More Like this

1. Discovery and potential ramifications of reduced iron-bearing nanoparticles—magnetite, wüstite, and zero-valent iron—in wildland–urban interface fire ashes

   https://doi.org/10.1039/d2en00439a  

   Baalousha, Mohammed ; Desmau, Morgane ; Singerling, Sheryl A. ; Webster, Jackson P. ; Matiasek, Sandrine J. ; Stern, Michelle A. ; Alpers, Charles N. ( November 2022 , Environmental Science: Nano)

   The increase in fires at the wildland–urban interface has raised concerns about the potential environmental impact of ash remaining after burning. Here, we examined the concentrations and speciation of iron-bearing nanoparticles in wildland–urban interface ash. Total iron concentrations in ash varied between 4 and 66 mg g −1 . Synchrotron X-ray absorption near-edge structure (XANES) spectroscopy of bulk ash samples was used to quantify the relative abundance of major Fe phases, which were corroborated by transmission electron microscopy measurements. Maghemite (γ-(Fe 3+ ) 2 O 3 ) and magnetite (γ-Fe 2+ (Fe 3+ ) 2 O 4 ) were detected in most ashes and accounted for 0–90 and 0–81% of the spectral weight, respectively. Ferrihydrite (amorphous Fe( iii )–hydroxide, (Fe 3+ ) 5 HO 8 ·4H 2 O), goethite (α-Fe 3+ OOH), and hematite (α-Fe 3+ 2 O 3 ) were identified less frequently in ashes than maghemite and magnetite and accounted for 0–65, 0–54, and 0–50% of spectral weight, respectively. Other iron phases identified in ashes include wüstite (Fe 2+ O), zerovalent iron, FeS, FeCl 2 , FeCl 3 , FeSO 4 , Fe 2 (SO 4 ) 3 , and Fe(NO 3 ) 3 . Our findings demonstrate the impact of fires at the wildland–urban interface on iron speciation; that is, fires can convert iron oxides ( e.g. , maghemite, hematite, and goethite) to reduced iron phases such as magnetite, wüstite, and zerovalent iron. Magnetite concentrations ( e.g. , up to 25 mg g −1 ) decreased from black to gray to white ashes. Based on transmission electron microscopy (TEM) analyses, most of the magnetite nanoparticles were less than 500 nm in size, although larger particles were identified. Magnetite nanoparticles have been linked to neurodegenerative diseases as well as climate change. This study provides important information for understanding the potential environmental impacts of fires at the wildland–urban interface, which are currently poorly understood. 

   more » « less
2. A structural study of size-dependent lattice variation: In situ X-ray diffraction of the growth of goethite nanoparticles from 2-line ferrihydrite

   https://doi.org/10.2138/am-2020-7217  

   Heaney, Peter J. ; Oxman, Matthew J. ; Chen, Si Athena ( May 2020 , American Mineralogist)

   Abstract Unlike most native metals, the unit cells of metal oxides tend to expand when crystallite sizes approach the nanoscale. Here we review different models that account for this behavior, and we present structural analyses for goethite (α-FeOOH) crystallites from ~10 to ~30 nm. The goethite was investigated during continuous particle growth via the hydrothermal transformation of 2-line ferrihydrite at pH 13.6 at 80, 90, and 100 °C using time-resolved, angle-dispersive synchrotron X-ray diffraction. Ferrihydrite gels were injected into polyimide capillaries with low background scattering, increasing the sensitivity for detecting diffraction from goethite nanocrystals that nucleated upon heating. Rietveld analysis enabled high-resolution extraction of crystallographic and kinetic data. Crystallite sizes for goethite increased with time at similar rates for all temperatures. With increasing crystallite size, goethite unit-cell volumes decreased, primarily as a result of contraction along the c-axis, the direction of closest-packing (space group Pnma). We introduce the coefficient of nanoscale contraction (CNC) as an analog to the coefficient of thermal expansion (CTE) to compare the dependence of lattice strain on crystallite size for goethite and other metal oxides, and we argue that nanoscale-induced crystallographic expansion is quantitatively similar to that produced when goethite is heated. In addition, our first-order kinetic model based on the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation yielded an activation energy for the transformation of ferrihydrite to goethite of 72.74 ± 0.2 kJ/mol, below reported values for hematite nucleation and growth. 

   more » « less
3. Isotopic fractionation accompanying CO2 hydroxylation and carbonate precipitation from high pH waters at The Cedars, California, USA

   https://doi.org/doi.org/10.1016/j.gca.2021.01.003  

   Christensen, J. ( January 2021 , Geochimica)

   Teagle, Damon A (Ed.)

