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DOE OSTI2022

Ice nucleating particle concentrations measured by the CSU-CFDC during the AGINSGP field experiment

Real-time, immersion mode ambient ice nucleating particle (INP) concentrations were measured at ARM’s Southern Great Plains (SGP) site during the AGINSGP field experiment using a continuous flow diffusion chamber (CFDC) from Colorado State University (CSU). The CSU-CFDC is an ice-thermal gradient diffusion chamber that optically detects the freezing of single aerosol particles (Rogers 1988; Rogers et al. 2001; and Eidhammer et al. 2010). The instrument was located in the guest instrument facility (GIF) and measured INP concentrations from April 8th to April 29th. Air was drawn into the GIF through custom aluminum stack inlets (6” inner diameter) attached vertically to the outer GIF wall and the GIF outside platform. A blower pulled air through the stacks at a velocity of 1 m/s. Aerosol instruments subsampled via wall ports, through either 3/8” or 1/4" copper lines, depending on sample flow of the instrument. Rogers, D. C., Development of a continuous flow thermal gradient diffusion chamber for ice nucleation studies, Atmospheric Research, 22(2), 149-181, doi:10.1016/0169-8095(88)90005-1, 1988. Rogers, D. C., P. J. DeMott, S. M. Kreidenweis and Y. Chen, A continuous flow diffusion chamber for airborne measurements of ice nuclei, J. Atmos. Oceanic Technol., 18, 725-741, doi:10.1175/1520-0426(2001)018<0725:ACFDCF>2.0.CO;2, 2001. Eidhammer, T., DeMott, P. J., Prenni, A. J., Petters, M. D., Twohy, C. H., Rogers, D. C., Stith, J., Heymsfield, A., Wang, Z., Haimov, S., French, J., Pratt, K., Prather, K., Murphy, S., Seinfeld, J., Subramanian, R., and Kreidenweis, S. M., Ice initiation by aerosol particles: Measured and predicted ice nuclei concentrations versus measured ice crystal concentrations in an orographic wave cloud, J. Atmos. Sci., 67, 2417-2436, doi:10.1175/2010JAS3266.1, 2010

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Fluorescent bioaerosol particle concentrations measured by the DU WIBS during the AGINSGP field experiment

Real-time, immersion mode ambient fluorescent bioaerosol concentrations were measured at ARM’s Southern Great Plains (SGP) site during the AGINSGP field experiment using a Wideband Integrated Bioaerosol Sensor (DMT Inc.; WIBS-4A). The WIBS-4A is an optical particle counter that also measures single particle fluorescence in three channels, along with particle asymmetry. Particles are grouped into different types depending on which channels they fluoresce in. The instrument was located in the guest instrument facility (GIF) and measured fluorescent particle concentrations from April 7th to April 29th. Data presented here are the concentrations for each particle type, binned in 5 minute increments. Air was drawn into the GIF through custom aluminum stack inlets (6” inner diameter) attached vertically to the outer GIF wall and the GIF outside platform. A blower pulled air through the stacks at a velocity of 1 m/s. Aerosol instruments subsampled via wall ports, through either 3/8” or 1/4" copper lines, depending on sample flow of the instrument. Particles were dried using a silica diffusion dryer prior to analysis.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2018

Preparation and characterization of microwave absorbing composite materials with GSs or FeCo/GS composites

Highlights: • It is found that adding GSs or FeCo/GSs composite into the sample SiC/NR can greatly increase RL and the absorbing peak shifts to low-frequency with increasing the adding amount. • The optimum adding amount of GSs is 2%. The sample GS-200-2% possesses the lowest RL value of −31.27 dB at 7.6 GHz. • The optimum adding amount of FeCo/GSs composite is 3%. The sample AGS-450-3% possesses the lowest RL value of −20.67 dB at 7.8 GHz. - Abstract: This study mainly explored the synthesis method of graphene sheets (GSs) and FeCo/graphene sheet (FeCo/GS) composites and evaluated the microwave absorbing characteristics of composite materials containing GSs or FeCo/GS composites. First, graphite oxide (GO) was synthesized by the modified Hummers method. The synthesized GO was further used to synthesize GSs and FeCo/GS composites. Afterward, GSs or FeCo/GS composites were mixed with silicon carbide (SiC) and natural rubber (NR) to prepare microwave absorbing materials with thicknesses of 2 mm. Finally, identification and characterization of these samples were performed by XRD, FE-SEM, TEM, TGA, ESCA, RS, AFM and VNA. GSs were synthesized successfully at a low annealing temperature of 200 °C, and their thicknesses were between 0.848 nm and 2.115 nm, which corresponds to 2–6 stacked layers of graphene. FeCo/GS composites were also synthesized successfully at three different annealing temperatures. The nanoparticles of metals and metal oxides were well-dispersed on the surfaces of and the spaces between GSs. It was found that adding GSs or FeCo/GS composites into the SiC/NR sample can greatly increase reflection loss (RL) and that the absorbing peak shifts to lower frequencies as the concentration of added particles increases. The optimum concentration of added GSs was 2 wt.%. The GS-200-2% sample possessed the lowest RL value of −31.27 dB at 7.6 GHz. The optimum concentration of added FeCo/GS composites was 3 wt.%. The AGS-450-3% sample possessed the lowest RL value of −20.67 dB at 7.8 GHz.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Direct observations of crystal defects in polycrystalline diamond

