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At least 217 records · Page 12

The Challenge of Achieving Site Closure of a Complex Groundwater Plume - 20531

Over the last three decades, DOE has made substantial progress in nearly every area of nuclear waste cleanup and has closed and transitioned 91 of the 107 sites in the EM complex. Several of the remaining groundwater plumes at Hanford, Los Alamos, Paducah, Oak Ridge, and Savannah River are complex and tend to have unique site or contaminant characteristics which provide an almost impossible challenge to remediate to regulatory levels. As a result, these complex sites will require a large investment to remediate. In order for DOE to achieve regulatory closure, a technically sound case must be developed and presented to regulators and stakeholders that clearly demonstrates that remedial goals have been or will be irreversibly achieved or that there is an alternate acceptable end-state. Five lines of evidence are required: - A conceptual site model that is as complete as possible, with the knowledge that it may continue to evolve with time; - Demonstration that trends in contaminant concentrations, or flux, versus time indicate that remedial goals will be achieved on schedule or within a reasonable time thereafter and that trends that deviate from this path are explainable by the conceptual model; - Demonstration that remobilization of attenuated contaminants is unlikely to occur in the future; - Explicit consideration of remedial contingencies, should deviations in the path toward remedial goals occur; - Development of an effective long-term monitoring plan to detect any conditions that might alter the path toward remedial goals. SRS has made significant progress in the remediation of contamination associated with the F-area and H-Area Seepage Basins, and it is currently developing a strategic closure path that addresses each of these lines of evidence and identifies both basic and applied scientific issues that will need to be addressed in order to obtain regulatory closure. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Comparison of Groundwater Sampling Technologies, Including Passive Diffusion Sampling, for Radionuclide Contamination - 20205

Using traditional high-flow purge methods for long-term water quality monitoring of deep groundwater wells can be expensive, affect contaminant migration, and produce excessive volumes of discharge water that can be difficult to manage. The use of low-flow pumping methods and depth discrete bailers (DDBs) can reduce the cost of sampling deep groundwater wells. In general, using different pumping methods to obtain reproducible and representative groundwater can be challenging. Passive diffusion samplers (PDSs) have successfully been used in long-term monitoring for volatile organic compounds, major ions, and trace-elements, but application has been limited for stable and radioactive isotopes. Beginning in 2018, the United States Geological Survey (USGS) conducted three sampling events to test the ability of PDSs and DDBs to obtain reproducible and representative groundwater samples. The sampled well is completed in a regional, permeable carbonate aquifer and is one in a set of wells that have historically been used for tritium tracer testing. All samples were obtained at 180 m (590 ft) below land surface (bls) in a 13.97 cm (5.5 inch) uncased well that has a total depth of 202 m (662 ft) bls. The first sampling event deployed a regenerated cellulose dialysis membrane (RCDM) PDS for 14 days with deionized water as the blank. The second sampling event deployed a RCDM for 27 days also with deionized water as the blank. The third sampling event deployed a Dual Membrane (DM) PDS for 65 days using a blank of tritium-dead carbonate water. The DM PDS was used to assess the effect of longer term deployment on tritium concentrations and address whether or not the PDSs reached equilibrium with ambient groundwater. The day after each of the three passive samplers were retrieved a DDB was used to obtain discrete non-integrated groundwater samples. For each DDB sampling day, the bailer was lowered into the well 10 consecutive times to determine if the water chemistry changed from the first to the last bailed sample. Quality assurance samples including blanks and duplicates were obtained during all three sampling events. All blank waters had tritium concentrations less than 21±33 pCi/L. Major ion (e.g. calcium, chloride, sodium, and sulfate) results were compared between all samples obtained with RCDM and DDB. Major ion concentrations showed a coefficient of variation of less than 6% between all RCDM and DDB samples; however, the coefficient of variation between the different deployment times and the two different methods for trace-element concentrations was much larger, particularly for manganese (82%), lead (41%), and zinc (33%). Stable isotope values were compared between the RCDM and DDB samples. The DDB sample results all fell within analytical uncertainty and were considered representative of the formation groundwater. The stable isotope values from the RCDM samples indicated that a longer deployment time was necessary to gain equilibrium and to obtain representative groundwater samples. Tritium results from groundwater samples obtained from the RCDM, DM, and DDB indicate that groundwaters obtained with PDSs produced tritium concentrations 2 to 3 times higher (between 1,426 and 3,060±87 pCi/L) than groundwaters obtained with a DDB (479 to 1,219±51 pCi/L). The longer the passive diffusion samplers were deployed, the higher the tritium concentration, suggesting that equilibrium with tritium was not reached within a 27-day deployment. DDB samples showed tritium results declining from the first to the last bailed sample for all three sampling events. This research suggests that tritium results from groundwater samples obtained from PDSs are more reproducible than samples obtained from DDBs. Also, PDSs likely do not accumulate isotopes of water but rather equilibrate with the ambient groundwater. On the other hand, both PDSs and DDBs were able to provide representative groundwater samples for major ions and have the potential to produce representative groundwater samples for stable isotopes of water (δD and δ{sup 18}O). Utilizing the most effective method for sampling groundwater is important for long-term groundwater monitoring. Quantifying the ability of passive diffusion groundwater samplers to obtain representative radioactive chemistry samples will help determine if these methods can be a useful alternative to pumping and purging wells for long-term monitoring. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Study on the Strategy for Final Disposal and Reuse of Decontamination Wastes after the Fukushima Daiichi NPP Accident - 20426

