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A Review of Global Precipitation Data Sets: Data Sources, Estimation, and Intercomparisons

Abstract In this paper, we present a comprehensive review of the data sources and estimation methods of 30 currently available global precipitation data sets, including gauge‐based, satellite‐related, and reanalysis data sets. We analyzed the discrepancies between the data sets from daily to annual timescales and found large differences in both the magnitude and the variability of precipitation estimates. The magnitude of annual precipitation estimates over global land deviated by as much as 300 mm/yr among the products. Reanalysis data sets had a larger degree of variability than the other types of data sets. The degree of variability in precipitation estimates also varied by region. Large differences in annual and seasonal estimates were found in tropical oceans, complex mountain areas, northern Africa, and some high‐latitude regions. Overall, the variability associated with extreme precipitation estimates was slightly greater at lower latitudes than at higher latitudes. The reliability of precipitation data sets is mainly limited by the number and spatial coverage of surface stations, the satellite algorithms, and the data assimilation models. The inconsistencies described limit the capability of the products for climate monitoring, attribution, and model validation.

54 ENVIRONMENTAL SCIENCES↗

Significance of aerosol radiative effect in energy balance control on global precipitation change

Historical changes of global precipitation in the 20th century simulated by a climate model are investigated. The results simulated with alternate configurations of cloud microphysics are analyzed in the context of energy balance controls on global precipitation, where the latent heat changes associated with the precipitation change is nearly balanced with changes to atmospheric radiative cooling. The atmospheric radiative cooling is dominated by its clear-sky component, which is found to correlate with changes to both column water vapor and aerosol optical depth (AOD). The water vapor-dependent component of the clear-sky radiative cooling is then found to scale with global temperature change through the Clausius–Clapeyron relationship. This component results in a tendency of global precipitation increase with increasing temperature at a rate of approximately 2%K -1 . Another component of the clear-sky radiative cooling, which is well correlated with changes to AOD, is also found to vary in magnitude among different scenarios with alternate configurations of cloud microphysics that controls the precipitation efficiency, a major factor influencing the aerosol scavenging process that can lead to different aerosol loadings. These results propose how different characteristics of cloud microphysics can cause different aerosol loadings that in turn perturb global energy balance to significantly change global precipitation. This implies a possible coupling of aerosol–cloud interaction with aerosol–radiation interaction in the context of global energy balance.

54 ENVIRONMENTAL SCIENCES↗

Reducing Antisolvent Use in the STRAP Process by Enabling a Temperature–Controlled Polymer Dissolution and Precipitation for the Recycling of Multilayer Plastic Films

The recently reported processing strategy called solvent-targeted recovery and precipitation (STRAP) enables deconstruction of multilayer plastic packaging films into their constituent resins by selective dissolution. It uses a series of solvent washes that are guided by thermodynamic calculations of polymer solubility. In this work, the use of antisolvents in the STRAP process was reduced and solvent mixtures were considered to enable the temperature-controlled dissolution and precipitation of the target polymers in multilayer films. This was considered as a means to further improve the STRAP process and its estimated costs. Two STRAP approaches were compared based on different polymer precipitation techniques: precipitation by the addition of an antisolvent (STRAP-A) and precipitation by decreasing the solvent temperature (STRAP-B). Both approaches were able to separate the constituent polymers in a post-industrial film composed primarily of polyethylene (PE), ethylene vinyl alcohol (EVOH), and polyethylene terephthalate (PET) with near 100 % material efficiency. Technoeconomic analysis indicates that the minimum selling price (MSP) of the recycled resins with STRAP-B is 21.0 % lower than that achieved with STRAP-A. This provides evidence that thermally driven polymer precipitation is an option to reduce the use of antisolvents, making the STRAP process more economically and environmentally attractive. A third process, STRAP-C, was demonstrated with another post-industrial multilayer film of a different composition. Here, the results demonstrate that this process can also recover polymers at similar costs to those of virgin resins, indicating that the STRAP technology is flexible and can remain economically competitive as the plastic feed complexity is increased.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relationship between isotope ratios in precipitation and stream water across watersheds of the National Ecological Observation Network