   The Cedars ultramafic block hosts alkaline springs (pH > 11) in which calcium carbonate forms upon uptake of atmospheric CO2 and at times via mixing with surface water. These processes lead to distinct carbonate morphologies with ‘‘floes” forming at the atmosphere-water interface, ‘‘snow” of fine particles accumulating at the bottom of pools and terraced constructions of travertine. Floe material is mainly composed of aragonite needles despite CaCO3 precipitation occurring in waters with low Mg/Ca (<0.01). Precipitation of aragonite is likely promoted by the high pH (11.5–12.0) of pool waters, in agreement with published experiments illustrating the effect of pH on calcium carbonate polymorph selection. The calcium carbonates exhibit an extreme range and approximately 1:1 covariation in d13C (
   9 to
   28‰ VPDB) and d18O (0 to
   20‰ VPDB) that is characteristic of travertine formed in high pH waters. The large isotopic fractionations have previously been attributed to kinetic isotope effects accompanying CO2 hydroxylation but the controls on the d13C-d18O endmembers and slope have not been fully resolved, limiting the use of travertine as a paleoenvironmental archive. The limited areal extent of the springs (0.5 km2) and the limited range of water sources and temperatures, combined with our sampling strategy, allow us to place tight constraints on the processes involved in generating the systematic C and O isotope variations. We develop an isotopic reaction–diffusion model and an isotopic box model for a CO2-fed solution that tracks the isotopic composition of each dissolved inorganic carbon (DIC) species and CaCO3. The box model includes four sources or sinks of DIC (atmospheric CO2, high pH spring water, fresh creek water, and CaCO3 precipitation). Model parameters are informed by new floe D44Ca data (
   0.75 ± 0.07‰), direct mineral growth rate measurements (4.8 to 8  10
   7 mol/m2/s) and by previously published elemental and isotopic data of local water and DIC sources. Model results suggest two processes control the extremes of the array: (1) the isotopically light end member is controlled by the isotopic composition of atmospheric CO2 and the kinetic isotope fractionation factor (KFF (‰) = (a
   1)  1000) accompanying CO2 hydroxylation, estimated here to be
   17.1 ± 0.8‰ (vs. CO2(aq)) for carbon and
   7.1 ± 1.1‰ (vs. ‘CO2(aq)+H2O’) for oxygen at 17.4 ± 1.0
   C. Combining our results with revised CO2 hydroxylation KFF values based on previous work suggests consistent KFF values of
   17.0 ± 0.3‰ (vs. CO2(aq)) for carbon and
   6.8 ± 0.8‰ for oxygen (vs. ‘CO2(aq)+H2O’) over the 17–28
   C temperature range. (2) The isotopically heavy endmember of calcium carbonates at The Cedars reflects the composition of isotopically equilibrated DIC from creek or surface water (mostly HCO- 3, pH = 7.8–8.7) that occasionally mixes with the high-pH spring water. The bulk carbonate d13C and d18O values of modern and ancient travertines therefore reflect the proportion of calcium carbonate formed by processes (1) and (2), with process (2) dominating the carbonate precipitation budget at The Cedars. These results show that recent advances in understanding kinetic isotope effects allow us to model complicated but common natural processes, and suggest ancient travertine may be used to retrieve past meteoric water d18O and atmospheric d13C values. There is evidence that older travertine at The Cedars recorded atmospheric d13C that predates large-scale combustion of fossil fuels. 

   more » « less
4. Reductive transformations of dichloroacetamide safeners: effects of agrochemical co-formulants and iron oxide + manganese oxide binary-mineral systems

   https://doi.org/10.1039/D0EM00331J  

   Ricko, Allison N. ; Psoras, Andrew W. ; Sivey, John D. ( October 2020 , Environmental Science: Processes & Impacts)

   null (Ed.)

