EMSL: Jim Amonette's Publications

Fang Y, SB Yabusaki, SJ Morrison, JE Amonette, and PE Long. 2009. "Multicomponent reactive transport modeling of uranium bioremediation field experiments." Geochimica et Cosmochimica Acta 73(20):6029-6051. Abstract Biostimulation field experiments with acetate amendment are being performed at a former uranium mill tailings site in Rifle, Colorado, to investigate subsurface processes controlling in situ bioremediation of uranium-contaminated groundwater. An important part of the research is identifying and quantifying field-scale models of the principal terminal electron-accepting processes (TEAPs) during biostimulation and the consequent biogeochemical impacts to the subsurface receiving environment. Integrating abiotic chemistry with the microbially mediated TEAPs in the reaction network brings into play geochemical observations (e.g., pH, alkalinity, redox potential, major ions, and secondary minerals) that the reactive transport model must recognize. These additional constraints provide for a more systematic and mechanistic interpretation of the field behaviors during biostimulation. The reaction network specification developed for the 2002 biostimulation field experiment was successfully applied without additional calibration to the 2003 and 2007 field experiments. The robustness of the model specification is significant in that 1) the 2003 biostimulation field experiment was performed with 3 times higher acetate concentrations than the previous biostimulation in the same field plot (i.e., the 2002 experiment), and 2) the 2007 field experiment was performed in a new unperturbed plot on the same site. The biogeochemical reactive transport simulations accounted for four TEAPs, two distinct functional microbial populations, two pools of bioavailable Fe(III) minerals (iron oxides and phyllosilicate iron), uranium aqueous and surface complexation, mineral precipitation, and dissolution. The conceptual model for bioavailable iron reflects recent laboratory studies with sediments from the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site that demonstrated that the bulk (~90%) of Fe(III) bioreduction is associated with the phyllosilicates rather than the iron oxides. The uranium reaction network includes a U(VI) surface complexation model based on laboratory studies with Old Rifle UMTRA sediments and aqueous complexation reactions that include ternary complexes (e.g., calcium-uranyl-carbonate). The bioreduced U(IV), Fe(II), and sulfide components produced during the experiments are strongly associated with the solid phases and may play an important role in long-term uranium immobilization.

Wang CM, DR Baer, JE Amonette, MH Engelhard, J Antony, and Y Qiang. 2009. "Morphology and Electronic Structure of the Oxide Shell on the Surface of Iron Nanoparticles." Journal of the American Chemical Society 131(25):8824–8832. doi:10.1021/ja900353f Abstract A iron nanoparticle exposed to air at room temperature will be instantly covered by an oxide shell of typical thickness of ~ 3 nm. This native oxide shell in combination with an underlying iron core determines the physical and chemical behavior of this type of core-shell nanoparticles. One of the great challenges for characterizing this type of nanoparticles is determination of the structure of the oxide shell, as it is FeO, Fe3O4, -Fe2O3, -Fe2O3, or anything else. Significant research effort, mostly based on x-ray diffraction and spectroscopy and electron diffraction and transmission electron microscopy imaging, has been made to determine the structure of this thin layer of iron oxide. Most of the experimental results have been framed with one of the known iron oxide structures, although it is not necessarily true that this thin layer of iron oxide consists of a standard iron oxide. In this paper, the structure of the oxide shell on iron nanoparticle is probed using electron energy loss spectroscopy (EELS) at O K-edge with a spatial resolution of several nanometers (individual particle). Two types of representative particles were studied: particles that are fully oxidized and core-shell particle which possesses a Fe core. We found that the O K-edge spectra collected on the oxide shell in the nanoparticles shows distinctive differences as compared with that of the known iron oxide. Based on finger printing and quantum mechanical calculations results, we conclude that the distances between the absorbing oxygen and the next-nearest neighbor oxygens are more widely distributed than that in bulk Fe3O4 for both of these two types of particles. For smaller and fully oxidized particles, there is also a broadened distribution between the absorbing oxygen and the nearest neighbor oxygens. These results clearly demonstrate that the coordination configuration in the oxide shell on Fe nanoparticle is defective as compared with that of their bulk counterpart. Of the two types particles examined in this work, the degree of disorder is larger for the smaller fully oxidized particles.

