmetry are introduced in the volumetric components by using a nonlinear function similar to a hyperbolic sine function but modified to model asymmetry. The nonlinear viscoelastic model is implemented in an ABAQUS user material subroutine. To model the random formation and coalescence of voids, each element is assigned a failure strain sampled from a lognormal distribution. An element is deleted when its volumetric strain exceeds its failure strain. Element deletion has been implemented within ABAQUS. Temporal increases in strains produce a sequential loss of elements (a model for void nucleation and growth), which in turn leads to failure. Nonlinear viscoelastic model parameters are determined from uniaxial tensile and compressive creep experiments on silicon nitride. The model is then used to predict the deformation of four-point bending and ball-on-ring specimens. Simulation is used to predict statistical moments of creep rupture lives. Numerical simulation results compare well with results of experiments of four-point bending specimens. The analytical model is intended to be used to predict the creep rupture lives of ceramic parts in arbitrary stress conditions.

Powers, Lynn M.↗
NASA NTRS2004

Bioavailability and Pharmacodynamics of Promethazine in Human Subjects

The acute effects of exposure to microgravity include the development of space motion sickness, which usually requires therapeutic intervention. The current drug of choice, promethazine (PMZ), is available to astronauts in three different dosage forms during space flight; its side effects include nausea, dizziness, sedation and impaired psychomotor performance. This ground-based study is designed to validate flight-suitable methods for pharmacodynamic evaluation of PMZ and to estimate bioavailability and pharmacodynamics of PMZ. Experimental design consists of intramuscular administration of three doses of PMZ (12.5,25 and 50 mg) and placebo in a randomized double blind fashion to human subjects and collecting blood, urine and saliva samples for 72 h. Subjects also complete cognitive performance test batteries, WinSCAT (Windows based Space Cognitive Assessment Test) and ARES (ANAM Readiness Evaluation System). Preliminary results indicate a significant relationship (p=9.88e-05) between circulating PMZ levels and cognitive performance parameters. Time to accurately complete memory tasks increases significantly with concentrations; higher concentrations also increase response time and decrease accuracy of substitution and matching tasks. AUC and half-life estimates for PMZ ranged between 0.12 and 1.7 mg.h/L and 15 and 50 h, respectively. These preliminary results indicate that PMZ may exhibit dose-dependent pharmacokinetics in humans; also, WinSCAT and ARES are sensitive for pharmacodynamic assessment of PMZ, and may be applicable for assessing the pharmacodynamics of other neurocognitive drugs.

Boyd, J. L.↗
NASA NTRS2020

Southern Colorado Disasters: Using NASA Observations to Map Aspen Extent and Recovery Due to Wildfire

Quaking aspen (Populus tremuloides) is an important species for wildlife, watershed health, and ecosystem resilience across its range. Heavy ungulate browsing and factors influenced by a changing climate including seasonal temperature changes and moisture deficit have led to reduced post-fire aspen regeneration rates in southern Colorado. This project partnered with Trinchera Ranch and the Colorado State Forest Service to estimate aspen recovery after the Spring Creek Fire, which ignited in June of 2018. The Southern Colorado Disasters team utilized field measurements and satellite imagery from Landsat Operational Land Imager (OLI), Sentinel-2 MultiSpectral Instrument (MSI), and the Shuttle Radar Topography Mission (SRTM) to train and run several random forest models that detect pre- and post-fire aspen extent. Ocular sampling of over 500 points on high-resolution pre-fire and post-fire images identified percentage aspen cover in 30 x 30-meter grid cells. This process provided training data for regression models, which were able to detect aspen across the landscape for both time periods using multiple remote sensing vegetation health indices. In addition, landscape suitability for aspen regeneration was modeled to provide a guide for managers on where to monitor for aspen regeneration post-fire.

