skip to main content


This content will become publicly available on December 12, 2024

Title: Removal of Aqueous Uranyl and Arsenate Mixtures after Reaction with Limestone, PO 4 3– , and Ca 2+
The co-occurrence of uranyl and arsenate in contaminated water caused by natural processes and mining is a concern for impacted communities, including in Native American lands in the U.S. Southwest. We investigated the simultaneous removal of aqueous uranyl and arsenate after the reaction with limestone and precipitated hydroxyapatite (HAp, Ca10(PO4)6(OH)2). In benchtop experiments with an initial pH of 3.0 and initial concentrations of 1 mM U and As, uranyl and arsenate coprecipitated in the presence of 1 g L−1 limestone. However, related experiments initiated under circumneutral pH conditions showed that uranyl and arsenate remained soluble. Upon addition of 1 mM PO43− and 3 mM Ca2+ in solution (initial concentration of 0.05 mM U and As) resulted in the rapid removal of over 97% of U via Ca−U−P precipitation. In experiments with 2 mM PO4 3− and 10 mM Ca2+ at pH rising from 7.0 to 11.0, aqueous concentrations of As decreased (between 30 and 98%) circa pH 9. HAp precipitation in solids was confirmed by powder X-ray diffraction and scanning electron microscopy/energy dispersive X-ray. Electron microprobe analysis indicated U was coprecipitated with Ca and P, while As was mainly immobilized through HAp adsorption. The results indicate that natural materials, such as HAp and limestone, can effectively remove uranyl and arsenate mixtures.  more » « less
Award ID(s):
1914490 1652619
NSF-PAR ID:
10480382
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
Environmental Science & Technology
Volume:
57
Issue:
49
ISSN:
0013-936X
Page Range / eLocation ID:
20881 to 20892
Subject(s) / Keyword(s):
["uranium, arsenic, uranyl, arsenate, hydroxyapatite, limestone, precipitation, adsorption"]
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    A rapid and sensitive method is described for measuring perchlorate (ClO 4 − ), chlorate (ClO 3 − ), chlorite (ClO 2 − ), bromate (BrO 3 − ), and iodate (IO 3 − ) ions in natural and treated waters using non-suppressed ion chromatography with electrospray ionization and tandem mass spectrometry (NS-IC-MS/MS). Major benefits of the NS-IC-MS/MS method include a short analysis time (12 minutes), low limits of quantification for BrO 3 − (0.10 μg L −1 ), ClO 4 − (0.06 μg L −1 ), ClO 3 − (0.80 μg L −1 ), and ClO 2 − (0.40 μg L −1 ), and compatibility with conventional LC-MS/MS instrumentation. Chromatographic separations were generally performed under isocratic conditions with a Thermo Scientific Dionex AS16 column, using a mobile phase of 20% 1 M aqueous methylamine and 80% acetonitrile. The isocratic method can also be optimized for IO 3 − analysis by including a gradient from the isocratic mobile phase to 100% 1 M aqueous methylamine. Four common anions (Cl − , Br − , SO 4 2− , and HCO 3 − /CO 3 2− ), a natural organic matter isolate (Suwannee River NOM), and several real water samples were tested to examine influences of natural water constituents on oxyhalide detection. Only ClO 2 − quantification was significantly affected – by elevated chloride concentrations (>2 mM) and NOM. The method was successfully applied to quantify oxyhalides in natural waters, chlorinated tap water, and waters subjected to advanced oxidation by sunlight-driven photolysis of free available chlorine (sunlight/FAC). Sunlight/FAC treatment of NOM-free waters containing 200 μg L −1 Br − resulted in formation of up to 263 ± 35 μg L −1 and 764 ± 54 μg L −1 ClO 3 − , and up to 20.1 ± 1.0 μg L −1 and 33.8 ± 1.0 μg L −1 BrO 3 − (at pH 6 and 8, respectively). NOM strongly inhibited ClO 3 − and BrO 3 − formation, likely by scavenging reactive oxygen or halogen species. As prior work shows that the greatest benefits in applying the sunlight/FAC process for purposes of improving disinfection of chlorine-resistant microorganisms are realized in waters with lower DOC levels and higher pH, it may therefore be desirable to limit potential applications to waters containing moderate DOC concentrations ( e.g. , ∼1–2 mg C L −1 ), low Br − concentrations ( e.g. , <50 μg L −1 ), and circumneutral to moderately alkaline pH ( e.g. , pH 7–8) to strike a balance between maximizing microbial inactivation while minimizing formation of oxyhalides and other disinfection byproducts. 