Bachelor PP, JI McIntyre, JE Amonette, JC Hayes, BD Milbrath, and P Saripalli. 2008. "Potential method for measurement of CO2 leakage from underground sequestration fields using radioactive tracers." Journal of Radioanalytical and Nuclear Chemistry 277(1):85-89. doi:10.1007/s10967-008-0713-8 Abstract Reduction of anthropogenic carbon dioxide (CO2) release to the environment is a pressing challenge that should be addressed to avert the potential devastating effects of global warming. Within the United States, the most abundant sources of CO2 emissions are those generate from coal- or gas-fired power plants; one method to control CO2 emissions is to sequester it in deep underground geological formations. From integrated assessment models the overall leakage rates from these storage locations must be less than 0.1% of stored volume per year for long-term control. The ability to detect and characterize nascent leaks, in conjunction with subsequent remediation efforts, will significantly decrease the amount of CO2 released back into the environment. Because potential leakage pathways are not necessarily known a priori, onsite monitoring must be performed; the monitoring region in the vicinity of a CO2 injection well may be as large as 100 km2, which represents the estimated size of a supercritical CO2 bubble that would form under typical injection scenarios. By spiking the injected CO2 with a radiological or stable isotope tracer, it will be possible to detect ground leaks from the sequestered CO2 using fewer sampling stations, with greater accuracy than would be possible using simple CO2 sensors. The relative merits of various sorbent materials, radiological and stable isotope tracers, detection methods and potential interferences will be discussed.

Baer DR, JE Amonette, MH Engelhard, DJ Gaspar, AS Karakoti, SVNT Kuchibhatla, P Nachimuthu, J Nurmi, Y Qiang, V Sarathy, S Seal, A Sharma, PG Tratnyek, and CM Wang. 2008. "Characterization Challenges for Nanomaterials." Surface and Interface Analysis 40(3-4):529-537. doi:10.1002/sia.2726 Abstract Nanostructured materials are increasingly subject to nearly every type of chemical and physical analysis possible. Because of their small feature size there is a significant focus on tools with high spatial resolution. Because of their high surface area, it is also natural to characterize nanomaterials using tools designed to analyze surfaces. Regardless of the approach, nanostructured materials present a variety of obstacles to adequate, useful and needed analysis. This paper provides short overviews to some of the issues and complications including: particle stability, environmental effects, specimen handling, surface coating, contamination and time. Some specific examples are provided from a our work focused on ceria nanoparticles and iron metal-core/oxide-shell nanoparticles in which we use a combination of tools for routine analysis including XPS, TEM, and XRD and apply other methods as needed to obtain essential information.

Borch T, AK Camper, JA Biederman, P Butterfield, R Gerlach, and JE Amonette. 2008. "Evaluation of Characterization Techniques for Iron Pipe Corrosion Products and Iron Oxide Thin Films." Journal of Environmental Engineering (ASCE) 134(10):835-844. Abstract A common problem faced by drinking water studies is that of properly characterizing the corrosion products (CP) in iron pipescor synthetic Fe (hydr)oxides used to simulate the iron pipe used in municipal drinking-water systems. The present work compares the relative applicability of a suite of imaging and analytical techniques for the characterization of CPs and synthetic Fe oxide thin films and provide an overview of the type of data that each instrument can provide as well as their limitations to help researchers and consultants choose the best technique for a given task. Crushed CP from a water distribution system and synthetic Fe oxide thin films formed on glass surfaces were chosen as test samples for this evaluation. The CP and synthetic Fe oxide thin films were analyzed by atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive spectroscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray powder diffractometry (XRD), grazing incident diffractometry (GID), transmission electron microscopy (TEM), selected area electron diffraction, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared, Mössbauer spectroscopy, Brunauer-Emmett-Teller N2 adsorption and Fe concentration was determined by the ferrozine method. XRD and GID were found to be the most suitable techniques for identification of the mineralogical composition of CP and synthetic Fe oxide thin films, respectively. AFM and a combined ToF-SIMS-AFM approach proved excellent for roughness and depth profiling analysis of synthetic Fe oxide thin films, respectively. Corrosion products were difficult to study by AFM due to their surface roughness, while synthetic Fe oxide thin films resisted most spectroscopic methods due to their limited thickness (118 nm). XPS analysis is not recommended for mixtures of Fe (hydr)oxides due to their spectral similarities. SEM and TEM provided great detail on mineralogical morphology.