After the Fukushima Daiichi NPP accident, a large area of East Japan was contaminated by radio-Cs. To discuss the final disposal of the contaminated wastes off-site and the required development of related technologies, it is important to understand the volume and radiation concentration of the wastes after various treatments. For a scientific investigation purpose, a research committee has been formed by the Society for the Remediation of Radioactive Contamination in the Environment, which is independent from the Ministry of Environment. This committee's work is focused on discussing various scenarios for the final disposal considering a mass balance evaluation of the entire process, economic evaluations, and stakeholder consultation for final consensus. The current discussions of this committee are herein reported. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Influence of soluble oligomeric aluminum on precipitation in the Al-KOH-H2O system

The role of oligomeric aluminate (Al(OH)4-) species in the precipitation of aluminum phases such as gibbsite (a-Al(OH)3) from aqueous hydroxide solutions remains unclear and difficult to probe directly, despite its importance to developing accurate predictions of Al solubility in highly alkaline systems. Precipitation in this system entails a transition from predominantly tetrahedrally coordinated Al species in solution to octahedrally coordinated Al in gibbsite. Here we report a quantitative study of dissolved Al in the Al-KOH-H2O system using a combination of molecular spectroscopies. We established a relationship between changes in 27Al NMR chemical shifts and the relative intensity of Raman vibrational bands, indicative of variations in the ensemble speciation of Al in solution, and the formation of unique contact ion pair interactions with the aluminate dimer, Al2O(OH)62 . A strong correlation between the extent of Al oligomerization and the amount of solvated Al was demonstrated by systematically varying the KOH:Al molar ratio. The concentration of dissolved oligomeric Al in solution also directly impacted the particle size and morphology of gibbsite; high concentrations of dimeric Al2O(OH)62-, yielded smaller and more numerous anhedral to subhedral gibbsite particles, while low concentrations yielded fewer and larger euhedral gibbsite platelets. The collective observations suggest a key role of the Al2O(OH)62- dimer in promoting gibbsite precipitation from solution, where the potassium ion-paired dimer possibly catalyzes a more rapid transformation of Al coordination from tetrahedral in solution to octahedral in gibbsite.