Highlights: • Electron channeling contrast imaging of crystal defects in polycrystalline diamond • Introducing acid etching as a novel protocol for diamond surface preparation • Characterization of {111} twins, {111} stacking faults and {111} helical dislocations in diamond using ECCI and EBSD - Abstract: Crystal defects are abundant in synthetic diamond produced by chemical vapor deposition (CVD). We present the first images of crystal defects in a bulk polycrystalline CVD diamond sample using general electron channeling contrast imaging (ECCI) in a field emission scanning electron microscope (FE-SEM). For enhancement of channeling contrast of this material, we introduce a novel protocol for diamond surface preparation that involves acid etching. Using this protocol, we imaged three types of crystal defects including twins, stacking faults and dislocations. Each defect was identified based on its appearance in electron channeling contrast (ECC) micrographs. We analyzed grains containing twins and dislocations using electron backscatter diffraction (EBSD) crystal orientation mapping. We found a large population of grains that contained Σ3 type twins on {111} planes with a 60°<111> angle–axis pair of misorientation for twin boundaries. In addition, we identified {111} stacking faults and {111} helical dislocations. These observations are in agreement with reports of crystal defects in CVD diamond thin foils studied by a transmission electron microscope (TEM).

36 MATERIALS SCIENCE↗

DOE OSTI2026

Physicochemical properties of digital light processing 3D-Printed alumina and mullite ceramics

Alumina ceramics fabricated using conventional techniques such as uniaxial pressing or injection molding are popular due to their low density, excellent insulation, and mechanical properties. However, these methods often limit the fabrication of complex geometries with high dimensional accuracy due to tooling constraints and limited design freedom. To overcome these limitations, this study employed Digital Light Processing (DLP) additive manufacturing (AM), which enables the production of precise structures. In addition, the optimization of sintering parameters to enhance the densification and performance of alumina and mullite ceramics was investigated, with a specific focus on how varying sintering temperatures and hold times affect part shrinkage, geometric accuracy, and material integrity. Flexural strength of both alumina and mullite specimens was clearly influenced by the way the layers was stacked. When layers were arranged across the direction of the applied load (Z = 4; XZ), the strength was higher than when they were stacked along the same direction as the load (Z = 3; XY). Weibull analysis based on these results showed high modulus values across all samples, indicating good reliability in the flexural strength measurements. This reliability, combined with the clear influence of sintering parameters, highlights how processing conditions effect the material properties and mechanical performance of parts produced through DLP additive manufacturing. In conclusion, these findings open new avenues for ceramic AM across various applications, enhancing the potential for innovation in fields such as aerospace, biomedical engineering, and energy.

36 MATERIALS SCIENCE↗

DOE OSTI2023

10 Be at iThemba LABS using a silicon nitride membrane stack as absorber for isobar suppression

10 Be is an important isotope for accelerator mass spectrometry (AMS) because of the demand for cosmogenic radionuclide dating methods in the earth science and paleo-sciences community. At the iThemba Laboratory for Accelerator Based Science (iThemba LABS) we implemented full suppression of the interfering isobar 10 B using a silicon nitride foil-stack, utilizing the 2+ charge state for high efficiency. We demonstrate the performance of this newly established AMS system using standards and test samples. Here we further present the results of an inter-comparison between iThemba LABS and the Center for Accelerator Mass Spectrometry/Lawrence Livermore National Laboratory, on AMS samples prepared from purified quartz at the University of Vermont. The results for 10 Be from the laboratories are in close agreement, fully consistent with cross-calibration between them. AMS results for 26 Al are in similarly good agreement, demonstrating the performance and accuracy of iThemba LABS for the most commonly measured in situ produced cosmogenic nuclides.