    more » « less
  2. Uranium (U) contamination of drinking water often affects communities with limited resources, presenting unique technology challenges for U 6+ treatment. Here, we develop a suite of chemically functionalized polymer (polyacrylonitrile; PAN) nanofibers for low pressure reactive filtration applications for U 6+ removal. Binding agents with either nitrogen-containing or phosphorous-based ( e.g. , phosphonic acid) functionalities were blended (at 1–3 wt%) into PAN sol gels used for electrospinning, yielding functionalized nanofiber mats. For comparison, we also functionalized PAN nanofibers with amidoxime (AO) moieties, a group well-recognized for its specificity in U 6+ uptake. For optimal N-based (Aliquat® 336 or Aq) and P-containing [hexadecylphosphonic acid (HPDA) and bis(2-ethylhexyl)phosphate (HDEHP)] binding agents, we then explored their use for U 6+ removal across a range of pH values (pH 2–7), U 6+ concentrations (up to 10 μM), and in flow through systems simulating point of use (POU) water treatment. As expected from the use of quaternary ammonium groups in ion exchange, Aq-containing materials appear to sequester U 6+ by electrostatic interactions; while uptake by these materials is limited, it is greatest at circumneutral pH where positively charged N groups bind negatively charged U 6+ complexes. In contrast, HDPA and HDEHP perform best at acidic pH representative of mine drainage, where surface complexation of the uranyl cation likely drives uptake. Complexation by AO exhibited the best performance across all pH values, although U 6+ uptake via surface precipitation may also occur near circumneutral pH values and at high (10 μM) dissolved U 6+ concentrations. In simulated POU treatment studies using a dead-end filtration system, we observed U removal in AO-PAN systems that is insensitive to common co-solutes in groundwater ( e.g. , hardness and alkalinity). While more research is needed, our results suggest that only 80 g (about 0.2 lbs.) of AO-PAN filter material would be needed to treat an individual's water supply (contaminated at ten-times the U.S. EPA maximum contaminant level for U) for one year. 
    more » « less
  3. Critical mineral deposits commonly form in magmatic-hydrothermal systems including carbonatites and/or alkaline syenites, and more evolved peralkaline granites where the rare earth element (REE) undergo a complex array of partitioning, transport and mineralization. Significant alteration and veining zones develop in these deposits and can be used to vector ore zones in the field [1]. The REE ore minerals typically reflect the characteristics of these systems, which are enriched in carbonate, fluoride, and phosphate or a combination thereof. The REE can also be incorporated into vein minerals such as calcite, fluorite and apatite where the REE3+ exchange for Ca2+ on the crystal lattice [2]. These minerals give us clues about the hydrothermal reaction paths of REE in critical mineral deposits. This study aims to: 1) present our recent findings from hydrothermal fluid-mineral REE partitioning experiments, 2) discuss thermodynamic models to simulate REE in critical mineral deposits, and 3) link the thermodynamic simulations to field observations. Hydrothermal fluid-calcite partitioning experiments were conducted between 100 and 200 °C by hydrothermal fluid mixing and precipitation [2] at near neutral to mildly alkaline pH (6 – 9). The REE concentrations in synthetic calcite crystals and aqueous fluids sampled in situ were used to fit the data to the lattice strain model [3] and using the Dual Thermodynamic approach [4]. A second type of experiment consisted of reacting natural fluorite and apatite crystals with acidic to mildly acidic (pH of 2 – 4) aqueous fluids in batch-type reactors to study the behavior of REE and mineral dissolution-precipitation reactions near crystal surfaces. The GEMS code package [5] was used to implement these new data into a thermodynamic model and simulate possible REE reaction paths in hydrothermal fluids. Two REE mineral deposits in New Mexico (Lemitar and Gallinas Mountains) present ideal case studies to illustrate how these models can be linked to field observations from natural systems. [1] Gysi et al. (2016), Econ. Geol. 111, 1241-1276; [2] Perry and Gysi (2020), Geochim. Cosmochim. Acta 286, 177-197; [3] Blundy and Wood (1994) Nature 372, 452-454; [4] Kulik (2006), Chem. Geol. 225, 189-212; [5] Kulik et al. (2013), Computat. Geosci. 17, 1-24. 