   The toxic effects of herbicides are often incompletely selective and can harm crops. Safeners are “inert” ingredients commonly added to herbicide formulations to protect crops from herbicide-induced injury. Dichloroacetamide safeners have been previously shown to undergo reductive dechlorination in anaerobic abiotic systems containing an iron (hydr)oxide mineral (goethite or hematite) amended with Fe( ii ). Manganese oxides ( e.g. , birnessite) are important redox-active species that frequently co-occur with iron (hydr)oxides, yet studies examining the effects of more than one mineral on transformations of environmental contaminants are rare. Herein, we investigate the reactivity of dichloroacetamide safeners benoxacor, furilazole, and dichlormid in binary-mineral, anaerobic systems containing Fe( ii )-amended hematite and birnessite. As the molar ratio of Fe( ii )-to-Mn( iv ) oxide increased, the transformation rate of benoxacor and furilazole increased. The safener dichlormid did not transform appreciably over the sampling period (6 hours). The concentration of pH buffer ([MOPS] = 10–50 mM), ionic strength ([NaCl] = 10–200 mM), and order of solute addition ( e.g. , safener followed by Fe( ii ) or vice versa ) do not appreciably affect transformation rates of the examined dichloroacetamide safeners in Fe( ii ) + hematite slurries. The presence of agrochemical co-formulants, including the herbicide S -metolachlor and three surfactants, in solutions containing Cr(H 2 O) 6 2+ (as a model homogeneous reductant) also did not substantially influence rates of safener transformation. This study is among the first to examine laboratory systems of intermediate complexity ( e.g. , systems containing mixtures of agrochemical co-formulants or mineral phases) when assessing the environmental fate of emerging contaminants such as dichloroacetamide safeners. 

   more » « less
5. High-temperature Stability of an Iron-rich Smectite: Implications for Smectite Formation on Mars

   Jenkins, D.M. ; DePasquale, B.M. ( December 2020 , American Geophysical Union meeting, Fall 2020 Meeting)

   null (Ed.)

   Iron-rich phyllosilicates on Mars comprise nearly 90% of the H2O- and OH-bearing phases observed directly by rovers and remotely by orbiters (Chemtob et al., 2017, JGR). Theories concerning the possible origin of Fe-rich smectite during Mars’ earliest history (phyllosian) are hard to test because of limited knowledge of the upper-thermal stability of Fe-rich phyllosilicates. In this study we present data on the upper-thermal stability of a pure-iron smectite to put some minimum constraints on its possible high-temperature origin early in Mars history either from a primordial atmosphere or by hydrothermal activity. Smectite coexisting with quartz and magnetite was synthesized from the oxides in the system Na2O-FeO-Fe2O3-Al2O3-SiO2-H2O at 500°C and 2 kbar and fO2 near FMQ. Reversal experiments involved mixtures with equal portions of the smectite-synthesis and breakdown products (quartz, fayalite, albite, magnetite (mt) treated in the presence of about 10 wt% H2O over the range of 1-3 kbar and 530-640°C. The average composition (electron microprobe) of smectite formed both in synthesis and in reversal experiments was Na0.35(Fe2+2.28Fe3+0.31Al0.41)(Al1.07Si2.93)O10(OH)2·nH2O, where ferric iron was calculated by summing the octahedral cations to 3.0. Reversals for the reaction smec+mt1 = fayalite+albite+mt2+quartz+H2O were obtained at 538±8, 590±10, and 610±10°C at 1, 2, and 3 kbar, respectively, where mt1 and mt2 have the approximate compositions Fe2.8Si0.2O4 and Fe2.8Al0.1O4, respectively, with all other phases being pure. This smectite has up to 2 interlayer H2O at 25°C (and high humidity), losing 1 H2O at <50°C, and the second at 125 ± 25°C. Thermodynamic modeling of this reaction was used to extrapolate the upper-thermal stability of this Fe-smectite down to 10 bars and approximately 239°C. Applications of these results indicate the maximum temperature for forming Fe-smectite from a dense primordial atmosphere of 100 bars is 390 ± 25°C. Crustal storage of water in Fe-smectite ranges up to a maximum of 10.7 wt% at ~2 km and 40°C, 7.4 wt% at 6 km and 120°C, and 3.8 wt% H2O at 32 km and 625°C for a Noachian geotherm of 20°C/km. Plain language summary: This study presents experimental limits on the temperatures at which the clay mineral smectite might form on Mars, either from a dense primordial atmosphere (390°C at 100 bars) or by high-temperature hydrothermal activity (625°C at 32 km). Because this study deals with iron end-member clay, these are minimum temperatures; any solid solution with magnesium will increase these temperatures. 

   more » « less