10-Be↗

DOE OSTI2011

Application of IDT sensors for structural health monitoring of windmill turbine blades made of composite material

Interdigital transducers (IDT) generate and receive ultrasonic surface waves without the complexity involved with secondary devices such as angled wedges or combs. The IDT sensors have been successfully applied for the NDE of homogeneous materials like metals in order to detect cracks and de-bond. However, these transducers have not been yet adapted for complex and anisotropic materials like fiber-reinforced composites. This work presents the possibility of using IDT sensors for monitoring structural damages in wind turbine blades, typically made of fiberglass composites. IDT sensors with a range of operating frequency between 250 kHz and 1 MHz are initially tested on representative composite test panels for ultrasonic surface wave properties including beam spread, propagation distance and effect of material's anisotropy. Based on these results, an optimum frequency range for the IDT sensor is found to be 250-500 kHz. Subsequently, IDT sensors with operating frequency 500 kHz are used to detect and quantify artificial defects created in the composite test samples. Discussions are made on the interaction of ultrasonic fields with these defects along with the effects of fiber directionality and composite layer stacking.

42 ENGINEERING↗

DOE OSTI2014

High strain in polycrystalline Ni{sub 48.8}Mn{sub 31.4}Ga{sub 19.8} Heusler alloys under overlapped static and oscillating magnetic fields

Martensitic polycrystalline Ni{sub 48.8}Mn{sub 31.4}Ga{sub 19.8} Heusler alloys, with a stacking period of 14 atomic planes at room temperature, were innovatively processed by combining high-energy ball milling and powder metallurgy. Bulk samples were mechanically coupled to a piezoelectric material in a parallel configuration, and the mechanical deformation of the studied system due to the twin's variant motion was investigated under overlapped static and oscillating magnetic fields. A reversible and high mechanical deformation is observed when the frequency of the oscillating magnetic field is tuned with the natural vibration frequency of this system. In this condition, a linear deformation as a function of the static magnetic field amplitude occurs in the ±4 kOe range, and a mechanical deformation of 2% at 10 kOe is observed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Effective pair potential for random fcc CoCrFeMnNi alloys

The single-phase equiatomic CoCrFeMnNi alloy is a random solid solution of five elements on the face-centered cubic lattice, whose pure constituents crystallize in very different structures and exhibit diverse magnetic properties. Due to the randomness of the alloy, 80% of nearest neighbor bonds are between unlike elements and thus the details of bonding in pure structures are less important. The elastic moduli of this alloy give rise to small Cauchy pressure C 12 - C 44 , which suggests that the dominant part of bonding may be described by a simple pair potential. We test this hypothesis by developing a long-range Lennard-Jones potential in which the equilibrium crystal structures of pure constituents are taken as reference. The standard mixing rules for regular solutions are then adopted to obtain parameters for bonds between unlike elements in the quinary system. The transferability of this potential to quaternary CoCrFeNi, ternary CoCrNi, and binary FeNi alloys is investigated and the predictions compared with experiments and density functional theory calculations. By sampling over a large number of random configurations, we investigate the effect of compositional randomness on misfit volumes, energies of point defects and stacking faults, and the dislocation friction stresses experienced by moving edge and screw dislocations.

Materials Science↗

DOE OSTI2012

EXTREME STAR FORMATION IN THE HOST GALAXIES OF THE FASTEST GROWING SUPERMASSIVE BLACK HOLES AT z = 4.8

We report new Herschel observations of 25 z {approx_equal} 4.8 extremely luminous optically selected active galactic nuclei (AGNs). Five of the sources have extremely large star-forming (SF) luminosities, L{sub SF}, corresponding to SF rates (SFRs) of 2800-5600 M{sub Sun} yr{sup -1} assuming a Salpeter initial mass function. The remaining sources have only upper limits on their SFRs, but stacking their Herschel images results in a mean SFR of 700 {+-} 150 M{sub Sun} yr{sup -1}. The higher SFRs in our sample are comparable to the highest observed values so far at any redshift. Our sample does not contain obscured AGNs, which enables us to investigate several evolutionary scenarios connecting supermassive black holes and SF activity in the early universe. The most probable scenario is that we are witnessing the peak of SF activity in some sources and the beginning of the post-starburst decline in others. We suggest that all 25 sources, which are at their peak AGN activity, are in large mergers. AGN feedback may be responsible for diminishing the SF activity in 20 of them, but is not operating efficiently in 5 others.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2021

