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DOE OSTI2014

Precipitation of calcium carbonate and calcium phosphate under diffusion controlled mixing

Multi-component mineral precipitation in porous, subsurface environments is challenging to simulate or engineer when in situ reactant mixing is controlled by diffusion. In contrast to well-mixed systems, the conditions that favor mineral precipitation in porous media are distributed along chemical gradients, which evolve spatially due to concurrent mineral precipitation and modification of solute transport in the media. The resulting physical and chemical characteristics of a mixing/precipitation zone are a consequence of coupling between transport and chemical processes, and the distinctive properties of individual chemical systems. We examined the spatial distribution of precipitates formed in “double diffusion” columns for two chemical systems, calcium carbonate and calcium phosphate. Polyacrylamide hydrogel was used as a low permeability, high porosity medium to maximize diffusive mixing and minimize pressure- and density-driven flow between reactant solutions. In the calcium phosphate system, multiple, visually dense and narrow bands of precipitates were observed that were reminiscent of previously reported Liesegang patterns. In the calcium carbonate system, wider precipitation zones characterized by more sparse distributions of precipitates and a more open channel structure were observed. In both cases, formation of precipitates inhibited, but did not necessarily eliminate, continued transport and mixing of the reactants. A reactive transport model with fully implicit coupling between diffusion, chemical speciation and precipitation kinetics, but where explicit details of nucleation processes were neglected, was able to qualitatively simulate properties of the precipitation zones. The results help to illustrate how changes in the physical properties of a precipitation zone depend on coupling between diffusion-controlled reactant mixing and chemistry-specific details of precipitation kinetics.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2012

Effect of solution annealing temperature on precipitation in 2205 duplex stainless steel

In the present study, effect of solution annealing temperature (1050 Degree-Sign C and 1100 Degree-Sign C) and isothermal ageing (700 Degree-Sign C: 15 min to 6 h) on the microstructural changes in 2205 duplex stainless steel has been investigated systematically. Scanning electron microscopy and X-ray diffraction were adopted to follow the microstructural evolution, while an energy dispersive spectrometer attached to scanning electron microscope was used to obtain localised chemical information of various phases. The ferritic matrix of the two phase 2205 duplex stainless steel ({approx} 45% ferrite and {approx} 55% austenite) undergoes a series of metallurgical transformations during ageing-formation of secondary austenite ({gamma}{sub 2}) and precipitation of Cr and Mo rich intermetallic (chi-{chi} and sigma-{sigma}) phases. For solution annealing at 1050 Degree-Sign C, significant amount of carbides were observed in the ferrite grains after 1 h of ageing at 700 Degree-Sign C. {chi} Phase precipitated after the precipitation of carbides-preferentially at the ferrite-ferrite and also at the ferrite-austenite boundaries. {sigma} Phase was not observed in significant quantity even after 6 h of ageing. The sequence of precipitation in samples solution annealed at 1050 Degree-Sign C was found to be carbides {yields} {chi} {yields} {sigma}. On the contrary, for samples solution annealed at 1100 Degree-Sign C, the precipitation of {chi} phase was negligible. {chi} Phase precipitated before {sigma} phase, preferentially along the ferrite-ferrite grain boundaries and was later consumed in the {sigma} phase precipitation. The {sigma} phase precipitated via the eutectoid transformation of ferrite to yield secondary austenite {gamma}{sub 2} and {sigma} phase in the ferrite and along the ferrite-austenite grain boundaries. An increase in the volume fraction of {gamma}{sub 2} and {sigma} phase with simultaneous decrease in the ferrite was evidenced with ageing. - Highlights: Black-Right-Pointing-Pointer Effect of solution annealing temperature on microstructural evolution is studied. Black-Right-Pointing-Pointer {chi} Phase precipitated preferentially in the samples solution annealed at 1050 Degree-Sign C. Black-Right-Pointing-Pointer {sigma} Phase precipitated preferentially in the samples solution annealed at 1100 Degree-Sign C. Black-Right-Pointing-Pointer For SA at 1050 Degree-Sign C, the sequence of precipitation was carbides {yields} {chi} phase {yields} {sigma} phase. Black-Right-Pointing-Pointer For SA at 1100 Degree-Sign C, {sigma} phase precipitated via the eutectoid reaction: ferrite (F) {yields} {sigma} + {gamma}{sub 2}.