The timescales associated with precipitation moving through watersheds reveal processes that are critical to understanding many hydrologic systems. Measurements of environmental stable water isotope ratios (δ 2 H and δ 18 O) have been used as tracers to study hydrologic timescales by examining how long it takes for incoming precipitation tracers become stream discharge, yet limited measurements both spatially and temporally have bounded macroscale evaluations so far. Here in this observation driven study across North American biomes within the National Ecological Observation Network (NEON), we examined δ 18 O and δ 2 H stable water isotope in precipitation (δP) and stream water (δQ) at 26 co-located sites. With an average 54 precipitation samples and 139 stream water samples per site collected over 2014–2022, assessment of local meteoric water lines and local stream water lines showed geographic variation across North America. Taking the ratio of estimated seasonal amplitudes of δP and δQ to calculate young water fractions (F yw ), showed a Fyw range from 1% to 93% with most sites having F yw below 20%. Calculate d mean transit times (MTT) based on a gamma convolution model showed a MTT range from 0.10 to 13.2 years, with half of the sites having MTT estimates lower than 2 years. Significant correlations were found between the F yw and watershed area, longest flow length, and the longest flow length/slope. Significant correlations were found between MTT and site latitude, longitude, slope, clay fraction, temperature, precipitation magnitude, and precipitation frequency. The significant correlations between water timescale metrics and the environmental characteristics we report share some similarities with those reported in prior studies, demonstrating that these quantities are primarily driven by site or area specific factors. The analysis of isotope data presented here provides important constraints on isotope variation in North American biomes and the timescales of water movement through NEON study sites.

54 ENVIRONMENTAL SCIENCES↗

Quantifying the influence of natural climate variability on in situ measurements of seasonal total and extreme daily precipitation

Abstract While various studies explore the relationship between individual sources of climate variability and extreme precipitation, there is a need for improved understanding of how these physical phenomena simultaneously influence precipitation in the observational record across the contiguous United States. In this work, we introduce a single framework for characterizing the historical signal (anthropogenic forcing) and noise (natural variability) in seasonal mean and extreme precipitation. An important aspect of our analysis is that we simultaneously isolate the individual effects of seven modes of variability while explicitly controlling for joint inter-mode relationships. Our method utilizes a spatial statistical component that uses in situ measurements to resolve relationships to their native scales; furthermore, we use a data-driven procedure to robustly determine statistical significance. In Part I of this work we focus on natural climate variability: detection is mostly limited to DJF and SON for the modes of variability considered, with the El Niño/Southern Oscillation, the Pacific–North American pattern, and the North Atlantic Oscillation exhibiting the largest influence. Across all climate indices considered, the signals are larger and can be detected more clearly for seasonal total versus extreme precipitation. We are able to detect at least some significant relationships in all seasons in spite of extremely large (> 95%) background variability in both mean and extreme precipitation. Furthermore, we specifically quantify how the spatial aspect of our analysis reduces uncertainty and increases detection of statistical significance while also discovering results that quantify the complex interconnected relationships between climate drivers and seasonal precipitation.

54 ENVIRONMENTAL SCIENCES↗

Climate models project increasing precipitation in the US Southwest in 2024–2100

We analyzed the measured precipitation in the southwestern US and found that, from 1900 to 2024, precipitation decreased at an average rate of − 1.2 cm per year per 100 years. The most significant precipitation decreases occurred in the three-month period from February to April. At the same time, precipitation during the southwestern monsoon season (July, August, and September) remained relatively stable. The ensemble mean of all CMIP6 (Coupled Model Intercomparison Project phase 6) climate models, along with the regression model incorporating anthropogenic aerosol (AER) and Pacific Decadal Oscillation (PDO) as predictors, projects precipitation to increase from 2024 to 2100. This projected precipitation increase relies on the anticipated decrease in emissions of anthropogenic aerosols, which is associated with the transition from fossil fuel burning to renewable and nuclear energy sources.