Comparison of NMC estimates with trans-stilbene, EJ-309, and He-3 detection systems

Neutron multiplicity counting (NMC) is a technique for the assay of fissile material. In this work, three detection systems are utilized for active interrogation assay of shells of the Rocky Flats shells (highly enriched uranium, 93% 235U) stacked from 13.25-54.92 kg assemblies. The singles ($R_1$) and doubles ($R_2$) rates are calculated with each system to estimate two sample parameters: $M_L$- the leakage multiplication and F - the sample fission rate. The estimated mass, m, is found by dividing F by a constant activity per unit mass. Since we are interrogating HEU, the α ratio of (α; n) to fission neutrons is taken to be zero. The system of equations to calculate these quantities was originally derived. The Neutron Multiplicity 3 He Array Detector (NOMAD) consists of 15 3 He tubes inside polyethylene and is the traditional, capture-based detection system for NMC. The polyethylene moderates incoming neutrons for thermal capture in individual tubes. The low gamma background, discrete capture signals, and high efficiency of the NOMAD are beneficial for NMC. However, the time to slow down neutrons to thermal energies leads to a system die away time on the scale of microseconds. Comparatively, the Rossi-alpha Measurements – Rapid Organic (n, γ) Discrimination Detector (RAMRODD) and the Organic Scintillator Array (OSCAR) are scatter-based detection systems. RAMRODD consists of 8, 5.08 by 5.08 cm EJ-309 liquid scintillators in 4 pairs, evenly-spaced with 90 degrees separation about the center of each assembly. OSCAR consists of a single array of 12, 5.08 by 5.08 cm trans-stilbene crystals aligned with the center of the assembly. Scatter-based systems detect fast neutrons without any moderation, leading to system die away times on the scale of tens of nanoseconds. This allows much shorter timing gate widths compared to thermal systems, thus increasing counting statistics of true correlated fission events. However, scatter-based systems are susceptible to neutron cross-talk when an incident neutron scatters off one detector and interacts in an adjacent detector, causing two seemingly correlated detection signals. The equations developed adjust for cross-talk to conduct NMC with scatter-based systems.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2015

Understanding the role of buried interface charges in a metal-oxide-semiconductor stack of Ti/Al{sub 2}O{sub 3}/Si using hard x-ray photoelectron spectroscopy

Hard X-ray photoelectron spectroscopy (HAXPES) analyses were carried out on metal-oxide-semiconductor (MOS) samples consisting of Si, thick and thin Al{sub 2}O{sub 3}, and a Ti metal cap. Using Si 1s and C 1s core levels for an energy reference, the Al 1s and Si 1s spectra were analyzed to reveal information about the location and roles of charges throughout the MOS layers. With different oxide thicknesses (2 nm and 23 nm), the depth sensitivity of HAXPES is exploited to probe different regions in the MOS structure. Post Ti deposition results indicated unexpected band alignment values between the thin and thick films, which are explained by the behavior of mobile charge within the Al{sub 2}O{sub 3} layer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Use of in-situ TEM to characterize the deformation-induced martensitic transformation in 304 stainless steel at cryogenic temperature

Highlights: • Unique experimental visualization of DIM transformation in 304SS in-situ in a TEM at cryogenic temperatures. • Three cases of DIM were captured in situ showing how stress and temperature are both effective on the transformation. • (i) formation of ε- martensite through overlapping/bundling of SFs (γ →SFs →ε), • (ii) direct (γ→ α’) transformation with interface migration upon pulling the sample at constant temperature, • (iii) direct γ→ α’ transformation upon cooling, without further pulling the sample. - Abstract: Tensile tests are conducted in-situ in a TEM at cryogenic temperatures (from − 100 °C to 0 °C) using a cooling TEM straining-stage with the goal of capturing the growth of the martensitic phase as it develops under stress in the material. The in-situ technique is used to explore the mechanism of deformation induced martensitic transformation in 304 and 304L austenitic stainless steels. The formation of stacking faults is captured, as well as the subsequent formation of ε-martensite, confirming the role played by Stacking faults (SFs) as intermediate step during the transformation from γ-austenite to ε-martensite. In addition, direct transformation from γ-austenite to α′-martensite is captured (i) upon straining at a fixed temperature and (ii) upon cooling after pulling on the sample, indicating how straining and temperature are both effective on the transformation.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Photoluminescence study of p-type vs. n-type Ag-doped ZnO films