36 MATERIALS SCIENCE↗

DOE OSTI2014

Characterisation of Laves phase precipitation and its correlation to creep rupture strength of ferritic steels

The Laves phase precipitation process was characterised by means of field emission scanning electron microscopy to demonstrate its effect on creep rupture strength of steels with a fully ferritic matrix. To eliminate the effects of carbide and carbonitride precipitations so that the creep rupture data can be analysed exclusively in relation to the Laves phase precipitation process, an alloy Fe–9Cr–3Co–3W (wt.%) without C and N additions was used for the study. Creep rupture strengths were measured and volume fraction and particle size of Laves phase precipitates in the ruptured specimens were analysed. It was found that the creep rupture strength started to collapse (or decrease more rapidly) long before the Laves phase precipitation reached equilibrium fraction. This was related to the onset of the coarsening of Laves phase particles, which precipitated only on grain boundaries and hence contributed little to precipitation strengthening. Creep deformation had no effect either on the precipitation kinetics or on the growth kinetics of Laves phase particles. - Highlights: • Laves phase precipitation at 650 °C was characterised for Fe–9Cr–3W–3Co alloy. • Laves phase precipitated predominantly on grain boundaries. • Creep deformation had no effect on Laves phase precipitation and growth kinetics. • Creep strength started to collapse long before Laves phase precipitation is ended. • Collapse of creep strength was attributed to the coarsening of Laves phase particles.

36 MATERIALS SCIENCE↗

DOE OSTI2018

The evolution of precipitate crystal structures in an Al-Mg-Si(-Cu) alloy studied by a combined HAADF-STEM and SPED approach

Highlights: • Scanning electron diffraction and machine learning complement lattice imaging • Developed approach gives increased objectivity in precipitate phase analysis • Precipitate phase fractions and solute content obtained with superior statistics • 0.01 at.% Cu changes the Al-Mg-Si system precipitation during overageing • Q’-phase eventually dominates precipitate structures and shows varying Cu-occupancy - Abstract: This work presents a detailed investigation into the effect of a low Cu addition (0.01 at.%) on precipitation in an Al-0.80Mg-0.85Si alloy during ageing. The precipitate crystal structures were assessed by scanning transmission electron microscopy combined with a novel scanning precession electron diffraction approach, which includes machine learning. The combination of techniques enabled evaluation of the atomic arrangement within individual precipitates, as well as an improved estimate of precipitate phase fractions at each ageing condition, through analysis of a statistically significant number of precipitates. Based on the obtained results, the total amount of solute atoms locked inside precipitates could be approximated. It was shown that even with a Cu content close to impurity levels, the Al-Mg-Si system precipitation was significantly affected with overageing. The principal change was due to a gradually increasing phase fraction of the Cu-containing Q′-phase, which eventually was seen to dominate the precipitate structures. The structural overtake could be explained based on a continuous formation of the thermally stable Q′-phase, with Cu atomic columns incorporating less Cu than what could potentially be accommodated.