DEVELOP Project Summary↗
NASA NTRS2020

Southern Colorado Disasters: Using NASA Earth Observations to Map Aspen Extent and Recovery Due to Wildfire

Quaking aspen (Populus tremuloides) is an important species for wildlife, watershed health, and ecosystem resilience across its range. Heavy ungulate browsing and factors influenced by a changing climate including seasonal temperature changes and moisture deficit have led to reduced post-fire aspen regeneration rates in southern Colorado. This project partnered with Trinchera Ranch and the Colorado State Forest Service to estimate aspen recovery after the Spring Creek Fire, which ignited in June of 2018. The Southern Colorado Disasters team utilized field measurements and satellite imagery from Landsat Operational Land Imager (OLI), Sentinel-2 MultiSpectral Instrument (MSI), and the Shuttle Radar Topography Mission (SRTM) to train and run several random forest models that detect pre- and post-fire aspen extent. Ocular sampling of over 500 points on high-resolution pre-fire and post-fire images identified percentage aspen cover in 30 x 30-meter grid cells. This process provided training data for regression models, which were able to detect aspen across the landscape for both time periods using multiple remote sensing vegetation health indices. In addition, landscape suitability for aspen regeneration was modeled to provide a guide for managers on where to monitor for aspen regeneration post-fire.

DEVELOP Technical Paper↗
NASA NTRSDate not supplied

Mineralogical, Elemental, and Tomographic Reconnaissance Investigation for CLPS (METRIC): A Proposed Mission to the Lunar South Pole-Aitken Basin

The global Lunar Magma Ocean (LMO) hypothesis is based on analyses of ferroan anorthosites (FAN), magnesian plutonic rocks (Mg-suite), and KREEPy (Potassium - K; Rare Earth Elements - REE; Phosphorous - P) material present at the Apollo landing sites and the assumed global distribution of these lithologies. However, orbital spacecraft data over the last two decades have highlighted that the location of the Apollo missions within and near the Procellarum KREEP Terrane (PKT) is compositionally anomalous and not representative of the entire lunar surface and suggests that Apollo samples provide a biased view of the Moon. Further, meteorites, which originate from random areas on the lunar surface, including those not visited by Apollo, Luna, or Chang’E-5, provide complementary datasets that reveal a more complex lunar formation and evolution than the simple LMO onion skin model. While many recent investigations support and refine the LMO model, other recent studies have questioned whether this mechanism alone is responsible for the primordial differentiation of the Moon. Thus, relating the distinct and asymmetrically distributed geochemical terranes on the Moon, especially KREEP which is a predicted global LMO product, to lunar formation and differentiation remains a fundamental goal of lunar science. The South Pole-Aitken (SPA) impact carved a two-and-a-half thousand-kilometer basin into the Moon’s ancient crust, excavating material from as deep as the upper mantle. Orbital remote sensing of the basin indicates compositions with elevated thorium (Th) contents and unique mineralogies that provide a window into early lunar structure and LMO processes. We propose to land a powerful characterization laboratory at Birkeland crater on the far side of the Moon–where Th-rich SPA ejecta have been re-exposed near the surface–in order to address outstanding questions about the evolution of the Moon.

K M Cannon↗
DOE OSTI2026

Efficient many-jet event generation with flow matching

We apply for the first time, to the best of our knowledge, the flow matching method to the problem of phase-space sampling for event generation in high-energy collider physics. By training the model to remap the random numbers used to generate the momenta and helicities of the scattering matrix elements as implemented in the portable partonic event generator pepper, we find substantial efficiency improvements in the studied processes. We focus our study on the highest final-state multiplicities in Drell-Yan and top-antitop pair production used in simulated samples for the Large Hadron Collider, which computationally are the most relevant ones. We find that the unweighting efficiencies improve by factors of 184 and 25, respectively, when compared to the standard approach of using a vegas-based optimization. We also compare continuous normalizing flows trained with flow matching against the previously studied normalizing flows based on coupling layers and find that the former leads to better results, faster training and a better scaling behavior across the studied multiplicity range, while the latter evaluate faster. When combining the advantages of both methods using the regflow approach, we find parton-level unweighted event generation walltime gains of about a factor of 10 at the highest final-state multiplicities.

Bothmann, E. [CERN; Gottingen U.] (ORCID:000000016↗
NASA NTRS2012

Geochemistry of Lunar Highland Meteorites Mil, 090034, 090036 AND 090070

Apollo and Luna samples were collected from a restricted area on the near side of the Moon, while the source craters of the lunar meteorites are randomly distributed. For example, Takeda et al. [1] and Yamaguchi et al. [2] found a variety of lithic clasts in Dho 489 and Y 86032 which were not represented by Apollo samples, and some of these clasts have lower rare earth elements (REE) and FeO abundances than Apollo anorthosites, respectively. Takeda et al. [1] and Yamaguchi et al. [2] concluded that Dho 489 and Y 86032 originated from the lunar farside. Therefore, lunar meteorites provide an opportunity to study lunar surface rocks from areas not sampled by Apollo and Luna missions. Three lunar anorthitic breccias (MIL 090034, 090036 and 090070) were found on the Miller Range Ice Field in Antarctica during the 2009-2010 ANSMET season [3]. In this study, we determined elemental abudnances for MIL 090034, 090036 and 090070 by using INAA and aimed to characterize these meteorites in chemical compositions in comparison with those for other lunar meteorites and Apollo samples.