54 ENVIRONMENTAL SCIENCES↗

Carbon Redistribution and Carbide Precipitation in a High-Strength Low-Carbon HSLA-115 Steel Studied on a Nanoscale by Atom Probe Tomography

HSLA-115 is a newly developed Cu-bearing high-strength low-carbon martensitic steel for use in Naval structural applications. This research provides, for the first time, a comprehensive compositional analysis of carbon redistribution and associated complex phase transformations in an isothermal aging study of HSLA-115 at 823 K (550 °C). Specifically, we characterize carbon segregation at lath boundaries, grain-refining niobium carbonitrides, cementite, and secondary hardening M2C carbides, in addition to copper precipitation, by 3D atom probe tomography (APT). Segregation of carbon (3 to 6 at. pct C) is observed at martensitic lath boundaries in the as-quenched and 0.12-hour aged microstructures. On further aging, carbon redistributes itself forming cementite and M2C carbides. Niobium carbonitride precipitates do not dissolve during the austenitizing treatment and are inherited in the as-quenched and aged microstructures; these are characterized along with cementite by synchrotron X-ray diffraction and APT. Sub-nanometer-sized M2C carbide precipitates are observed after the formation of Cu precipitates, co-located with the latter, indicating heterogeneous nucleation of M2C. The temporal evolution of the composition and morphology of M2C carbides at 823 K (550 °C) is described using APT; their precipitation kinetics is intertwined with Cu precipitates, affecting the bulk mechanical properties of HSLA-115. Phase compositions determined by APT are compared with computed compositions at thermodynamic equilibrium using ThermoCalc.

36 MATERIALS SCIENCE↗

Concurrent Precipitation of Nb(C,N) and Metastable M 23 C 6 in Alloy 347H at 700°C and 750°C: Computer Simulations and Comparison to Experiment

Here, we present our results for the concurrent precipitation of metastable M 23 C 6 , Nb(C,N) secondary precipitates, and the Nb(C,N) primary crystals in 347H austenitic stainless steel. For precipitation modeling, we have accounted for the elastic contribution to interfacial energy, and for the Fe-spin-polarization for NbC/Fe and M 23 C 6 /Fe interfacial energy values: for NbC/Fe ~ 0.63 J/m 2 . For M 23 C 6 precipitates, an error function was used to describe the interfacial energy growth with particle size. In precipitation simulations, the average size of the primary Nb(C,N) particles remained ~ 1 μm at 700°C and ~ 0.3 μm at 750°C. The M 23 C 6 precipitates at 750°C dissolved after 120 h (our simulations) compared to 300 h (experiments). The Nb(C,N)/Fe interfacial energy was not affected by the nitrogen additions. With these modifications, reasonable agreement with the available experimental data was obtained, which allows using them in the development of the 2nd-phase particle-informed creep theory.

36 MATERIALS SCIENCE↗

Topographic Controls on the Distribution of Summer Monsoon Precipitation over South Asia

In this work, we use a high-resolution (9 km) one-way nested regional climate modeling framework to systematically evaluate individual and aggregate roles of various components of topography in the precipitation distribution during South Asian Summer Monsoon (SASM). While it is not the arrival but the north-northwestward extent of summer monsoon precipitation that is regulated by the presence of elevated surfaces in South Asia, both the thermal and mechanical topographic forcing play a role. Topography not only provides mechanical uplifting and prevents dry air entrainment, it also helps regulate the strength of upper level anticyclone and tropical easterly jet, all of which are necessary to sustain a conducive environment for monsoon precipitation in the South Asian summer. In turn, precipitation feedbacks positively by accelerating the tropospheric diabatic warming through atmospheric latent heating and by maintaining the moisture supply through local recycling. Modifications in the topography, particularly the removal of the Tibetan Plateau, substantially modulates the moist flow in the lower troposphere and the anticyclonic circulation in the upper troposphere to an extent that the northern branch of SASM becomes substantially weaker. These changes give way to negative precipitation anomalies and eventually to an environment where the cycle of feedbacks that runs the process of monsoon progression over land becomes inefficient. The design of topographic modification experiments can influence precipitation response; therefore, we advise caution in the interpretation of these and previously reported results.