36 MATERIALS SCIENCE↗

DOE OSTI2012

Synthesis of high surface area ZnO powder by continuous precipitation

Graphical abstract: High surface area ZnO powders are synthesized by a low temperature continuous precipitation under ultrasonication. Urea is used as precipitating agent so that no contamination of ZnO powder emanating from precipitating agent, such as, alkalis, is observed. pH and type of precursor greatly affects the surface area and other properties. In this manuscript, we report a very simple and effective continuous precipitation to synthesize high surface area ZnO powder. Highlights: Black-Right-Pointing-Pointer The synthesis of high surface area ZnO powder was achieved at 90 Degree-Sign C in a continuous precipitation unit. Black-Right-Pointing-Pointer Continuous precipitation unit was ultrasonicated to improve final product homogeneity. Black-Right-Pointing-Pointer Precipitation intermediate, hydrozincite, was led to high surface area ZnO powder. Black-Right-Pointing-Pointer The synthesized ZnO nanoparticles had a rather uniform mesoporous structure. -- Abstract: Synthesis of high surface area ZnO powder was achieved by continuous precipitation using zinc ions and urea at low temperature of 90 Degree-Sign C. The powder precipitated resulted in high-purity single-phase ZnO powder when calcined at 280 Degree-Sign C for 3 h in air. The solution pH and the precipitation duration strongly affected the surface area of the calcined ZnO powder. Detailed structural characterizations demonstrated that the synthesized ZnO powder were single crystalline with wurtzite hexagonal phase. The powdered samples precipitated by homogeneous precipitation crystallized directly to hydrozincite without any intermediate phase formation. The phase structures, morphologies and properties of the final ZnO powders were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), dynamic light scattering particle size analysis (DLS), and nitrogen physisorption in order to determine the specific surface area (BET) and the pore size distribution (BJH).

36 MATERIALS SCIENCE↗

DOE OSTI2021

Understanding the interaction of extension twinning and basal-plate precipitates in Mg-9Al using precession electron diffraction

Precession electron diffraction is used to characterize the interaction between ${10\bar{1}2}$ tensile twins and basal plate-like precipitates in a post-deformed, precipitate-dispersed Mg-9Al micropillar. We observed a heterogeneous distribution of precipitates in the micropillar sample, which enabled the study of the different stages involved in twin precipitate interactions. We show that twin nucleation was promoted, taking place on the surface, as well as from the interior of the micropillar. Twin tip propagation and twin growth were hindered by the precipitates. Twin tips either were arrested by precipitates and new twins formed on the other side of the precipitate, or continued to grow around the precipitate without the re-nucleation events. During twin thickening, the precipitates did not significantly alter the shear-dominant twin boundary migration mechanism, as evidenced by the relatively flat twin boundaries around the partially embedded precipitates. However, the twin boundary migration was retarded by the precipitates, especially in regions confined by closely-spaced precipitates.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Extreme Precipitation Over the Southern Slope of the Tibetan Plateau and the Associated Atmospheric Circulation Anomalies

The southern slope of the Tibetan Plateau (SSTP) is one of the rainiest regions in the world where geological hazards caused by extreme precipitation often occur. This study investigates the characteristics and mechanisms of extreme precipitation over SSTP from June to September during 2001–2020 using Global Precipitation Measurement satellite observation. The extreme precipitation days are defined as the days with top 5% of regional-mean daily precipitation over SSTP in this period, which has an average precipitation of 27.2 mm/d. Averaging over the extreme precipitation days, precipitation peaks at an altitude of about 300 m, coinciding with the climatological maximum precipitation, but with a much larger value of 37.2 mm/d than the climatology of 11.9 mm/d. Composite analysis of circulations on extreme days reveals significant circulation anomalies in both the lower and upper troposphere. Specifically, the lower-tropospheric circulations are characterized by significant westerly anomalies over northern India, and the upper-tropospheric circulations are characterized by northerly anomalies over the central Tibetan Plateau, which are statistically independent. The lower-tropospheric westerly anomalies blowing toward SSTP are blocked by the topography, favoring extreme precipitation over SSTP. The upper-tropospheric northerly anomalies, on the other hand, correspond to anomalous northeasterlies north of SSTP in the middle troposphere and southeasterlies to the south in the lower troposphere, and the convergence of these circulation anomalies favors extreme precipitation over SSTP. Lastly, the lower-tropospheric westerly and upper-tropospheric northerly anomalies, respectively, correspond to less precipitation over the South Asian monsoon region and the Tibetan Plateau.