Silver doped ZnO films have been grown on sapphire (0001) substrates by pulsed laser deposition. Hall measurements indicate that p-type conductivity is realized for the films deposited at 500 °C and 750 °C. Transmission electron microscopy images show more obvious and higher density of stacking faults (SFs) present in the p-type ZnO films as compared to the n-type films. Top view and cross sectional photoluminescence of the n- and p-type samples revealed free excitonic emission from both films. A peak at 3.314 eV, attributed to SF emission, has been observed only for the n-type sample, while a weak neutral acceptor peak observed at 3.359 eV in the p-type film. The SF emission in the n-type sample suggests localization of acceptor impurities nearby the SFs, while lack of SF emission for the p-type sample indicates the activation of the Ag acceptors in ZnO.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Experimental study of three-dimensional CO 2 -water drainage and fracture-matrix interactions in fractured porous media

Estimation of CO 2 storage capacity in fractured porous reservoirs requires a better understanding of the CO 2 -water flow fundamentals in fracture-matrix systems. There are few core-flood experiments on three-dimensional CO 2 -water drainage in a fracture-matrix system, yet none have examined the impacts of the capillary continuity of fractures and fracture-matrix interactions. In this study, twelve drainage experiments were conducted in four fracture-matrix columns, each comprising a vertical stack of a cylindrical rock core, a filter paper serving as an analogue to a horizontal fracture, and a ceramic plate. Here, the core sample was surrounded by open space at the top and circumferential sides to model fractures, allowing for 3-D CO 2 -water drainage in the rock core and displaced water draining across the horizontal fracture. X-ray computed tomography was conducted to visualize the dynamic invasion/drainage processes in four rock core samples showing contrasts in anisotropy, permeability, and heterogeneity. Experimental results show (1) the equilibrium CO 2 saturations in the rock matrix vary from 0.10 to 0.60 at controlled capillary pressures up to 200 kPa, (2) the CO 2 saturations in the matrix increase with water saturation in the horizontal fracture resulting in better capillary continuity for water to drain across the fracture, and (3) the fracture water saturation can be enhanced by the non-uniform fracture capillary pressure and countercurrent flow of CO 2 and water across the fracture-matrix interface. In the case of high fracture water saturation, matrix CO 2 saturation largely depends on matrix anisotropy and heterogeneity. The core-scale experimental results contribute to understand the fracture-matrix interactions and CO 2 storage efficiency in fractured porous media.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

No correlation of the Lyman continuum escape fraction with spectral hardness

The properties that govern the production and escape of hydrogen-ionizing photons (Lyman continuum, LyC; with energies > 13.6 eV) in star-forming galaxies are still poorly understood, but they are key to identifying and characterizing the sources that reionized the Universe. Here we empirically explore the relation between the hardness of ionizing radiation and the LyC leakage in a large sample of low- z star-forming galaxies from the recent Hubble Space Telescope Low- z Lyman Continuum Survey. Using Sloan Digital Sky Survey stacks and deep X-shooter observations, we investigate the hardness of the ionizing spectra ( Q He + / Q H ) between 54.4 eV (He + ) and 13.6 eV (H) from the optical recombination lines He II 4686 Å and Hβ 4861 Å for galaxies with LyC escape fractions spanning a wide range, f esc (LyC) ≃ 0–90%. We find that the observed intensity of He II/Hβ is primarily driven by variations in the metallicity, but is not correlated with LyC leakage. Both very strong (< f esc (LyC)> ≃ 0.5) and nonleakers (< f esc (LyC)> ≃ 0) present similar observed intensities of He II and Hβ at comparable metallicity, between ≃0.01 and ≃0.02 for 12 + log(O/H)> 8.0 and < 8.0, respectively. Our results demonstrate that Q He + / Q H does not correlate with f esc (LyC), which implies that strong LyC emitters do not show harder ionizing spectra than nonleakers at similar metallicity.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2022

Dark Energy Survey Year 3 results: Measurement of the baryon acoustic oscillations with three-dimensional clustering