54 ENVIRONMENTAL SCIENCES↗

Crystal structure, energetics, and phase stability of strengthening precipitates in Mg alloys: A first-principles study

Magnesium alloys have attracted increasing interest due to their potential use as light-weight structural materials but their application is limited by their low strength compared to conventional alloys. Age hardening is commonly employed to form strengthening precipitates in such alloys, which impedes the motion of dislocations, and leads to improved strength. However, the exact composition, crystal structure, and energetics of many of these strengthening precipitates are either unknown or not clearly resolved, making the precise engineering and design of such alloys difficult. Toward this end, we use first-principles density functional theory calculations to elucidate the crystal structures and energetics of a very large set of precipitates in magnesium alloys. For cases where the precipitate crystal structure is not known, we comprehensively search over decorations of many prototype structures, including hcp superstructures, and in addition, perform global structural optimization using the Minima Hopping Method to predict suitable crystal structures. For all the strengthening precipitates, we calculate the formation energies, construct the respective zero temperature convex hulls, and analyze their stabilities. Here, we show that the bulk formation energies per solute atom (essentially, the solute chemical potentials) decrease along the observed sequences of precipitation, validating our calculations in Mg-{Nd, Gd, Y, Y-Nd, Nd-Zn, Gd-Zn, Y-Zn, Al, Zn, Sn, Al-Ca, Ca-Zn} alloy systems. In addition, we construct a monolayer model for the Guinier-Preston zones (GP zones) observed in the Mg-Nd-Zn system during early stages of age hardening, and thereby explain the formation of the γ" (Mg 5 (Nd,Zn)) phase from the GP zones, as observed in experiments.

36 MATERIALS SCIENCE↗

Combining solution-, precipitation- and load-transfer strengthening in a cast Al-Ce-Mn- Sc -Zr alloy

Here, a cast Al-9Ce-0.75Mn-0.18Sc-0.12Zr (wt%) alloy is designed to combine three strengthening phases: (i) micron-scale Al 11 Ce 3 platelets formed during eutectic solidification, (ii) nano-scale L1 2 -Al 3 (Sc,Zr) precipitates formed during aging, and (iii) Mn in solid solution in the α-Al matrix. Microstructural analyses by SEM, TEM, and atom-probe tomography reveal that Mn remains in solid solution in the as-cast alloy, providing solution strengthening with no influence on the eutectic Al-Al 11 Ce 3 microstructure, which provides precipitation- and load-transfer strengthening. During long-term over-aging at 400 °C, Mn-rich precipitates grow at the Al-Al 11 Ce 3 interface, with no effect on the microhardness. However, after short aging at 350 °C, a high number density of fine L1 2 -Al 3 (Sc,Zr) nanoprecipitates form in the Al matrix (with a coarser size at the Al-Al 11 Ce 3 interface), providing precipitation strengthening. The synergistic combination of the three strengthening mechanisms (solution, precipitation, and load transfer) in our Al-Ce-Mn-Sc-Zr alloy results in higher microhardness after aging at 350 and 400 °C, and higher creep resistance at 300 °C, as compared to alloys with two strengthening mechanisms: an Al-10Ce-0.93Mn control alloy (without precipitation strengthening from Sc and Zr), Al-Ce-Sc-Zr (without solution strengthening from Mn), and Al-Mn-Zr-Er (without load-transfer strengthening from Ce). Furthermore, these dual-strengthened alloys are more creep resistant than alloys with a single strengthening mechanism (Al-Ce, Al-Mn, and Al-Sc-Zr), confirming that the three mechanisms can be combined in pairs or all together.