Extreme precipitation, Tibetan Plateau↗

DOE OSTI2025

Evaluation of historical precipitation interannual variability in CMIP6 over the United States

Interannual precipitation variability profoundly influences society via its effects on agriculture, water resources, infrastructure, and disaster risks. In this study, we use daily in situ precipitation observations from the global historical climatology network-daily (GHCN-D) to assess the ability of 21 Coupled Model Intercomparison Project Phase 6 (CMIP6) models, including the 50-member fifth-generation Canadian Earth System Model single model initial-condition large ensemble (CanESM5_SMILE), to realistically simulate historical interannual precipitation variability trends within 17 regions of the contiguous United States (CONUS). We assess how accurately the CMIP6 simulations align with observational data across annual, summer, and winter periods, focusing on four key hydrometeorological metrics, including interannual precipitation variability, relative interannual precipitation variability (coefficient of variation), annual mean precipitation, and annual wet day frequency. Our findings reveal that CMIP6 ensemble members generally reproduce the spatial patterns of observed trends in annual mean precipitation. In most regions, models agree well with the signs of observed changes in annual mean precipitation, though discrepancies in trend magnitude are evident. Further, observed trends in winter mean precipitation broadly exhibit a spatial pattern similar to that of the observed annual mean. However, analysis of the CanESM5_SMILE shows that trends in precipitation variability may primarily be the result of model-simulated internal variability, suggesting caution in interpreting multi-model single-realization ensemble results. Challenges in accurately simulating interannual precipitation variability underscore the need for ongoing model refinement and validation to enhance climate projections, especially in regions vulnerable to extreme precipitation events.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2015

A cross-biome synthesis of soil respiration and its determinants under simulated precipitation changes

Soil respiration (R s ) is the second-largest terrestrial carbon (C) flux. Although R s has been extensively studied across a broad range of biomes, there is surprisingly little consensus on how the spatiotemporal patterns of Rs will be altered in a warming climate with changing precipitation regimes. Here, we present a global synthesis Rs data from studies that have manipulated precipitation in the field by collating studies from 113 increased precipitation treatments, 91 decreased precipitation treatments, and 14 prolonged drought treatments. Our meta-analysis indicated that when the increased precipitation treatments were normalized to 28% above the ambient level, the soil moisture, R s ,and the temperature sensitivity (Q 10 ) values increased by an average of 17%, 16%, and 6%, respectively, and the soil temperature decreased by -1.3%. The greatest increases in R s and Q 10 were observed in arid areas, and the stimulation rates decreased with increases in climate humidity. When the decreased precipitation treatments were normalized to 28% below the ambient level, the soil moisture and Rs values decreased by an average of -14% and -17%, respectively, and the soil temperature and Q 10 values were not altered. The reductions in soil moisture tended to be greater in more humid areas. Prolonged drought without alterations in the amount of precipitation reduced the soil moisture and Rs by -12% and -6%, respectively, but did not alter Q 10 . Overall, our synthesis suggests that soil moisture and Rs tend to be more sensitive to increased precipitation in more arid areas and more responsive to decreased precipitation in more humid areas. The responses of R s and Q 10 were predominantly driven by precipitation-induced changes in the soil moisture, whereas changes in the soil temperature had limited impacts. Finally, our synthesis of prolonged drought experiments also emphasizes the importance of the timing and frequency of precipitation events on ecosystem C cycles. Given these findings, we urge future studies to focus on manipulating the frequency, intensity, and seasonality of precipitation with an aim to improving our ability to predict and model feedback between R s and climate change.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2026

Object-Based Evaluation of Dynamical and Statistical Downscaled Precipitation Products over CONUS

High-resolution precipitation data, generated through dynamical downscaling (DD) or statistical downscaling (SD) of global climate model output, provide critical information for regional climate assessment and adaptation planning. Most downscaling development and validation have focused on accurate gridscale precipitation construction and ignored the spatial structure of precipitation across model grids and at the event scale. However, many applications, e.g., hydrologic modeling and the analysis using the downscaled precipitation, require a reasonable representation of the spatial structure of precipitation within watersheds. Therefore, a set of standard metrics to evaluate the representation of the spatial structure of individual storms across diverse downscaled precipitation products is desired. To address this need, we conducted an object-based evaluation of precipitation in decades-long DD and SD products over the contiguous United States (CONUS). Specifically, we evaluate their ability to reproduce various features of precipitation objects in the observations: total volume, precipitation area, peak intensity, and spatial structure. Multiple metrics (bias, Perkins score, and nonparametric statistical tests) are used to quantify model performance. Our evaluation reveals notable variations in performance among individual products across different climate zones and seasons, as well as between extreme and nonextreme events. In general, most DD products exhibit balanced performance across the four precipitation object features, while SD products vary more significantly in their performance across products. Based on this comprehensive evaluation, we provide guidance on choosing downscaled products for specific regions, seasons, and precipitation object features. These findings and recommendations can inform precipitation-relevant modeling and analysis over CONUS, guide future downscaling technique developments, and provide actionable information for climate impact assessment and adaptation.