Shirai, N.aoki↗
NASA NTRS1977

Testing the accuracy of remote sensing land use maps

Some of the main aspects that need to be considered in a remote sensing sampling design are: (1) the frequency that any one land use type (on the ground) is erroneously attributed to another class by the interpreter; (2) the frequency that the wrong land use (as observed on the ground) is erroneously included in any one class by the remote sensing interpreter; (3) the proportion of all land (as determined in the field) that is mistakenly attributed by the interpreter; and (4) the determination of whether the mistakes are random (so that the overall proportions are approximately correct) or subject to a persistent bias. A sampling and statistical testing procedure is presented which allows an approximate answer to each of these aspects. The concept developed and described incorporates the probability of making incorrect interpretations at particular prescribed accuracy levels, for a certain number of errors, for a particular sample size. It is considered that this approach offers a meaningful explanation of the interpretation accuracy level of an entire remote sensing land use survey.

Vangenderen, J. L.↗
DOE OSTI2025

The polarized-signal density matrix: A practical way to recover molecular frame information from isotropic samples

We present a novel approach to model ultrafast time-dependent nonlinear optical polarization sensitive signals emitted from randomly oriented molecules. By projecting the laboratory-frame analyzer polarization axis into the molecular-frame and linking that axis with the density matrix through a tensor product, we demonstrate an approach to find a specific molecular orientation that yields a good approximation to simulated four-wave mixing signals produced by the same model but with averaging over molecular orientation.

Thurston, Richard L↗
DOE OSTI2016

STRUCTURAL STUDIES OF EIGHT BRIGHT RIMMED CLOUDS IN THE SOUTHERN HEMISPHERE

We carried out deep- and wide-field near- and mid-infrared observations for a sample of eight bright-rimmed clouds (BRCs). Supplemented with the Spitzer archival data, we have identified and classified 44 to 433 young stellar objects (YSOs) associated with these BRCs. The Class I sources are generally located toward the places with higher extinction and are relatively closer to each other than the Class II sources, confirming that the young protostars are usually found in regions with denser molecular material. On the other hand the comparatively older population, Class II objects, are more randomly found throughout the regions, which can be due to their dynamical evolution. Using the minimal sampling tree analyses, we have extracted 13 stellar cores of eight or more members, which contain 60% of the total YSOs. The typical core is ∼0.6 pc in radii and somewhat elongated (aspect ratio of 1.45), of relatively low stellar density (surface density 60 pc{sup −2}), consisting of a small (35) number of YSOs of relatively young sources (66% Class I), and partially embedded (median A{sub K} = 1.1 mag). But the cores show a wide range in their mass distribution (∼20 to 2400 M {sub ⊙}), with a median value of around 130 M {sub ⊙}. We found the star-formation efficiencies in the cores to be between 3% and 30% with an average of ∼14%, which agrees with the efficiencies needed to link the core mass function to the initial mass function. We also found a linear relation between the density of the clouds and the number of YSOs. The peaked nearest neighbor spacing distributions of the YSOs and the ratio of Jeans lengths to the YSO separations indicates a significant degree of non-thermally driven fragmentation in these BRCs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