36 MATERIALS SCIENCE↗

Selectivity of tris complexation for Ni(II), Co(II), and Fe(II) and its effect on carbonate precipitation under alkaline conditions

Simultaneous critical element recovery and ex-situ carbon mineralization of low-grade ultramafic deposits have garnered increasing interest. Understanding the selectivity of metal complexing organic ligands for various divalent metals present in ultramafic rocks during carbonate mineralization is required to optimize this process. Here we evaluate 2-amino-2-(hydroxymethyl)-1,3-propanediol (i.e., Tris) as a model for bidentate ligands that bind divalent metals with both amine and alcohol groups in alkaline conditions (pH 8–10.5) at 25 °C and 80 °C in carbonate-buffered solutions. Protonated Tris forms a stronger complex with metal ions and is selective for trace metals with Ni(II) > Co(II) > Fe(II) during carbonate precipitation, with the rates decreasing but selectivity increasing at lower temperature and lower pH. At 25 °C, metastable amorphous hydrated carbonates form, regardless of the amount of Tris present or pH values. At 80 °C and pH 8, the Co and Fe carbonates that form are a mixture of rosasite-group minerals (Co 2 CO 3 (OH) 2 (H 2 O) and Fe 2 CO 3 (OH) 2 ) and pure carbonates (sphaerocobaltite: CoCO 3 and siderite: FeCO 3 ), with the latter more stabilized with increasing Tris concentration. In mixed metal solutions without Tris at 25 °C where Fe:Ni or Fe:Co is 2:1, Fe increases the rates of Ni or Co carbonate precipitation. However, with increasing Tris concentration the presence of Ni or Co inhibits Fe carbonate precipitation. At 80 °C without Tris, Ni or Co substitute into the iron chukanovite (Fe 2 CO 3 (OH) 2 ) lattice, increasing Ni or Co carbonate precipitation rates. Increasing Tris concentration only slightly inhibits Fe and Co precipitation, but slows Ni precipitation up to 10 times, with Fe progressively partitioning into more pure carbonate phases with distinct crystalline morphologies. These findings suggest bidentate amine-bearing ligands may be effective at Ni and Co recovery during carbon mineralization of Fe-bearing ultramafic deposits at relatively low temperatures and slightly alkaline pH.

54 ENVIRONMENTAL SCIENCES↗

Effect of Co-solutes on the Products and Solubility of Uranium(VI) Precipitated with Phosphate

Uranyl phosphate solids are often found with uranium ores, and their low solubility makes them promising target phases for in situ remediation of uranium-contaminated subsurface environments. The products and solubility of uranium(VI) precipitated with phosphate can be affected by the pH, dissolved inorganic carbon (DIC) concentration, and co-solute composition (e.g. Na+/Ca2+) of the groundwater. Batch experiments were performed to study the effect of these parameters on the products and extent of uranium precipitation induced by phosphate addition. In the absence of co-solute cations, chernikovite [H3O(UO2)(PO4)•3H2O] precipitated despite uranyl orthophosphate [(UO2)3(PO4)2•4H2O] being thermodynamically more favorable under certain conditions. As determined using X-ray diffraction, electron microscopy, and laser induced fluorescence spectroscopy, the presence of Na+ or Ca2+ as a co-solute led to the precipitation of sodium autunite ([Na2(UO2)2(PO4)2] and autunite [Ca(UO2)2(PO4)2]), which are structurally similar to chernikovite. In the presence of sodium, the dissolved U(VI) concentrations were generally in agreement with equilibrium predictions of sodium autunite solubility. However, in the calcium-containing systems, the observed concentrations were below the predicted solubility of autunite, suggesting the possibility of uranium adsorption to or incorporation in a calcium phosphate precipitate in addition to the precipitation of autunite.

