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Summary of resources available to small water systems for meeting the 10 ppb arsenic drinking water limit

Krumhansl, James L.; Larese, Kathleen C.

With the lowering of the EPA maximum contaminant level of arsenic from 50 parts per billion (ppb) to 10 ppb, many public water systems in the country and in New Mexico in particular, are faced with making decisions about how to bring their system into compliance. This document provides detail on the options available to the water systems and the steps they need to take to achieve compliance with this regulation. Additionally, this document provides extensive resources and reference information for additional outreach support, financing options, vendors for treatment systems, and media pilot project results.

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Sequestration of radionuclides and heavy metals by hydroxyapatite doped with Fe, Cu and Sn

Helean, Katheryn B.; Walton, Fotini W.; Neidel, Linnah L.; Larese, Kathleen C.; Salas, Fred S.

Apatite, Ca{sub 5}(PO{sub 4}){sub 3}(F,OH,Cl)(P6{sub 3}/m, Z=2), is the most abundant phosphate mineral on Earth. The end-member hydroxyapatite, Ca{sub 5}(PO{sub 4}){sub 3}OH(P2{sub 1}/b), is the primary mineral component in bones and teeth and tends to scavenge and sequester heavy metals in the human body. Hydroxyapatite has also been shown to be effective at sequestering radionuclides and heavy metals in certain natural systems (Dybowska et al., 2004). Hydroxyapatite has been the focus of many laboratory studies and is utilized for environmental remediation of contaminated sites (Moore et al., 2002). The crystal structure of apatite tolerates a great deal of distortion caused by extensive chemical substitutions. Metal cations (e.g. REE, actinides, K, Na, Mn, Ni, Cu, Co, Zn, Sr, Ba, Pb, Cd, Fe) substitute for Ca, and oxyanions (e.g. AsO{sub 4}{sup 3-}, SO{sub 4}{sup 2-}, CO{sub 3}{sup 2-}, SiO{sub 4}{sup 4-}, CrO{sub 4}{sup 2-}) replace PO{sub 4}{sup 3-} through a series of coupled substitutions that preserve electroneutrality. Owing to the ability of apatite to incorporate 'impurities'(including actinides) gives rise to its proposed use as a waste form for radionuclides. Recent work at Sandia National Laboratory demonstrated that hydroxyapatite has a strong affinity for U, Pu, Np, Sr and Tc reduced from pertechnetate (TcO{sub 4}{sup -}) by SnCl{sub 2} (Moore et al., 2002). Based on these earlier promising results, an investigation was initiated into the use of apatite-type materials doped with aliovalent cations including Fe, Cu and Sn as Tc-scavengers. Synthetic Fe and Cu-doped hydroxyapatite samples were prepared by precipitation of Ca, from Ca-acetate, and P, from ammonium phosphate. The Fe and Cu were introduced as chlorides into the Ca-acetate solution. Stannous chloride was used as a reducing agent and was apparently incorporated into the crystal structures of the hydroxyapatite samples in small, as yet undetermined quantities.

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Containment of uranium in the proposed Egyptian geologic repository for radioactive waste using hydroxyapatite

Hasan, Ahmed H.; Larese, Kathleen C.; Headley, Thomas J.; Zhao, Hongting Z.; Salas, Fred S.

Currently, the Egyptian Atomic Energy Authority is designing a shallow-land disposal facility for low-level radioactive waste. To insure containment and prevent migration of radionuclides from the site, the use of a reactive backfill material is being considered. One material under consideration is hydroxyapatite, Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}, which has a high affinity for the sorption of many radionuclides. Hydroxyapatite has many properties that make it an ideal material for use as a backfill including low water solubility (K{sub sp}>10{sup -40}), high stability under reducing and oxidizing conditions over a wide temperature range, availability, and low cost. However, there is often considerable variation in the properties of apatites depending on source and method of preparation. In this work, we characterized and compared a synthetic hydroxyapatite with hydroxyapatites prepared from cattle bone calcined at 500 C, 700 C, 900 C and 1100 C. The analysis indicated the synthetic hydroxyapatite was similar in morphology to 500 C prepared cattle hydroxyapatite. With increasing calcination temperature the crystallinity and crystal size of the hydroxyapatites increased and the BET surface area and carbonate concentration decreased. Batch sorption experiments were performed to determine the effectiveness of each material to sorb uranium. Sorption of U was strong regardless of apatite type indicating all apatite materials evaluated. Sixty day desorption experiments indicated desorption of uranium for each hydroxyapatite was negligible.