Downscaling↗

DOE OSTI2019

Evaluation of Modeled Precipitation in Oceanic Extratropical Cyclones Using IMERG

Using a high-spatial- and high-temporal-resolution precipitation dataset, Integrated Multi-satellite Retrievals for GPM (IMERG), extratropical cyclone precipitation is evaluated in two reanalyses and two climate models. Based on cyclone-centered composites, all four models overestimate precipitation in the western subsiding and dry side of the cyclones, and underestimate the precipitation in the eastern ascending and moist side. By decomposing the composites into frequency of occurrence and intensity (mean precipitation rate when precipitating), the analysis reveals a tendency for all four models to overestimate frequency and underestimate intensity, with the former issue dominating in the western half and the latter in the eastern half of the cyclones. Differences in frequency are strongly dependent on cyclone environmental moisture, while the differences in intensity are strongly impacted by the strength of ascent within the cyclone. There are some uncertainties associated with the observations: IMERG might underreport frozen precipitation and possibly exaggerate rates in vigorously ascending regions. Nevertheless, the analysis suggests that all models produce extratropical cyclone precipitation too often and too lightly. These biases have consequences when evaluating the changes in precipitation characteristics with changes in cyclone properties: the models disagree on the magnitude of the change in precipitation intensity with a change in environmental moisture and in precipitation frequency with a change in cyclone strength. This complicates accurate predictions of precipitation changes in a changing climate.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2021

Evaluation of GEOS Precipitation Flagging for SMAP Soil Moisture Retrieval Accuracy

The precipitation flag in the Soil Moisture Active Passive (SMAP) Level 2 passive soil moisture (L2SMP) retrieval product indicates the presence or absence of heavy precipitation at the time of the SMAP overpass. The flag is based on precipitation estimates from the Goddard Earth Observing System (GEOS) Forward Processing numerical weather prediction system. An error in flagging during an active or recent precipitation event can produce either 1) an overestimation of soil moisture due to short-term surface wetting of vegetation and/or surface ponding (if soil moisture retrieval was attempted in the presence of rain) or 2) an unnecessary nonretrieval of soil moisture and loss of data (if retrieval is flagged due to an erroneous indication of rain). Satellite precipitation estimates from the Integrated Multisatellite Retrievals for GPM (IMERG), version 06, Early Run (latency of ~4 h) precipitationCal product are used here to evaluate the GEOS-based precipitation flag in the L2SMP product for both the 1800 local time (LT) ascending and 0600 LT descending SMAP overpasses over the first five years of the mission (2015–20). Consisting of blended precipitation measurements from the Global Precipitation Mission (GPM) satellite constellation, IMERG is treated as the “truth” when comparing to the GEOS model forecasts of precipitation used by SMAP. Key results include (i) IMERG measurements generally show higher spatial variability than the GEOS forecast precipitation, (ii) the IMERG product has a higher frequency of light precipitation amounts, and (iii) the effect of incorporating IMERG rainfall measurements in lieu of GEOS precipitation forecasts are minimal on the L2SMP retrieval accuracy (determined vs in situ soil moisture measurements at core validation sites). Our results indicate that L2SMP retrievals continue to meet the mission’s accuracy requirement [standard deviation of the unbiased RMSE (ubRMSE) less than 0.04 cu. m/cu. m].