Dembowski, Mateusz↗

Development of a Testbed for Pipeline Flushing - 20425

Pipelines which carry high-level waste within the DOE complex should be properly flushed in the cases where stationary or moving beds of solid sediment occur, or lines are prone to hydrogen gas buildup. Present guidelines establish a minimum for the amount of water (flush volume) and flush velocity values used for post-transfer flushing operations to achieve satisfactory cleaning of pipelines. However, further studies are needed to find optimal operating velocity modes/values in order to minimizing the flush volume and consequent downstream waste. These efforts are significantly helpful to DOE waste remediation sites by preserving tank storage, preventing additional waste processing, and minimizing dilution and changes in waste chemistry. An experimental test loop was recently developed for study of non-Newtonian slurry flushing at the Florida International University (FIU). This loop was designed to create sediment beds of various materials and bed heights and investigate parameters that effect the efficiency of flushing operations. The objective is to find flush velocity values/modes which lead to satisfactory cleaning of transport lines with a minimum amount of water usage. A 165 ft experimental test loop made of 3-inch carbon steel pipes was constructed and used in initial testing campaigns. This pipe loop was equipped with real-time monitoring instruments to record variation of pressure, density, mass flow rate, and temperature during testing. Post-flush in-situ no-flow evaluations were performed using ultrasonic, endoscopy, and visual inspection. Additional post-flush evaluations were conducted using filtration and density monitoring of residuals within a designated circulations loop. These provisions enable comparison of pipeline cleanness before the start and after termination of flushing operations for efficiency evaluation. This paper presents efforts associated with flushing of kaolin-water mixtures at different concentrations and with various flush volume and flush velocity values/modes. In initial testing, efforts focused on creating repeatable sediment beds inside the pipeline in both fully-flooded (no pre-flush drainage) and gravity-drained (pre-flush drained) systems. Bed characterization (i.e., measurement of sediment height and solids concentration) was conducted to ensure about consistency of initial conditions between tests. Preliminary results for flushing study of 10% vol. kaolin-water mixtures starting from a fully-flooded initial condition showed that flushing with 1-line volume (65 gallons) could remove up to 72 percent of solids from the pipeline. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Achieving the End State for the Pahute Mesa Corrective Action Units at the Nevada National Security Site - 20355

Underground nuclear testing at the Nevada National Security Site (NNSS) ended in 1992. To address the impact of radionuclide contamination from underground nuclear testing on the groundwater resources of Nevada, the U.S. Department of Energy (DOE) Environmental Management (EM) Nevada Program created the Underground Test Area (UGTA) activity to characterize the radionuclides in groundwater, understand the nature and extent of radionuclide migration, and forecast the distribution of radionuclides in groundwater for 1,000 years. The UGTA activity is regulated by the Federal Facility Agreement and Consent Order (FFACO), an agreement negotiated between the Nevada Division of Environmental Protection (NDEP), DOE, and the U.S. Department of Defense (DoD). DOE is close to achieving the end state (closure in place with monitoring and institutional control) for three of the five UGTA corrective action units (CAUs) on the NNSS. A number of challenges remain to achieve the end state of the other two CAUs, both located on Pahute Mesa. Pahute Mesa was the location of 82 underground nuclear tests, less than 10% of the total number of tests on the NNSS. Yet, Pahute Mesa contains slightly more than 60% of the total radionuclides (in curies). Based on groundwater sampling in monitoring wells, two radionuclide plumes have migrated several kilometers (km) in groundwater from selected test cavities and have crossed the boundary of the NNSS (yet remain within the boundaries of Federally controlled land). The path to achieve the end state continues to evolve as more data are collected and a better understanding of radionuclide migration in groundwater is developed. DOE has invested in drilling and sampling more than 50 characterization and monitoring groundwater wells over the past 25 years. The data indicate that the primary radionuclide of concern is tritium as it is about 89% of the total radionuclide inventory (in curies). As well, only tritium has been measured in groundwater outside of cavities at concentrations exceeding the Safe Drinking Water Act (SDWA) standard. For one of the tritium plumes that has migrated across the NNSS boundary, the average rate of migration has been measured as about 45 meters (m) per year with the rate of migration at the leading edge of the plume of about 85 meters per year. At that rate of migration, the tritium plume will decay to safe levels and not reach the publicly accessible environment at concentrations above the SDWA standard. Other radionuclides, at concentrations below the SDWA standards, will be monitored to ensure they remain at safe levels. Consequently, the end state path forward for Pahute Mesa has evolved to take full advantage of the data from the monitoring network to constrain uncertainty in model forecasts and to reduce reliance on probabilistic simulations. The focus of the end state approach relies on developing a monitoring well network that is protective of human health by increasing confidence that no radionuclide plume in the groundwater will migrate undetected to the accessible environment, located about 22 km from the nearest up-gradient underground nuclear test. Using the measured data to remove uncertainty, the evaluation of radionuclide migration from Pahute Mesa is directed toward meeting the goals of the end state. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Constitutive modelling of lubricants in concentrated contacts at high slide to roll ratios