    more » « less
  4. Rare earth element (REE) deposits are found in association with carbonatite and alkaline systems, where metasomatism plays a significant role in the late-stage transport and enrichment of REE [1]. Fluorite is a common gangue mineral in these mineral deposits and can incorporate varying REE concentrations by substitutions of REE3+ for Ca2+. Fluorite-hosted fluid inclusions contain significant REE concentrations [2], providing a potential record of the hydrothermal ore-forming fluids. The fluorite-fluid REE partitioning mechanisms, however, are largely unknown. To date, only one study [3] measured the partitioning of REE between fluorite and aqueous fluid at 60 °C. Here, we evaluate these REE partitioning mechanisms by combining laboratory experiments with characteristics of natural fluid inclusions that provide a range of salinities and homogenization temperatures relevant to natural systems. Batch-type experiments will be conducted between 100 and 250 °C in Teflon-lined reactors, in which millimeter-sized natural fluorite crystals (Cooke’s Peak, New Mexico) will be reacted with fluids of varying initial REE concentration, pH, and salinity. Kinetic experiments were carried out at 150 °C to test for attainment of a steady state between the fluorite crystals and the aqueous solutions. The reacted fluorite crystals will be studied using SEM, CL and EMPA. Major cations and anions in the quenched fluids will be analyzed using IC and ICP-OES; REE will be determined using solution ICP-MS. These results will permit deriving REE fluorite-fluid partition coefficients. Fluid inclusions in hydrothermal fluorite veins from the fluorite-bastnäsite REE deposits in the Gallinas Mountains in New Mexico are studied to constrain temperatures, salinities, and REE concentrations of hydrothermal ore-forming fluids in alkaline systems. Fluid inclusion assemblages were identified in growth zones and will be further studied using microthermometry. Previous studies found maximum temperatures of 400 °C in sulfate-rich NaCl-KCl brines [4]. The goal will be to link partition coefficients derived from the experiments to the REE partitioning behavior found in the natural fluorite. [1] Gysi et al. (2016), Econ. Geol. 111, 1241-1276; [2] Vasyukova and Williams-Jones (2018) Chem. Geol. 483, 385-396; [3] van Hinsberg et al. (2010), Geology 38, 847-850; [4] Williams-Jones et al. (2000), Econ. Geol. 95, 327-341. 
    more » « less
  5. Lead (Pb) solubility is commonly limited by dissolution–precipitation reactions of secondary mineral phases in contaminated soils and water. In the research described here, Pb solubility and free Pb2+ ion activities were measured following the precipitation of Pb minerals from aqueous solutions containing sulfate or carbonate in a 1:5 mole ratio in the absence and presence of phosphate over the pH range 4.0–9.0. Using X-ray diffraction and Fourier-transform infrared spectroscopic analysis, we identified anglesite formed in sulfate-containing solutions at low pH. At higher pH, Pb carbonate and carbonate-sulfate minerals, hydrocerussite and leadhillite, were formed in preference to anglesite. Precipitates formed in the Pb-carbonate systems over the pH range of 6 to 9 were composed of cerussite and hydrocerussite, with the latter favored only at the highest pH investigated. The addition of phosphate into the Pb-sulfate and Pb-carbonate systems resulted in the precipitation of Pb3(PO4)2 and structurally related pyromorphite minerals and prevented Pb sulfate and carbonate mineral formation. Phosphate increased the efficiency of Pb removal from solution and decreased free Pb2+ ion activity, causing over 99.9% of Pb to be precipitated. Free Pb2+ ion activities measured using the ion-selective electrode revealed lower values than predicted from thermodynamic constants, indicating that the precipitated minerals may have lower KSP values than generally reported in thermodynamic databases. Conversely, dissolved Pb was frequently greater than predicted based on a speciation model using accepted thermodynamic constants for Pb ion-pair formation in solution. The tendency of the thermodynamic models to underestimate Pb solubility while overestimating free Pb2+ activity in these systems, at least in the higher pH range, indicates that soluble Pb ion-pair formation constants and KSP values need correction in the models. 
    more » « less