IMERG-precipitationCal↗

DOE OSTI2022

Partitioning behavior and mechanisms of rare earth elements during precipitation in acid mine drainage

Rare earth elements (REEs) are frequently found concentrated in acid mine drainage (AMD). The recovery of REEs from AMD has been successfully achieved using selective chemical precipitation. However, a portion of the REEs is often lost to the precipitates of the dominant metal contaminant ions. To better understand the REE partitioning behavior and mechanisms during the precipitation process, a systematic study was performed on both natural and synthetic AMD solutions. Precipitation test results show that REE removal was noticeably elevated at pH 4.0 after adding H 2 O 2 to convert ferrous to ferric ions, causing nearly complete precipitation of iron. Solution equilibrium calculations suggested that the REE removal increase was realized through adsorption onto the surfaces of the ferric precipitates. The presence of aluminum species in the solutions reduced the adsorption of REEs on the ferric precipitates. Based on electro-kinetic test results, it was concluded that aluminum species neutralize the negative surface charge of the ferric precipitates and compete with REEs for the adsorption active sites. The presence of ferrous ions in the solutions reduced REE adsorption on the aluminum precipitates at lower pH values (e.g., 5.0) due to competitive adsorption. However, at higher pH values (e.g., 6.0), REE removal to the precipitate product increased due to the precipitation of ferrous ions. Additionally, to the electro-kinetic tests and solution equilibrium calculations, mineralogy characterization, specific surface area measurement, particle size analysis, and morphology analysis were also conducted to investigate and identify the partitioning mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Object-Based Evaluation of Dynamical and Statistical Downscaled Precipitation Products over CONUS

Environmental sciences↗

DOE OSTI2019

Thermodynamic and Dynamic Mechanisms for Hydrological Cycle Intensification over the Full Probability Distribution of Precipitation Events

Abstract Precipitation changes in a warming climate have been examined with a focus on either mean precipitation or precipitation extremes, but changes in the full probability distribution of precipitation have not been well studied. This paper develops a methodology for the quantile-conditional column moisture budget of the atmosphere for the full probability distribution of precipitation. Analysis is performed on idealized aquaplanet model simulations under 3-K uniform SST warming across different horizontal resolutions. Because the covariance of specific humidity and horizontal mass convergence is much reduced when conditioned onto a given precipitation percentile range, their conditional averages yield a clear separation between the moisture (thermodynamic) and circulation (dynamic) effects of vertical moisture transport on precipitation. The thermodynamic response to idealized climate warming can be understood as a generalized “wet get wetter” mechanism, in which the heaviest precipitation of the probability distribution is enhanced most from increased gross moisture stratification, at a rate controlled by the change in lower-tropospheric moisture rather than column moisture. The dynamic effect, in contrast, can be interpreted by shifts in large-scale atmospheric circulations such as the Hadley cell circulation or midlatitude storm tracks. Furthermore, horizontal moisture advection, albeit of secondary role, is important for regional precipitation change. Although similar mechanisms are at play for changes in both mean precipitation and precipitation extremes, the thermodynamic contributions of moisture transport to increases in high percentiles of precipitation tend to be more widespread across a wide range of latitudes than increases in the mean, especially in the subtropics.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2017

Twenty-First-Century Changes in U.S. Regional Heavy Precipitation Frequency Based on Resolved Atmospheric Patterns

Precipitation-gauge observations and atmospheric reanalysis are combined to develop an analogue method for detecting heavy precipitation events based on prevailing large-scale atmospheric conditions. Combinations of atmospheric variables for circulation (geopotential height and wind vector) and moisture (surface specific humidity, column and up to 500-hPa precipitable water) are examined to construct analogue schemes for the winter [December–February (DJF)] of the “Pacific Coast California” (PCCA) region and the summer [June–August (JJA)] of the Midwestern United States (MWST). The detection diagnostics of analogue schemes are calibrated with 1979–2005 and validated with 2006–14 NASA Modern-Era Retrospective Analysis for Research and Applications (MERRA). All analogue schemes are found to significantly improve upon MERRA precipitation in characterizing the occurrence and interannual variations of observed heavy precipitation events in the MWST. When evaluated with the late twentieth-century climate model simulations from phase 5 of the Coupled Model Intercomparison Project (CMIP5), all analogue schemes produce model medians of heavy precipitation frequency that are more consistent with observations and have smaller intermodel discrepancies than model-based precipitation. Under the representative concentration pathways (RCP) 4.5 and 8.5 scenarios, the CMIP5-based analogue schemes produce trends in heavy precipitation occurrence through the twenty-first century that are consistent with model-based precipitation, but with smaller intermodel disparity. The median trends in heavy precipitation frequency are positive for DJF over PCCA but are slightly negative for JJA over MWST. Overall, the analyses highlight the potential of the analogue as a powerful diagnostic tool for model deficiencies and its complementarity to an evaluation of heavy precipitation frequency based on model precipitation alone.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2011