A constitutive lubricant friction model for rolling/sliding concentrated contacts such as gears and cams was developed, based upon the Johnson and Tevaarwerk fluid rheology model developed earlier. The friction model reported herein differs from the earlier rheological models in that very large slide to roll ratios can now be accommodated by modifying the thermal response of the model. Also the elastic response of the fluid has been omitted from the model, thereby making it much simpler for use in the high slide to roll contacts. The effects of this simplification are very minimal on the outcome of the predicted friction losses (less than 1%). In essence then the lubricant friction model developed for the high slide to roll ratios treats the fluid in the concentrated contact as consisting of a nonlinear viscous element that is pressure, temperature, and strain rate dependent in its shear response. The fluid rheological constants required for the prediction of the friction losses at different contact conditions are obtained by traction measurements on several of the currently used gear lubricants. An example calculation, using this model and the fluid parameters obtained from the experiments, shows that it correctly predicts trends and magnitude of gear mesh losses measured elsewhere for the same fluids tested here.

Tevaarwerk, J. L.↗

Progress Towards Extended Cycle Life Si-based Anodes: Investigation of Fluorinated Local High Concentration Electrolytes

Silicon (Si) anodes are promising candidates for Li-ion batteries due to their high specific capacity and low operating potential. Implementation has been challenged by the significant Si volume changes during (de)lithiation and associated growth/regrowth of the solid electrolyte interphase (SEI). In this report, fluorinated local high concentration electrolytes (FLHCEs) were designed such that each component of the electrolyte (solvent, salt, diluent) is fluorinated to modify the chemistry and stabilize the SEI of high (30%) silicon content anodes. FLHCEs were formulated to probe the electrolyte salt concentration and ratio of the fluorinated carbonate solvents to a hydrofluoroether diluent. Higher salt concentrations led to higher viscosities, conductivities, and contact angles on polyethylene separators. Electrochemical cycling of Si-graphite/NMC622 pouch cells using the FLHCEs delivered up to 67% capacity retention after 100 cycles at a C/3 rate. Post-cycling X-ray photoelectron spectroscopy (XPS) analyses of the Si-graphite anodes indicated the FLHCEs formed a LiF rich solid electrolyte interphase (SEI). The findings show that the fluorinated local high concentration electrolytes contribute to stabilizing the Si-graphite electrode over extended cycling.

36 MATERIALS SCIENCE↗

Is lunar bulk material similar to earth's mantle?

In an attempt to ascertain whether or not lunar bulk material is similar to the earth's mantle, consideration is given to the following parameters of both planetary bodies: oxygen isotopic composition, metal/silicate ratio, siderophile trace element concentrations, refractory lithophile trace element concentrations, volatile element ratios and volatile/refractory element ratios, bulk Mg /(Mg + Fe) ratio, Fe/Mn ratios, and redox state. The values of these parameters are estimated and various hypotheses for lunar origin are examined in their light.

Drake, Michael J.↗

Europium mass balance in polymict samples and implications for plutonic rocks of the lunar crust

The mean concentrations of Sm and Eu in the lunar surface crust were analyzed by correlating the Sm concentration and the Sm/Eu ratio with Th concentration obtained from published data on a large number of polymict samples from various locations in the lunar highlands, and using the value of 0.91 microg/g for the mean Th concentration of the highlands surface crust obtained by the orbiting gamma-ray experiments. The mean concentration of Sm in the lunar surface crust was found to be between 2 and 3 microg/g, and that of Eu between 0.7 and 1.2 microg/g. The results indicate that there is no significant enrichment or depletion of Eu, compared to Sm, relative to chondritic abundances; i.e., there is no significant 'Eu anomaly' in average upper crust, contrary to predictions by some earlier investigators.