Environmental Molecular Sciences Laboratory↗

Mineral Dissolution and Secondary Precipitation on Quartz Sand in Simulated Hanford Tank Solutions Affecting Subsurface Porosity

Highly alkaline nuclear waste solutions have been released from underground nuclear waste storage tanks and pipelines into the vadose zone at the U.S. Department of Energy’s Hanford Site in Washington, causing mineral dissolution and re-precipitation upon contact with subsurface sediments. High pH caustic NaNO3 solutions with and without dissolved Al were reacted with quartz sand through flow-through columns stepwise at 45, 51, and 89°C to simulate possible reactions between leaked nuclear waste solution and primary subsurface mineral. Upon reaction, Si was released from the dissolution of quartz sand, and nitrate-cancrinite [Na8Si6Al6O24(NO3)2] precipitated on the quartz surface as a secondary mineral phase. Both steady-state dissolution and precipitation kinetics were quantified, and quartz dissolution apparent activation energy was determined. Mineral alteration through dissolution and precipitation processes results in pore volume and structure changes in the subsurface porous media. In this study, the column porosity increased up to 40.3% in the pure dissolution column when no dissolved Al was present in the leachate, whereas up to a 26.5% porosity decrease was found in columns where both dissolution and precipitation were observed because of the presence of Al in the input solution. The porosity change was also confirmed by calculation using the dissolution and precipitation rates and mineral volume changes.

alkaline nuclear waste solution↗

Synthesis of YAG nanopowder by the co-precipitation method: Influence of pH and study of the reaction mechanisms

YAG nanopowders with an average grain size of 30 nm have been successfully synthesized by the co-precipitation method using nitrates with precipitant of ammonium hydrogen carbonate. The influence of precipitation conditions such as pH, aging time and calcination temperature on the formation of secondary phases has been studied. The accurate control of pH value at every stage of precipitation process is crucial to avoid the presence of YAM (Yttrium Aluminium Monoclinic, Y{sub 4}Al{sub 2}O{sub 9}) and yttrium oxide (Y{sub 2}O{sub 3}) after calcination. The reaction mechanisms have been investigated using different techniques such as infrared spectroscopy, x-ray diffraction and thermal analyses. The YAG phase is formed around 1050 Degree-Sign C passing through an intermediate phase called YAP (Yttrium Aluminium Perovskite, YAlO{sub 3}). Local chemical heterogeneities are responsible for the deviation of the Y:Al ratio and the formation of YAP during heat treatment. - Graphical abstract: Synthesis of YAG nanopowder by the co-precipitation method: Influence of pH and study of the reaction mechanisms, Marlot et al. Highlights: Black-Right-Pointing-Pointer Synthesis of pure YAG nanoparticles by the co-precipitation method. Black-Right-Pointing-Pointer Influence of pH value on the formation of secondary phases all along the process. Black-Right-Pointing-Pointer Study of the importance of pH using titration method. Black-Right-Pointing-Pointer Chemical evolution of the precursor during calcinations. Black-Right-Pointing-Pointer Proposition for reaction mechanisms.

36 MATERIALS SCIENCE↗

Structural and compositional evolution of Al{sub 3}(Zr,Y) precipitates in Al-Zr-Y alloy