Inducing mineral precipitation in groundwater by addition of phosphate

Background: Induced precipitation of phosphate minerals to scavenge trace elements from groundwater is a potential remediation approach for contaminated aquifers. The success of engineered precipitation schemes depends on the particular phases generated, their rates of formation, and their long term stability. The purpose of this study was to examine the precipitation of calcium phosphate minerals under conditions representative of a natural groundwater. Because microorganisms are present in groundwater, and because some proposed schemes for phosphate mineral precipitation rely on stimulation of native microbial populations, we also tested the effect of bacterial cells (initial densities of 10 5 and 10 7 mL -1 ) added to the precipitation medium. In addition, we tested the effect of a trace mixture of propionic, isovaleric, formic and butyric acids (total concentration 0.035 mM). Results: The general progression of mineral precipitation was similar under all of the study conditions, with initial formation of amorphous calcium phosphate, and transformation to poorly crystalline hydroxylapatite (HAP) within one week. The presence of the bacterial cells appeared to delay precipitation, although by the end of the experiments the overall extent of precipitation was similar for all treatments. The stoichiometry of the final precipitates as well as Rietveld structure refinement using x-ray diffraction data indicated that the presence of organic acids and bacterial cells resulted in an increasing a and decreasing c lattice parameter, with the higher concentration of cells resulting in the greatest distortion. Uptake of Sr into the solids was decreased in the treatments with cells and organic acids, compared to the control. Conclusions: Our results suggest that the minerals formed initially during an engineered precipitation application for trace element sequestration may not be the ones that control long-term immobilization of the contaminants. In addition, the presence of bacterial cells appears to be associated with delayed HAP precipitation, changes in the lattice parameters, and reduced incorporation of trace elements as compared to cell-free systems. Schemes to remediate groundwater contaminated with trace metals that are based on enhanced phosphate mineral precipitation may need to account for these phenomena, particularly if the remediation approach relies on enhancement of in situ microbial populations.

58 GEOSCIENCES↗

DOE OSTI2016

Precipitation Depth-Duration-Frequency Analysis for the Nevada National Security Site and Surrounding Areas

Accurate precipitation frequency data are important for Environmental Management Soils Activities on the Nevada National Security Site (NNSS). These data are important for environmental assessments performed for regulatory closure of Soils Corrective Action Unit (CAU) Sites, as well as engineering mitigation designs and post-closure monitoring strategies to assess and minimize potential contaminant migration from Soils CAU Sites. Although the National Oceanic and Atmospheric Administration (NOAA) Atlas 14 (Bonnin et al., 2011) provides precipitation frequency data for the NNSS area, the NNSS-specific observed precipitation data were not consistent with the NOAA Atlas 14 predicted data. This is primarily due to the NOAA Atlas 14 products being produced from analyses without including the approximately 30 NNSS precipitation gage records, several of which approach or exceed 50 year of record. Therefore, a study of precipitation frequency that incorporated the NNSS precipitation gage records into the NOAA Atlas 14 dataset, was performed specifically for the NNSS to derive more accurate site-specific precipitation data products. Precipitation frequency information, such as the depth-duration-frequency (DDF) relationships, are required to generate synthetic standard design storm hydrographs and assess actual precipitation events. In this study, the actual long-term NNSS precipitation gage records, some of which are the longest gage records in southern and central Nevada, were analyzed to allow for more accurate precipitation DDF estimates to be developed for the NNSS. Gridded maps of precipitation frequency for the NNSS and surrounding areas were then produced.

54 ENVIRONMENTAL SCIENCES↗