Korotev, Randy L.↗

Sulfate reduction and other sedimentary biogeochemistry in a northern New England salt marsh

Sulfate reduction rates, dissolved iron and sulfide concentrations, and titration alkalinity were measured in salt marsh soils along a transect that included areas inhabited by both the tall and short forms of Spartina alterniflora and by Spartina patens. Pore waters were collected with in situ 'sippers' to acquire temporal data from the same location without disturbing plant roots. During 1984, data collected at weekly intervals showed rapid temporal changes in belowground biogeochemical processes that coincided with changes in S. alterniflora physiology. Rates of SO4(-2) reduction increased fivefold (to greater than 2.5 micromol ml(sup -1)d(sup -1)) when plants began elongating aboveground yet decreased fourfold upon plant flowering. This rapid increase in rates of SO4(-2) reduction must have been fueled by dissolved organic matter released from roots only during active growth. Once plants flowered, the supply of oxidants to the soil decreased and sulfide and alkalinity concentrations increased despite decreases in SO4(-2) reduction and increases in SO4(-2):Cl(-) ratios. Sulfide concentrations were highest in soils inhabited by tallest plants. During 1985, S. alterniflora became infested with fly larvae (Chaetopsis apicalis John) and aboveground growth ceased in late June. This cessation was accompanied by decreased rates of SO4(-2) reduction similar to those noted during the previous year when flowering occurred. After the fly infestation, the pore-water chemical profiles of these soils resembled profiles of soils inhabited by the short form of S. alterniflora. The SO4(-2) reduction rates in S. patens soils are the first reported. Rates were similar to those in S. alterniflora except that they did not increase greatly when S. patens was elongating. Tidal and rainfall events produced desiccation-saturation cycles that altered redox conditions in the S. patens soils, resulting in rapid changes in the dissolution and precipitation of iron and in the magnitude and spatial distribution of SO4(-2) reduction.

Hines, Mark E.↗

Measurements of soot formation and hydroxyl concentration in near critical equivalence ratio premixed ethylene flame

The testing and development of existing global and detailed chemical kinetic models for soot formation requires measurements of soot and radical concentrations in flames. A clearer understanding of soot particle inception relies upon the evaluation and refinement of these models in comparison with such measurements. We present measurements of soot formation and hydroxyl (OH) concentration in sequences of flat premixed atmospheric-pressure C2H4/O2/N2 flames and 80-torr C2H4/O2 flames for a unique range of equivalence ratios bracketting the critical equivalence ratio (phi(sub c)) and extending to more heavily sooting conditions. Soot volume fraction and number density profiles are measured using a laser scattering-extinction apparatus capable of resolving a 0.1 percent absorption. Hydroxyl number density profiles are measured using laser-induced fluorescence (LIF) with broadband detection. Temperature profiles are obtained from Rayleigh scattering measurements. The relative volume fraction and number density profiles of the richer sooting flames exhibit the expected trends in soot formation. In near-phi(sub c) visibility sooting flames, particle scattering and extinction are not detected, but an LIF signal due to polycyclic aromatic hydrocarbons (PAH's) can be detected upon excitation with an argon-ion laser. A linear correlation between the argon-ion LIF and the soot volume fraction implies a common mechanistic source for the growth of PAH's and soot particles. The peak OH number density in both the atmospheric and 80-torr flames declines with increasing equivalence ratio, but the profile shape remains unchanged in the transition to sooting, implying that the primary reaction pathways for OH remain unchanged over this transition. Chemical kinetic modeling is demonstrated by comparing predictions using two current reaction mechanisms with the atmospheric flame data. The measured and predicted OH number density profiles show good agreement. The predicted benzene number density profiles correlate with the measured trends in soot formation, although anomalies in the benzene profiles for the richer and cooler sooting flames suggest a need for the inclusion of benzene oxidation reactions.