Hayes JA, DM Schubert, JE Amonette, P Nachimuthu, and RS Disselkamp. 2008. "Ultraviolet stimulation of hydrogen peroxide production using aminoindazole, diaminopyridine, and phenylenediamine solid polymer complexes of Zn(II)." Journal of Photochemistry and Photobiology. A, Chemistry 197(2-3):245-252. doi:10.1016/j.jphotochem.2007.12.031 Abstract Hydrogen peroxide is a valuable chemical commodity whose production relies on expensive methods. If an efficient, sustainable, and inexpensive solar-mediated production method could be developed from the reaction between dioxygen and water then its use as a fuel may be possible and gain acceptance. Hydrogen peroxide at greater than 10 M possesses a high specific energy, is environmentally clean, and is easily stored. However, the current method of manufacturing H2O2 via the anthraquinone process is environmentally unfriendly making the unexplored nature of its photochemical production from solar irradiation of interest. Here the concentration and quantum yield of hydrogen peroxide produced in an ultraviolet (UV-B) irradiated environment using aromatic and nitrogen-heterocyclic ring complexes of zinc(II) as solid substrates was studied. The amino-substituted isomers of the substrates indazole, pyridine, and phenylenediamine solid polymer complexes are examined. Samples exposed to the ambient atmosphere (e.g., aerated) were irradiated with a low power lamp with emission from 280-360 nm. Irradiation of various zinc complexes revealed Zn-5-aminoindazole to have the greatest first-day production of 63 mM/day with a 37% quantum yield. Para-phenylenediamine (PPAM) showed the greatest long-term stability and thus suggests H2O2 is produced photocatalytically. Isomeric forms of the catalyst’s organic components (e.g., amino groups) did have an effect on the production. Irradiation of diaminopyridine isomers indicated 2,3-diamino and 3,4-diamino structures were the most productive, each generating 32 mM/day hydrogen peroxide. However, the 2,5-diamino isomer showed no peroxide production. A significant decrease in hydrogen peroxide production in all but PPAM was noticed in the samples, suggesting the possibility of a catalyst poisoning mechanism. The samples ability to produce H2O2 is rationalized by proposing a reaction mechanism and examining the stability of the resonance structures of the different isomers.

Sarathy V, PG Tratnyek, J Nurmi, DR Baer, JE Amonette, CL Chun, RL Penn, and EJ Reardon. 2008. "Aging of Iron Nanoparticles in Aqueous Solution: Effects on Structure and Reactivity." Journal of Physical Chemistry C 112(7):2286-2293. doi:10.1021/jp0777418 Abstract Aging (or longevity) is one of the most important and potentially limiting factors in the use of nano-Fe0 to reduce groundwater contaminants. We investigated the aging of FeH2 (Toda RNIP-10DS) in water with a focus on changes in (i) the composition and structure of the particles (by XPS, XRD, TEM, and bulk Fe0 content), and (ii) the reactivity of the particles (by carbon tetrachloride reaction kinetics and electrochemical corrosion potentials). Our results show that the FeH2 becomes more reactive between 0 and ~2 days aging, and then gradually loses reactivity over the next few hundred days. These changes in reactivity correlate with evidence for rapid destruction of the original Fe(III) oxide film on FeH2 during immersion and the subsequent formation of a new passivating mixed-valence Fe(II)-Fe(III) oxide shell. The behavior of “unaged” nano-Fe0 in the laboratory may be similar to that in field-scale applications for source-zone treatment due to the short reaction times involved. Long-term aged FeH2 acquires properties that are relatively stable over weeks or even months.

