Abstract Americium is a highly radioactive actinide element found in used nuclear fuel. Its adsorption on aluminum (hydr)oxide minerals is important to study for at least two reasons: (i) aluminum (hydr)oxide minerals are ubiquitous in the subsurface environment and (ii) bentonite clays, which are proposed engineered barriers for the geologic disposal of used nuclear fuel, have the same ≡AlOH sites as aluminum (hydr)oxide minerals. Surface complexation modeling is widely used to interpret the adsorption behavior of heavy metals on mineral surfaces. While americium sorption is understudied, multiple adsorption studies for europium, a chemical analog, are available. In this study we compiled data describing Eu(III) adsorption on three aluminum (hydr)oxide minerals—corundum (α-Al 2 O 3 ), γ-alumina (γ-Al 2 O 3 ) and gibbsite (γ-Al(OH) 3 )—and developed surface complexation models for Eu(III) adsorption on these minerals by employing diffuse double layer (DDL) and charge distribution multisite complexation (CD-MUSIC) electrostatic frameworks. We also developed surface complexation models for Am(III) adsorption on corundum (α-Al 2 O 3 ) and γ-alumina (γ-Al 2 O 3 ) by employing a limited number of Am(III) adsorption data sourced from literature. For corundum and γ-alumina, two different adsorbed Eu(III) species, one each for strong and weak sites, were found to be important regardless of which electrostatic framework was used. The formation constant of the weak site species was almost 10,000 times weaker than the formation constant for the corresponding strong site species. For gibbsite, two different adsorbed Eu(III) species formed on the single available site type and were important for the DDL model, whereas the best-fit CD-MUSIC model for Eu(III)-gibbsite system required only one Eu(III) surface species. The Am(III)-corundum model based on the CD-MUSIC framework had the same set of surface species as the Eu(III)-corundum model. However, the log K values of the surface reactions were different. The best-fit Am(III)-corundum model based on the DDL framework had only one site type. Both the CD-MUSIC and the DDL model developed for Am(III)-γ-alumina system only comprised of one site type and the formation constant of the corresponding surface species was ~ 500 times stronger and ~ 700 times weaker than the corresponding Eu(III) species on the weak and the strong sites, respectively. The CD-MUSIC model for corundum and both the DDL and the CD-MUSIC models for γ-alumina predicted the Am(III) adsorption data very well, whereas the DDL model for corundum overpredicted the Am(III) adsorption data. The root mean square of errors of the DDL and CD-MUSIC models developed in this study were smaller than those of two previously-published models describing Am(III)-γ-alumina system, indicating the better predictive capacity of our models. Overall, our results suggest that using Eu(III) as an analog for Am(III) is practical approach for predicting Am(III) adsorption onto well-characterized minerals. Graphical Abstract
more »
« less
This content will become publicly available on May 18, 2024
Heterogeneous chemistry of methyl ethyl ketone on mineral oxide surfaces: impacts of relative humidity and nitrogen dioxide on product formation
Despite their atmospheric abundance, heterogeneous and multiphase reactions of carbonyl compounds are poorly understood. In this study, we investigate the surface adsorption and surface chemistry of methyl ethyl ketone (MEK), the second most abundant ketone in the atmosphere, with several mineral oxide surfaces including SiO 2 , α-Fe 2 O 3 and TiO 2 . In particular, the chemistry of MEK with these common components of mineral dust, under both dry and high relative humidity (RH%) conditions, has been investigated. Furthermore, reactions of adsorbed MEK with gas-phase NO 2 were also examined. We show that MEK molecularly and reversibly adsorbs on SiO 2 whereas irreversible adsorption occurs on both α-Fe 2 O 3 and TiO 2 surfaces, followed by the formation of higher molar mass species resulting from dimerization and oligomerization reactions. Isotope labeling experiments confirmed the incorporation of H atoms from surface hydroxyl groups and strongly adsorbed water into these oligomer products. Most interesting is that at 80% RH, oligomer formation on α-Fe 2 O 3 shifts toward a higher relative abundance of MEK tetramer relative to the dimer while on TiO 2 there was no change in product distribution. In the presence of gas-phase NO 2 , MEK undergoes degradation to formaldehyde and acetaldehyde, followed by the formation of aldol condensation products of these aldehydes on the α-Fe 2 O 3 surface. Overall, this study provides mechanistic insights on mineralogy-specific heterogeneous chemistry of a prevalent and atmospherically abundant ketone.