Inbody, Michael Andrew↗

Development and testing of a high cycle life 30 A-h sealed AgO-Zn battery

A two-phase program was initiated to investigate design parameters and technology to develop an improved AgO-Zn battery. The basic performance goal was 100 charge/discharge cycles (22 h/2 h) at 50 percent depth of discharge following a six-month period of charged stand at room temperature. Phase 1, cell evaluation, involved testing 70 cells in five-cell groups. The major design variables were active material ratios, electrolyte concentrations, separator systems, and negative plate shape. Phase 1 testing showed that cycle life could be improved 10 percent to 20 percent by using greater ratios of zinc to silver oxide and higher electrolyte concentrations. Wedge-shaped negatives increased cycle life by nearly 100 percent. Phase 2 battery evaluation, which was initiated before the Phase 1 results were known completely, involved evaluation of six designs as 19-cell batteries. Only one battery exceeded 100 cycles following nine months charged stand.

Bogner, R. S.↗

Coral Pigments: Quantification Using HPLC and Detection by Remote Sensing

Widespread coral bleaching (loss of pigments of symbiotic dinoflagellates), and the corresponding decline in coral reef health worldwide, mandates the monitoring of coral pigmentation. Samples of the corals Porites compressa and P. lobata were collected from a healthy reef at Puako, Hawaii, and chlorophyll (chl) a, peridinin, and Beta-carotene (Beta-car) were quantified using reverse-phase high performance liquid chromatography (HPLC). Detailed procedures are presented for the extraction of the coral pigments in 90% acetone, and the separation, identification, and quantification of the major zooxanthellar pigments using spectrophotometry and a modification of the HPLC system described by Mantoura and Llewellyn (1983). Beta-apo-8-carotenal was found to be inadequate as in internal standard, due to coelution with chl b and/or chl a allomer in the sample extracts. Improvements are suggested, which may result in better resolution of the major pigments and greater accuracy in quantification. Average concentrations of peridinin, chl a, and Beta-car in corals on the reef were 5.01, 8.59, and 0.29, micro-grams/cm(exp 2), respectively. Average concentrations of peridinin and Beta-car did not differ significantly between the two coral species sampled; however, the mean chl a concentration in P. compressa specimens (7.81 ,micro-grams/cm(exp 2) was significantly lower than that in P. lobata specimens (9.96 11g/cm2). Chl a concentrations determined spectrophotometrically were significantly higher than those generated through HPLC, suggesting that spectrophotometry overestimates chl a concentrations. The average ratio of chl a-to-peridinin concentrations was 1.90, with a large (53%) coefficient of variation and a significant difference between the two species sampled. Additional data are needed before conclusions can be drawn regarding average pigment concentrations in healthy corals and the consistency of the chl a/peridinin ratio. The HPLC pigment concentration values contribute to the limited database of pigment concentrations in healthy corals, from which quantitative definitions of 'healthy' vs. 'bleached' coral may emerge. They also serve as ground-truth, corresponding to fluorescence data collected from the reef at Puako using airborne remote sensing of laser induced fluorescence. Fluorescence spectra from several overflights using the NASA AOL (airborne oceanographic lidar) system show consistent chlorphyll fluorescence peaks around 685 nm, as well as consistence peaks in the 400-600 nm range which may emanate from granules in the coral tissue. These data, along with results from previous studies of coral fluorescence, suggest that remote sensing of laser-induced fluorescence may become a rapid and efficient means of monitoring coral pigmentation and coral reef bleaching.