An adaptive Hessian approximated stochastic gradient MCMC method

Bayesian approaches have been successfully integrated into training deep neural networks. One popular family is stochastic gradient Markov chain Monte Carlo methods (SG-MCMC), which have gained increasing interest due to their ability to handle large datasets and the potential to avoid overfitting. Although standard SG-MCMC methods have shown great performance in a variety of problems, they may be inefficient when the random variables in the target posterior densities have scale differences or are highly correlated. Here, we present an adaptive Hessian approximated stochastic gradient MCMC method to incorporate local geometric information while sampling from the posterior. The idea is to apply stochastic approximation (SA) to sequentially update a preconditioning matrix at each iteration. The preconditioner possesses second-order information and can guide the random walk of a sampler efficiently. Instead of computing and saving the full Hessian of the log posterior, we use limited memory of the samples and their stochastic gradients to approximate the inverse Hessian-vector multiplication in the updating formula. Moreover, by smoothly optimizing the preconditioning matrix via SA, our proposed algorithm can asymptotically converge to the target distribution with a controllable bias under mild conditions. To reduce the training and testing computational burden, we adopt a magnitude-based weight pruning method to enforce the sparsity of the network. Our method is user-friendly and demonstrates better learning results compared to standard SG-MCMC updating rules. The approximation of inverse Hessian alleviates storage and computational complexities for large dimensional models. Numerical experiments are performed on several problems, including sampling from 2D correlated distribution, synthetic regression problems, and learning the numerical solutions of heterogeneous elliptic PDE. The numerical results demonstrate great improvement in both the convergence rate and accuracy.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS2007

Non-Random Spatial Distribution of Impacts in the Stardust Cometary Collector

In January 2004, the Stardust spacecraft flew through the coma of comet P81/Wild2 at a relative speed of 6.1 km/sec. Cometary dust was collected at in a 0.1 sq m collector consisting of aerogel tiles and aluminum foils. Two years later, the samples successfully returned to earth and were recovered. We report the discovery that impacts in the Stardust cometary collector are not distributed randomly in the collecting media, but appear to be clustered on scales smaller than approx.10 cm. We also report the discovery of at least two populations of oblique tracks. We evaluated several hypotheses that could explain the observations. No hypothesis was consistent with all the observations, but the preponderance of evidence points toward at least one impact on the central Whipple shield of the spacecraft as the origin of both clustering and low-angle oblique tracks. High-angle oblique tracks unambiguously originate from a noncometary impact on the spacecraft bus just forward of the collector. Here we summarize the observations, and review the evidence for and against three scenarios that we have considered for explaining the impact clustering found on the Stardust aerogel and foil collectors.

Westphal, Andrew J.↗
NASA NTRS2003

Estimating Terrestrial Carbon Exchange from Space: How Often and How Well?

Data from a new space mission measuring integrated light-use efficiency could provide a breakthrough in understanding of global carbon, water, and energy dynamics, and greatly improve the accuracy of model predictions for terrestrial carbon cycles and climate. Over the past decade, Gamon and others have shown that changes in photo-protective pigments are sensitive indicators of declines in light-use efficiency of plants and plant canopies. The requirements for integrated diurnal measurements from space need to be defined, before a space mission can be formulated successfully using this concept. We used towerbased CO 2 flux data as idealized proxies for remote measurements, examining their sampling properties. Thousands of half-hourly CO 2 flux measurements are needed before their average begins to converge on an average annual net CO 2 exchange. Estimates of daily integrated fluxes (i.e., diurnal curves) are more statistically efficient, especially if the spacing between measured days is quasiregular, rather than random. Using a few measurements per day one can distinguish among days with different net CO 2 exchanges. Fluxes sampled between mid-morning to mid-afternoon are more diagnostic than early morning or late afternoon measurements. Similar results (correlation >0.935) were obtained using 2 measurements per day with high accuracy ([:plusmn:]5%), 3 measurements per day with medium accuracy ([:plusmn:] 10%), or 5 measurements per day at lower accuracy ([:plusmn:]20%). An observatory in a geosynchronous or near-geosynchronous orbit could provide appropriate observations, as could a multi-satellite constellation in polar orbits, but there is a potential trade-off between the required number of observations per day and quality of each observation.

Knox, Robert G.↗
NASA NTRS2006

Precipitation and Latent Heating Distributions from Satellite Passive Microwave Radiometry. Part II: Evaluation of Estimates Using Independent Data