more »
« less
- Award ID(s):
- 2002607
- NSF-PAR ID:
- 10426172
- Date Published:
- Journal Name:
- Environmental Science: Atmospheres
- Volume:
- 3
- Issue:
- 5
- ISSN:
- 2634-3606
- Page Range / eLocation ID:
- 799 to 815
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract Early‐age hydration of cement is enhanced by slightly soluble mineral additives (ie, fillers, such as quartz and limestone). However, few studies have attempted to systematically compare the effects of different fillers on cementitious hydration rates, and none have quantified such effects using fillers with comparable, size‐classified particle size distributions (PSDs). This study examines the influence of size‐classified fillers [ie, limestone (CaCO3), quartz (SiO2), corundum (Al2O3), and rutile (TiO2)] on early‐age hydration kinetics of tricalcium silicate (C3S) using a combination of experimental methods, while also employing a modified phase boundary and nucleation and growth model. In prior studies, wherein fillers with broad PSDs were used, it has been reported that between quartz and limestone, the latter is a superior filler due to its ability to partake in anion‐exchange reactions with C‐S‐H. Contrary to prior investigations, this study shows that when size‐classified and
area matched fillers are used—which, essentially, eliminate degrees of freedom associated with surface area and agglomeration of filler particulates—the filler effect of quartz is broadly similar to that of limestone as well as rutile. Results also show that unlike quartz, limestone, and rutile—which enhance C3S hydration kinetics—corundum suppresses hydration of C3S during the first several hours after mixing. Such deceleration in C3S hydration kinetics is attributed to the adsorption of aluminate anions—released from corundum's dissolution—onto anhydrous particulates’ surfaces, which impedes both the dissolution of C3S and heterogeneous nucleation of C‐S‐H. -
Determination of the surface hydrophobicity or wettability of nanomaterials and nanoparticles (NPs) is often challenged by the heterogeneous properties of NPs that vary with particle size, shape, surface charge, aggregation states, and surface sorption or coating. This study first summarized inherent limitations of the water contact angle, octanol–water partition coefficient ( K ow ) and surface adsorption of probe molecules in probing nanomaterial hydrophobicity. Then, we demonstrated the principle of a scanning probe method based on atomic force microscopy (AFM) for the local surface hydrophobicity measurement. Specifically, we measured the adhesion forces between functionalized AFM tips and self-assembled monolayers (SAMs) to establish a linear relationship between the adhesion forces and water contact angles based on the continuum thermodynamic approach (CTA). This relationship was used to determine the local surface hydrophobicity of seven different NPs ( i.e. , TiO 2 , ZnO, SiO 2 , CuO, CeO 2 , α-Fe 2 O 3 , and Ag), which agreed well with bulk contact angles of these NPs. Some discrepancies were observed for Fe 2 O 3 , CeO 2 and SiO 2 NPs, probably because of surface hydration and roughness effects. Moreover, the solution pH and ionic strength had negligible effects on the adhesion forces between the AFM tip and MWCNTs or C 60 , indicating that the hydrophobicity of carbonaceous nanomaterials is not influenced by pH or ionic strength (IS). By contrast, natural organic matter (NOM) appreciably decreased the hydrophobicity of MWCNTs and C 60 due to surface coating of hydrophilic NOM. This scanning probe method has been proved to be reliable and robust toward the accurate measurement of the nanoscale hydrophobicity of individual NPs or nanomaterials in liquid environments.more » « less
-
more » « less
Abstract Ozone, O3, is a strong oxidizing agent often used for water purification. O3is typically produced in dielectric barrier discharges (DBDs) by electron-impact dissociation of O2, followed by three-body association reactions between O and O2. Previous studies on O3formation in low-temperature plasma DBDs have shown that O3concentrations can drop to nearly zero after continued operation, termed the ozone-zero phenomenon (OZP). Including small (<4%) admixtures of N2can suppress this phenomenon and increase the O3production relative to using pure O2in spite of power deposition being diverted from O2to N2and the production of nitrogen oxides, N
x Oy . The OZP is hypothesized to occur because O3is destroyed on the surfaces in contact with the plasma. Including N2in the gas mixture enables N atoms to occupy surface sites that would otherwise participate in O3destruction. The effect of N2in ozone-producing DBDs was computationally investigated using a global plasma chemistry model. A general surface reaction mechanism is proposed to explain the increase in O3production with N2admixtures. The mechanism includes O3formation and destruction on the surfaces, adsorption and recombination of O and N, desorption of O2and N2, and NOx reactions. Without these reactions on the surface, the density of O3monotonically decreases with increasing N2admixture due to power absorption by N2leading to the formation of nitrogen oxides. With N-based surface chemistry, the concentrations of O3are maximum with a few tenths of percent of N2depending on the O3destruction probability on the surface. The consequences of the surface chemistry on ozone production are less than the effect of gas temperature without surface processes. An increase in the O3density with N-based surface chemistry occurs when the surface destruction probability of O3or the surface roughness was decreased. -
The study of water adsorption on mineral surfaces is fundamental to soil and atmospheric science. The physiochemical effects of mineral aerosol influence atmospheric chemistry and climate as well as soil moisture. Iron-containing minerals are abundant on Earth as well as Mars, where the existence and location of surface water is uncertain. Experimental water adsorption measurements have been conducted as a function of relative humidity (RH) on goethite (α-FeO(OH)), a common component of atmospheric mineral dust and Martian crustal material. Water adsorption on goethite was monitored using Horizontal Attenuated Total Reflectance Fourier Transform Infrared (HATR-FTIR) spectroscopy equipped with a flow cell and quantified according to Beer’s Law. Water content as a function of RH was analyzed using type II adsorption isotherms to model multilayer water adsorption. Brunauer Emmet and Teller (BET), Frenkel Halsey and Hill (FHH) and Freundlich adsorption isotherms were applied to model the experimental data. Monolayer water coverage was found to be 4.758x1013 molecules/cm2 based on BET analysis. FHH Adsorption Activation Theory (AT) was used to predict cloud condensation nuclei (CCN) activity of goethite under Earth’s atmospheric conditions. Results aid in the effort of climate prediction on Earth as well as locating liquid water on Mars’ surface.more » « less