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Overview on backfill materials and permeable reactive barriers for nuclear waste disposal facilities

Larese, Kathleen C.; Larese, Kathleen C.; Hasan, Ahmed H.

A great deal of money and effort has been spent on environmental restoration during the past several decades. Significant progress has been made on improving air quality, cleaning up and preventing leaching from dumps and landfills, and improving surface water quality. However, significant challenges still exist in all of these areas. Among the more difficult and expensive environmental problems, and often the primary factor limiting closure of contaminated sites following surface restoration, is contamination of ground water. The most common technology used for remediating ground water is surface treatment where the water is pumped to the surface, treated and pumped back into the ground or released at a nearby river or lake. Although still useful for certain remediation scenarios, the limitations of pump-and-treat technologies have recently been recognized, along with the need for innovative solutions to ground-water contamination. Even with the current challenges we face there is a strong need to create geological repository systems for dispose of radioactive wastes containing long-lived radionuclides. The potential contamination of groundwater is a major factor in selection of a radioactive waste disposal site, design of the facility, future scenarios such as human intrusion into the repository and possible need for retrieving the radioactive material, and the use of backfills designed to keep the radionuclides immobile. One of the most promising technologies for remediation of contaminated sites and design of radioactive waste repositories is the use of permeable reactive barriers (PRBs). PRBs are constructed of reactive material(s) to intercept and remove the radionuclides from the water and decontaminate the plumes in situ. The concept of PRBs is relatively simple. The reactive material(s) is placed in the subsurface between the waste or contaminated area and the groundwater. Reactive materials used thus far in practice and research include zero valent iron, hydroxyapatite, magnesium oxide, and others. As the contaminant moves through the reactive material, the contaminant is either sorbed by the reactive material or chemically reacts with the material to form a less harmful substance. Because of the high risk associated with failure of a geological repository for nuclear waste, most nations favor a near-field multibarrier engineered system using backfill materials to prevent release of radionuclides into the surrounding groundwater.

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Anionic sorbents for arsenic and technetium species

Larese, Kathleen C.; Larese, Kathleen C.; Zhao, Hongting Z.; Hasan, Ahmed H.; Bontchev, Ranko P.; Salas, Fred S.; Lucero, Daniel A.

Two sorbents, zirconium coated zeolite and magnesium hydroxide, were tested for their effectiveness in removing arsenic from Albuquerque municipal water. Results for the zirconium coated zeolite indicate that phosphate present in the water interfered with the sorption of arsenic. Additionally, there was a large quantity of iron and copper present in the water, corrosion products from the piping system, which may have interfered with the uptake of arsenic by the sorbent. Magnesium hydroxide has also been proven to be a strong sorbent for arsenic as well as other metals. Carbonate, present in water, has been shown to interfere with the sorption of arsenic by reacting with the magnesium hydroxide to form magnesium carbonate. The reaction mechanism was investigated by FT-IR and shows that hydrogen bonding between an oxygen on the arsenic species and a hydrogen on the Mg(OH)2 is most likely the mechanism of sorption. This was also confirmed by RAMAN spectroscopy and XRD. Technetium exists in multiple oxidation states (IV and VII) and is easily oxidized from the relatively insoluble Tc(IV) form to the highly water soluble and mobile Tc(VII) form. The two oxidation states exhibit different sorption characteristics. Tc(VII) does not sorb to most materials whereas Tc(IV) will strongly sorb to many materials. Therefore, it was determined that it is necessary to first reduce the Tc (using SnCl2) before sorption to stabilize Tc in the environment. Additionally, the effect of carbonate and phosphate on the sorption of technetium by hydroxyapatite was studied and indicated that both have a significant effect on reducing Tc sorption.

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Containment of uranium in the proposed Egyptian geologic repository for radioactive waste using hydroxyapatite

Larese, Kathleen C.; Hasan, Ahmed H.; Larese, Kathleen C.; Headley, Thomas J.; Zhao, Hongting Z.; Salas, Fred S.