Cottone, Mary C.↗

Noble gas concentrations and cosmic ray exposure ages of eight recently fallen chondrites

Abundances and isotopic compositions of He, Ne, Ar, and Xe have been measured in eight recently fallen chondrites. Ratios of concentrations of cosmic ray-produced He-3, Ne-21, Ne-22, and Ar-38 indicate that all eight samples experienced less than average cosmic ray shielding. He-3 and Ne-21 exposure ages were calculated using shielding corrected chondritic production rates and the measured Ne-22/Ne-21. Exposure ages calculated from Na-22/Ne-22 and Al-26/Ne-21 ratios and constant relative production rates show a bias between the two ages due to variations in Na-22/Al-26. Arguments are presented that this bias is due to irradiation hardness differences, and therefore the use of constant values for both the Na-22/Ne-22 and Al-26/Ne-21 production ratios is not permitted.

Bogard, D. D.↗

Significance of pH and iron-sulfur chemistry for molybdenum sequestration under sulfidic conditions

Molybdenum (Mo), a redox-sensitive trace metal, plays an important role in recording ancient oxygenation and deoxygenation events as a paleoredox proxy. The mobility and reactivity of Mo in aqueous conditions are closely tied to the chemistry of reduced sulfur and iron species. However, our current knowledge on the formation, structure, stability, and condensation pathways of FeMoS clusters in aqueous settings remains limited, which has driven the current study. In this study, we conducted systematic experiments investigating the interactions between dissolved Mo (initially introduced as molybdate, MoO 4 2– , or tetrathiomolybdate, MoS 4 2– ), ferrous iron (Fe 2+ ), and sulfide (ΣH 2 S aq ) in variously defined abiotic sulfidic systems to determine the external conditions (i.e., pH, and reactant concentrations and ratios) necessary for the formation of solid-phase Fe-Mo sulfides. Solution samples of each system were monitored using ultraviolet-visible spectroscopy (UV–vis) to track the degree of thiolation of dissolved Mo species. Precipitates were analyzed using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) to determine their elemental compositions and valences, and structure (i.e., crystalline or amorphous), respectively. All FeMoS precipitates were amorphous and contained 76–90% Mo(IV) and 10–24% Mo(V) with a trend toward lower Mo(IV):Mo(V) ratios with increasing pH. The degree of Mo thiolation, which was strongly dependent on solution pH and Fe 2+ concentrations, greatly affected the amount of Mo sequestered (i.e., an increased degree of Mo thiolation in solution led to an increased amount of Mo in the final FeMoS precipitate). Furthermore, these findings suggest that changes in pH and Fe 2+ concentrations may be responsible for the sulfide-independent variations in Mo behavior observed in euxinic basins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Aqueous Phase Acidity on Ln(III) Coordination by N , N , N ', N '-Tetraoctyldiglycolamide

Here, this study highlights the importance of combining distribution ratio measurements with multiple spectroscopic techniques to provide a more comprehensive understanding of organic phase Ln coordination chemistry. Solvent extraction investigations with N,N,N',N'-tetraoctyldiglycolamide (TODGA) in n-heptane reveal the sensitivity of Ln complexation to the HNO 3 concentration. Distribution ratio measurements in tandem with UV–Vis demonstrated that increasing the concentration of HNO3 above 0.5 M with a constant NO 3 – of 1 M increases the number of coordinating TODGA molecules, from a 1:2 to a 1:3 Ln:TODGA complex. At each concentration of HNO 3 considered herein (from 0.01 to 1 M), Eu lifetime analysis demonstrated no evidence of H 2 O coordination. Results from Fourier transform infrared investigations suggest the presence of inner-sphere NO 3 – under low concentrations of HNO 3 when the 1:2 Ln:TODGA complex is present. Increasing the HNO 3 concentration above 0.5 M increases the propensity for outer-sphere interactions by removing the coordinated NO 3 – and saturating the Ln coordination sphere with three TODGA molecules, resulting in the well-established cationic, trischelate homoleptic [Ln(TODGA) 3 ] 3+ complex. This work demonstrates the importance in considering the NO 3 – source for solvent extraction systems. In particular, for systems with an affinity for outer-sphere interactions with molar concentrations of HNO 3 , changing the NO 3 – source can change the inner-sphere coordination of the Ln complex, which, in turn, affects the separation efficacy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