The three-dimensional correlation function offers an effective way to summarize the correlation of the large-scale structure even for imaging galaxy surveys. We have applied the projected three-dimensional correlation function, ξ p to measure the baryonic acoustic oscillations (BAO) scale on the first-three years Dark Energy Survey data. The sample consists of about 7 million galaxies in the redshift range 0.6< z p < 1.1 over a footprint of 4108 deg 2 . Our theory modeling includes the impact of realistic true redshift distributions beyond Gaussian photo-z approximation. ξ p is obtained by projecting the three-dimensional correlation to the transverse direction. To increase the signal-to-noise of the measurements, we have considered a Gaussian stacking window function in place of the commonly used top-hat. ξ p is sensitive to D M (z eff )/r s , the ratio between the comoving angular diameter distance and the sound horizon. Using the full sample, D M (z eff )/r s is constrained to be19.00 ± 0.67 (top-hat) and 19.15 ± 0.58 (Gaussian) at z eff = 0.835. The constraint is weaker than the angular correlation w constraint 18.84 ± 0.50), and we trace this to the fact that the BAO signals are heterogeneous across redshift. While ξ p responds to the heterogeneous signals by enlarging the error bar, w can still give a tight bound on D M s in this case. When a homogeneous BAO-signal subsample in the range 0.7 < z p <1.0 (z eff = 0.845) is considered, ξp yields 19.80 ± 0.67 (top-hat) and 19.84 ± 0.53 (Gaussian). The latter is mildly stronger than the w constraint (19.86 ± 0.55). We find that the ξ p results are more sensitive to photo-z because ξ p keeps the three-dimensional clustering information causing it to be more prone to photo-z noise. The Gaussian window gives more robust results than the top-hat as the former is designed to suppress the low signal modes. ξ p and the angular statistics such as w have their own pros and cons, and they serve an important crosscheck with each other.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2017

Influence of Structural Defects on Biomineralized ZnS Nanoparticle Dissolution: An In-Situ Electron Microscopy Study

The dissolution of metal sulfides, such as ZnS, plays an important role in the fate of metal contaminants in the environment. Here we have examined the dissolution behavior of ZnS nanoparticles synthesized via several abiotic and biological pathways. Specifically, the biogenic ZnS nanoparticles were produced by an anaerobic, metal-reducing bacterium Thermoanaerobacter sp. X513 in a Zn-amended, thiosulfate-containing growth medium, whereas the abiogenic ZnS nanoparticles were produced by mixing an aqueous Zn solution with either H 2 S-rich gas or Na 2 S solution. For biogenic synthesis, we prepared two types of samples, in the presence or absence of trace silver (Ag). The size distribution, crystal structure, aggregation behavior, and internal defects of the synthesized ZnS nanoparticles were primarily examined using high-resolution transmission electron microscopy coupled with X-ray energy dispersive spectroscopy. The characterization results show that both the biogenic and abiogenic samples were dominantly composed of sphalerite. In the absence of Ag, the biogenic ZnS nanoparticles were significantly larger (i.e., ~10 nm) than the abiogenic ones (i.e., ~3–5 nm) and contained structural defects (e.g., twins and stacking faults). The presence of trace Ag showed a restraining effect on the particle size of the biogenic ZnS, resulting in quantum-dot-sized nanoparticles (i.e., ~3 nm). In situ dissolution experiments for the synthesized ZnS were conducted with a liquid-cell coupled to a transmission electron microscope (LCTEM), and the primary factors (i.e., the presence or absence structural defects) were evaluated for their effects on the dissolution behavior using the biogenic and abiogenic ZnS nanoparticle samples with the largest average particle size. Analysis of the dissolution results (i.e., change in particle radius with time) using the Kelvin equation shows that the defect-bearing biogenic ZnS nanoparticles (γ = 0.799 J/m 2 ) have a significantly higher surface energy than the abiogenic ZnS nanoparticles (γ = 0.277 J/m 2 ), suggesting that larger defect-bearing ZnS nanoparticles may be more reactive than the smaller quantum-dot-sized ZnS nanoparticles. These findings provide new insight into the factors that govern the dissolution of metal sulfide nanoparticles in relevant natural and engineered scenarios, and have implication for tracking the fate of zinc at contaminated sites. Moreover, our study exemplified the use of an in situ method (i.e., LCTEM) to investigate nanoparticle behavior (e.g., dissolution) in aqueous solutions.

54 ENVIRONMENTAL SCIENCES↗