Currently, the Egyptian Atomic Energy Authority is designing a shallow-land disposal facility for low-level radioactive waste. To insure containment and prevent migration of radionuclides from the site, the use of a reactive backfill material is being considered. One material under consideration is hydroxyapatite, Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}, which has a high affinity for the sorption of many radionuclides. Hydroxyapatite has many properties that make it an ideal material for use as a backfill including low water solubility (K{sub sp} > 10{sup -40}), high stability under reducing and oxidizing conditions over a wide temperature range, availability, and low cost. However, there is often considerable variation in the properties of apatites depending on source and method of preparation. In this work, we characterized and compared a synthetic hydroxyapatite with hydroxyapatites prepared from cattle bone calcined at 500 C, 700 C, 900 C and 1100 C. The analysis indicated the synthetic hydroxyapatite was similar in morphology to 500 C prepared cattle hydroxyapatite. With increasing calcination temperature the crystallinity and crystal size of the hydroxyapatites increased and the BET surface area and carbonate concentration decreased. Batch sorption experiments were performed to determine the effectiveness of each material to sorb uranium. Sorption of U was strong regardless of apatite type indicating all apatite materials evaluated. Sixty day desorption experiments indicated desorption of uranium for each hydroxyapatite was negligible.

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Formation of hydroxyapatite in soils using calcium citrate and sodium phosphate for control of strontium migration

Larese, Kathleen C.; Larese, Kathleen C.; Hasan, Ahmed H.; Zhao, Hongting Z.; Salas, Fred S.

{sup 90}Sr contamination is a major problem at several U.S. sites. At some sites, {sup 90}Sr has migrated deep underground making site remediation difficult. In this paper, we describe a novel method for precipitation of hydroxyapatite, a strong sorbent for {sup 90}Sr, in soil. The method is based on mixing a solution of calcium citrate and sodium phosphate in soil. As the indigenous soil microorganisms mineralize the citrate, the calcium is released and forms hydroxyapatite. Soil, taken from the Albuquerque desert, was treated with a sodium phosphate solution or a sodium phosphate/calcium citrate solution. TEM and EDS were used to identify hydroxyapatite with CO{sub 3}{sup 2-} substitutions, with a formula of (Ca{sub 4.8}Na{sub 0.2})[(PO{sub 4}){sub 2.8}(CO{sub 3}){sub 0.2}](OH), in the soil treated with the sodium phosphate/calcium citrate solution. Untreated and treated soils were used in batch sorption experiments for Sr uptake. Average Sr uptake was 19.5, 77.0 and 94.7% for the untreated soil, soil treated with sodium phosphate, and soil with apatite, respectively. In desorption experiments, the untreated soil, phosphate treated soil and apatite treated soil released an average of 34.2, 28.8 and 4.8% respectively. The results indicate the potential of forming apatite in soil using soluble reagents for retardation of radionuclide migration.

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Sorption of Arsenic from Drinking Water to Mg(OH)2 Sorrel's Cements, and Zirconium Doped Materials

Zhao, Hongting Z.; Sanchez, Charles A.; Larese, Kathleen C.; Salas, Fred S.; Hasan, Ahmed H.; Lucero, Daniel A.; Larese, Kathleen C.

It was discovered that MgO or Mg(OH){sub 2} when it reacts with water is a very strong sorbent for arsenic. Distribution constants, or K{sub d} values, are as high as 1 x 10{sup 6} L/mole. In this work, Mg(OH){sub 2} and other compounds have been investigated as sorbents for arsenic and other contaminants. This work has resulted in several major accomplishments including: (1) design, construction, and testing of a pressure sand filter to remove Mg(OH){sub 2} after it has sorbed arsenic from water, (2) stabilization of Mg(OH){sub 2} as a Sorrel's cement against reaction with carbonate that results in MgCO{sub 3} formation decreasing the efficiency of Mg(OH){sub 2} to sorb arsenic, and (3) the development of a new, very promising sorbent for arsenic based on zirconium. Zirconium is an environmentally benign material found in many common products such as toothpaste. It is currently used in water treatment and is very inexpensive. In this work, zirconium has been bonded to activated carbon, zeolites, sand and montmorillonite. Because of its high charge in ionic form (+6), zirconium is a strong sorbent for many anions including arsenic. In equilibrium experiments arsenic concentrations in water were reduced from 200 ppb to less than 1 ppb in less than 1 minute of contact time. Additionally, analytical methods for detecting arsenic in water have also been investigated. Various analytical techniques including HPLC, AA and ICP-MS are used for quantification of arsenic. Due to large matrix interferences HPLC and AA techniques are not very selective and are time consuming. ICP-MS is highly efficient, requires a low sample volume and has a high tolerance for interferences. All these techniques are costly and require trained staff, and with the exception of ICP-MS, these methods cannot be used at low ppb arsenic concentration without using a pre-concentration step. An alternative to these traditional techniques is to use a colorimetric method based on leucocrystal violet dye interaction with iodine. This method has been adapted in our facility for quantifying arsenic concentrations down to 14 ppb.

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22 Results
22 Results