Rainfall rate estimates from spaceborne microwave radiometers are generally accepted as reliable by a majority of the atmospheric science community. One of the Tropical Rainfall Measuring Mission (TRMM) facility rain-rate algorithms is based upon passive microwave observations from the TRMM Microwave Imager (TMI). In Part I of this series, improvements of the TMI algorithm that are required to introduce latent heating as an additional algorithm product are described. Here, estimates of surface rain rate, convective proportion, and latent heating are evaluated using independent ground-based estimates and satellite products. Instantaneous, 0.5 deg. -resolution estimates of surface rain rate over ocean from the improved TMI algorithm are well correlated with independent radar estimates (r approx. 0.88 over the Tropics), but bias reduction is the most significant improvement over earlier algorithms. The bias reduction is attributed to the greater breadth of cloud-resolving model simulations that support the improved algorithm and the more consistent and specific convective/stratiform rain separation method utilized. The bias of monthly 2.5 -resolution estimates is similarly reduced, with comparable correlations to radar estimates. Although the amount of independent latent heating data is limited, TMI-estimated latent heating profiles compare favorably with instantaneous estimates based upon dual-Doppler radar observations, and time series of surface rain-rate and heating profiles are generally consistent with those derived from rawinsonde analyses. Still, some biases in profile shape are evident, and these may be resolved with (a) additional contextual information brought to the estimation problem and/or (b) physically consistent and representative databases supporting the algorithm. A model of the random error in instantaneous 0.5 deg. -resolution rain-rate estimates appears to be consistent with the levels of error determined from TMI comparisons with collocated radar. Error model modifications for nonraining situations will be required, however. Sampling error represents only a portion of the total error in monthly 2.5 -resolution TMI estimates; the remaining error is attributed to random and systematic algorithm errors arising from the physical inconsistency and/or nonrepresentativeness of cloud-resolving-model-simulated profiles that support the algorithm.

Yang, Song↗
NASA NTRS1998

Development of a Probabilistic Dynamic Synthesis Method for the Analysis of Nondeterministic Structures

Accounting for the statistical geometric and material variability of structures in analysis has been a topic of considerable research for the last 30 years. The determination of quantifiable measures of statistical probability of a desired response variable, such as natural frequency, maximum displacement, or stress, to replace experience-based "safety factors" has been a primary goal of these studies. There are, however, several problems associated with their satisfactory application to realistic structures, such as bladed disks in turbomachinery. These include the accurate definition of the input random variables (rv's), the large size of the finite element models frequently used to simulate these structures, which makes even a single deterministic analysis expensive, and accurate generation of the cumulative distribution function (CDF) necessary to obtain the probability of the desired response variables. The research presented here applies a methodology called probabilistic dynamic synthesis (PDS) to solve these problems. The PDS method uses dynamic characteristics of substructures measured from modal test as the input rv's, rather than "primitive" rv's such as material or geometric uncertainties. These dynamic characteristics, which are the free-free eigenvalues, eigenvectors, and residual flexibility (RF), are readily measured and for many substructures, a reasonable sample set of these measurements can be obtained. The statistics for these rv's accurately account for the entire random character of the substructure. Using the RF method of component mode synthesis, these dynamic characteristics are used to generate reduced-size sample models of the substructures, which are then coupled to form system models. These sample models are used to obtain the CDF of the response variable by either applying Monte Carlo simulation or by generating data points for use in the response surface reliability method, which can perform the probabilistic analysis with an order of magnitude less computational effort. Both free- and forced-response analyses have been performed, and the results indicate that, while there is considerable room for improvement, the method produces usable and more representative solutions for the design of realistic structures with a substantial savings in computer time.

Brown, A. M.↗
DOE OSTI2024

Sampling Size Optimization for Bioburden Density Estimation in Planetary Protection