Structural and compositional evolution of Al{sub 3}(Zr,Y) precipitates in aged Al-Zr-Y alloy was investigated through atom probe tomography (APT) and transmission electron microscope (TEM) analysis and first principles calculations. The results show that short-bar-shaped D0{sub 19}-Al{sub 3}Y with some Zr atoms dissolved in precipitated at the very beginning of decomposition and worked as heterogeneous nuclei for L1{sub 2}-Al{sub 3}Zr with spherical morphology after being aged at 400 °C for 2 h. Quasi-static coarsening happened as the aging treatment lasted from 2 h to 200 h. However, distribution of Zr and Y atoms in Al{sub 3}(Zr,Y) is nearly uniform and Al{sub 3}(Zr,Y) do not have the typical “Al{sub 3}RE core-Al{sub 3}Zr shell” structure which observed in other RE containing Al-Zr-RE alloys with L1{sub 2}-Al{sub 3}RE as nuclei. First principles calculations revealed that binding energy between Y and Zr is strong during the growth of Al{sub 3}(Zr,Y), which led to the co-precipitation of Y and Zr atoms and attribute to the evolution of Al{sub 3}(Zr,Y). - Highlights: •Al{sub 3}Y precipitated firstly and then became nuclei for Al{sub 3}Zr during aging of Al-Zr-Y. •Al{sub 3}(Zr,Y) precipitates do not have the typical “Al{sub 3}Y core-Al{sub 3}Zr shell” structure. •Strong binding between Y and Zr led to the co-precipitation of Y and Zr atoms.

36 MATERIALS SCIENCE↗

Warming and increased precipitation frequency on the Colorado Plateau: Implications for biological soil crusts and soil processes

Frequent hydration and drying of soils in arid systems can accelerate desert carbon and nitrogen mobilization due to respiration, microbial death, and release of intracellular solutes. Because desert microinvertebrates can mediate nutrient cycling, and the autotrophic components of crusts are known to be sensitive to rapid desiccation due to elevated temperatures after wetting events, we studied whether altered soil temperature and frequency of summer precipitation can also affect the composition of food web consumer functional groups. We conducted a two-year field study with experimentally-elevated temperature and frequency of summer precipitation in the Colorado Plateau desert, measuring the change in abundance of nematodes, protozoans, and microarthropods. We hypothesized that microfauna would be more adversely affected by the combination of elevated temperature and frequency of summer precipitation than either effect alone, as found previously for phototrophic crust biota. Microfauna experienced normal seasonal fluctuations in abundance, but the effect of elevated temperature and frequency of summer precipitation was statistically non-significant for most microfaunal groups, except amoebae. The seasonal increase in abundance of amoebae was reduced with combined elevated temperature and increased frequency of summer precipitation compared to either treatment alone, but comparable with control (untreated) plots. Based on our findings, we suggest that desert soil microfauna are relatively more tolerant to increases in ambient temperature and frequency of summer precipitation than the autotrophic components of biological soil crust at the surface.

54 ENVIRONMENTAL SCIENCES↗

Influence of phosphate and silica on U(VI) precipitation from acidic and neutralized wastewaters

Uranium speciation and physical-chemical characteristics were studied in solids precipitated from synthetic acidic to circumneutral wastewaters in the presence and absence of dissolved silica and phosphate to examine thermodynamic and kinetic controls on phase formation. Composition of synthetic wastewater was based on disposal sites 216-U-8 and 216-U-12 Cribs at the Hanford site (WA, USA). In the absence of dissolved silica or phosphate, crystalline or amorphous uranyl oxide hydrates, either compreignacite or meta-schoepite, precipitated at pH 5 or 7 after 30 d of reaction, in agreement with thermodynamic calculations. In the presence of 1 mM dissolved silica representative of groundwater concentrations, amorphous phases dominated by compreignacite precipitated rapidly at pH 5 or 7 as a metastable phase and formation of poorly-crystalline boltwoodite, the thermodynamically stable uranyl silicate phase, was slow. In the presence of phosphate (3 mM), meta-ankoleite initially precipitated as the primary phase at pH 3, 5, or 7 regardless of the presence of 1 mM dissolved silica. Analysis of precipitates by U LIII-edge EXAFS indicated that “autunite-type” sheets of meta-ankoleite transformed to “phosphuranylite-type” sheets after 30 d of reaction, probably due to Ca substitution in the structure. Low solubility of uranyl phosphate phases limits dissolved U(VI) concentrations but differences in particle size, crystallinity, and precipitate composition vary with pH and base cation concentration, which will influence the thermodynamic and kinetic stability of these phases.

acid waste↗