Jastrow JD, JE Amonette, and VL Bailey. 2007. "Mechanisms controlling soil carbon turnover and their potential application for enhancing carbon sequestration ." Climatic Change 80(1-2):5-23. Abstract Two major mechanisms, (bio)chemical alteration and physicochemical protection, stabilize soil organic carbon (SOC) and thereby control soil carbon turnover. With (bio)chemical alteration, SOC is transformed by biotic and abiotic processes to chemical forms that are more resistant to decomposition and, in some cases, more easily retained by sorption to soil solids. With physicochemical protection, biochemical attack of SOC is inhibited by organomineral interactions at molecular to millimeter scales. Stabilization of otherwise decomposable SOM can occur via sorption to soil surfaces, complexation with soil minerals, occlusion within aggregates, and deposition in pores inaccessible to decomposers and extracellular enzymes. Soil structure (i.e., the arrangement of solids and pores in the soil) is a master integrating variable that both controls and indicates the SOC stabilization status of a soil. To enhance SOC sequestration, the best option is to modify the soil physicochemical environment to favor the activities of fungi. Specific practices that accomplish this include minimizing tillage, maintaining a near-neutral soil pH and an adequate base cation exchange capacity (particularly Ca), ensuring adequate drainage, and minimizing erosion by water and wind. In some soils, amendments with various high-specific-surface micro- and mesoporous sorbents such as fly ash or charcoal can be beneficial.

Marsili E, H Beyenal, L Di Palma, C Merli, A Dohnalkova, JE Amonette, and Z Lewandowski. 2007. "Uranium immobilization by sulfate-reducing biofilms grown on hematite, dolomite, and calcite." Environmental Science & Technology 41(24):8349-8354. doi:10.1021/es071335k Abstract Biofilms of sulfate-reducing bacteria Desulfovibrio desulfuricans G20 wereused to reduce dissolved U(VI)and subsequently immobilize U(IV) in the presence of uranium-complexing carbonates. The biofilms were grown in three identically operated fixed bed reactors, filled with three types of minerals: one noncarbonate-bearing mineral(hematite) and two carbonate-bearing minerals (calcite and dolomite). The source of carbonates in the reactors filled with calcite and dolomite were the minerals, while in the reactor filled with hematite it was a 10 mM carbonate buffer, pH 7.2, which we added to the growth medium. Our five-month study demonstrated that the sulfate-reducing biofilms grown in all reactors were able to immobilize/reduce uranium efficiently, despite the presence of uranium-complexing carbonates.

Palumbo AV, JR Tarver, LA Fagan, MS McNeilly, R Ruther, LS Fisher, and JE Amonette. 2007. "Comparing metal leaching and toxicity from high pH, low pH, and high ammonia fly ash." Fuel 86(10-11):1623-1630. doi:10.1016/j.fuel.2006.11.018 Abstract Previous work with both class F and class C fly ash indicated minimal leaching from most fly ashes tested. However, the addition of NOx removal equipment might result in higher levels of ammonia in the fly ash. We have recently been testing fly ash with a wide range of pH (3.7–12.4) originating from systems with NOx removal equipment. Leaching experiments were done using dilute CaCl2 solutions in batch and columns and a batch nitric acid method. All methods indicated that the leaching of heavy metals was different in the highest ammonia sample tested and the high pH sample. However, toxicity testing with the Microtox* system has indicated little potential toxicity in leachates except for the fly ash at the highest pH (12.4). When the leachate from the high pH fly ash was neutralized, toxicity was eliminated.