Planetary protection (PP) is a discipline that focuses on minimizing the biological contamination of spacecraft to ensure compliance with international policy. Precise estimation of bioburden - the total number of microbes in or on spacecraft hardware – and the bioburden density are of utmost importance for PP. Such estimation is the way concordance with requirements is demonstrated, and it is critical for quantifying the potential risk of inadvertently contaminating other planetary bodies. Although a suite of molecular techniques have been used to thoroughly characterize and profile the microbiome of various cleanroom environments and spacecraft, the gold standard remains the physical enumeration of microbes via culturing of samples directly taken from spacecraft and associated surfaces. However, due to technical, budgetary, and programmatic constraints, only a manageable portion (around 10%) of the entire spacecraft surface is directly sampled with cotton swabs or wipes. To generate the bioburden current best estimate (CBE) for components not directly verifiable, the accepted approach is to apply a NASA-defined bioburden estimate based on the components’ manufacturing or assembly environment. This approach utilizes a prespecified bioburden density estimation that applies a maximum value across the total surface area of the specified component. For hardware components that underwent similar assembly processes, an implied bioburden is adopted for all components, based on a direct verification of a representative component within the same lot. Once all components have a CBE, the bioburden estimates are generated. In previous publication [ 1], we have shown that statistical risks quantifying the accuracy of the estimates for sampled, prespecified, and implied components can be derived and ranked. For mean squared error (MSE) function, the risks are available analytically and hence a cost function can be obtained to optimize the risks with respect to the sampling area and sampling cost. Since the sampling area and sampling cost are two complimentary variables, their sum will have a well-defined minimum. This paper presents the multivariate optimization of the integrated risk of an empirical Bayes estimator to determine the optimal sampling schedule for a given number of components. It is assumed that given a number of components, N, the bioburden density for each component can either be sampled, implied, or prespecified. The multivariate optimization searches through different options to sample, imply or prespecify the bioburden density for a component, and account for the component’s surface area and cost of sampling. The idea of the optimization is based on the observation that the statistical risk of using an estimator is a monotonically decreasing function of the sampled area. The larger the sampled area, the lower the risk of using the estimator as the estimator becomes more and more accurate as the sampling area increases. On the other hand, the cost of sampling is monotonically increasing as the sampled surface grows. This makes the risk and total cost of sampling complimentary variables which can be counterbalanced to achieve an optimal overall value with respect to the sampled surface. In this paper, the integrated risk has been used to quantify the accuracy of the estimator. This risk has been selected because it depends on neither the true value of the parameter nor on the collected data. The cost of each sample was also available to obtain the total cost of sampling of N components. The paper will present the results based on computer-simulated data as well as the data collected during the InSight mission. The computer-simulated data have N components with randomly generated total areas and each component assigned to one of the three categories according to the method of estimating of bioburden density: sampled, implied, or prespecified. The cost of sampling is also available. The cost of sampling is estimated based on a cost model provided by the planetary protection group at JPL. For this paper, the overall cost was assumed to be a linear function of exposure. The optimization process finds the allocation of the components to the three categories that minimizes the tradeoff between integrated risk and total cost. For the InSight data, a set of components is selected representing all three categories, and optimization is performed to determine if the performed allocation was optimal or if a better allocation could have been obtained. To the best of our knowledge, this work is the first attempt not only perform an accurate estimation of bioburden density but also do it in an optimal way.

97 - MATHEMATICS AND COMPUTING↗
DOE OSTI2016

Highly-defective nanocrystals of ZnS formed via dissimilatory bacterial sulfate reduction: A comparative study with their abiogenic analogues

The physicochemical properties of a (nano)mineral are strongly affected by its formation processes, and thus, may indicate the (nano)mineral’s formation environment and mechanism. This correlation, although relevant to a myriad of geological, environmental, and material-science processes, has not yet been fully appreciated and systematically explored. In this study, using the Zn–S system, we demonstrate that biological and abiotic processes at similar experimental conditions can produce distinctive particle size, morphology, and crystal structure in the formed ZnS. Specifically, bacterial sulfate reduction led to the formation of highly-defective nanocrystals of mixed sphalerite and wurtzite in a range of ~4–12 nm. By comparison, the abiotic procedures of titration- or diffusion-controlled precipitation resulted in the formation of polycrystalline aggregates that contained randomly-oriented, ultrafine crystals below ~2–3 nm. The poor crystallinity in the abiogenic samples, regardless of the sulfide addition rates, reveals an overall nucleation-dominated, crystal growth-restricted pathway for the formation of ZnS from low-temperature aqueous solutions. The difficulty in the ZnS crystallization likely stems from the intrinsic surface instability of the ZnS growth units (i.e., in the form of nanoclusters) resulting from the dipole–dipole interactions of the unit with surrounding water molecules. In the biogenic samples, the ZnS crystallinity was significantly improved, indicating that the presence of bacterial metabolites somehow promoted the crystallization process. With evidence for the enlarged {1 1 1} planes in the biogenic nanocrystals, we attribute this enhancement mainly to the selective interaction of the bacterial metabolites with polar faces of the ZnS growth units, which might have effectively screened the dipole moments in the growth units and enabled their crystallographic assembly. By revealing the intrinsic difficulty and specific pathways for the ZnS crystallization, we also present viable explanations for the exclusive occurrence of structural defects in {1 1 1} planes of the biogenic nanocrystals. The findings of our study provide insight into the origin and fate of metal sulfide nanoparticles in the environment, and have implications for biomineralization, bioremediation of metal-contaminated sites, and bacterial production of functional nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