Simultaneous application of dissolution/precipitation and surface complexation/surface precipitation modeling to contaminant leaching

This paper discusses the modeling of anion and cation leaching from complex matrixes such as weathered steel slag. The novelty of the method is its simultaneous application of the theoretical models for solubility, competitive sorption, and surface precipitation phenomena to a complex system. Selective chemical extractions, pH dependent leaching experiments, and geochemical modeling were used to investigate the thermodynamic equilibrium of 12 ions (As, Ca, Cr, Ba, SO4, Mg, Cd, Cu, Mo, Pb, V, and Zn) with aqueous complexes, soluble solids, and sorptive surfaces in the presence of 12 background analytes (Al, Cl, Co, Fe, K, Mn, Na, Ni, Hg, NO3, CO3, and Ba). Modeling results show that surface complexation and surface precipitation reactions limit the aqueous concentrations of Cd, Zn, and Pb in an environment where Ca, Mg, Si, and CO3 dissolve from soluble solids and compete for sorption sites. The leaching of SO4, Cr, As, Si, Ca, and Mg appears to be controlled by corresponding soluble solids.     

Mineralogy of air-pollution-control residues from a secondary lead smelter: environmental implications

The mineralogy and solubility of air-pollution-control (APC) residues from a secondary lead (Pb) smelter have been studied on samples from the Príbram smelter, Czech Republic, recycling car batteries, with the emphasis on their potential environmental effect. The presence of dominant anglesite (PbSO4) and laurionite (Pb(OH)Cl) was observed in a sintered residue from after-burning chambers (800-1000 degrees C). In contrast, low-temperature Pb-bearing phases, such as KCl x 2PbCl2 and caracolite (Na3Pb2(SO4)3Cl), were detected in the major APC residue from bag-type fabric filters. Metallic elements, zinc (Zn), cadmium (Cd), and tin (Sn) were found homogeneously distributed within this residue. The formation of anglesite, cotunnite (PbCl2), (Zn,Cd)2SnO4, and (Sb,As)2O3 was observed during the sintering of this APC residue at 500 degrees C in a rotary furnace. The 168 h leaching test on filter residue, representing the fraction that may escape the flue gas treatment system, indicated rapid release of Pb and other contaminants. Caracolite and KCl x 2PbCl2 are significantly dissolved, and anglesite and cotunnite form the alteration products, as was confirmed by mineralogical analysis and PHREEQC-2 modeling. The observed Pb-bearing chlorides have significantly higher solubility than anglesite and, following emission from the smelter stack, can readily dissolve, transferring Pb into the environmental milieu (soils, water, inhabited areas).     

Removal of B,Cr, Mo,and Se from wastewater by incorporation into hydrocalumite and ettringite

Boron, chromium, molybdenum, and selenium often occur in high concentrations in fly ash leachates. During the leaching of fly ash in alkaline environments, hydrocalumite (Ca4Al2(OH)12(OH)2 x 6H2O) and ettringite (Ca6Al2(OH)12(SO4)3 x 26H20) form as secondary precipitates. In this study, the removal of B, Cr, Mo, and Se oxyanions from high pH waters by incorporation into hydrocalumite and ettringite was examined. Experiments were performed by precipitating these minerals in solutions containing B, Cr, Mo, and Se oxyanions at conditions relevant to lime-leaching of fly ash as well as to fly ash containing concrete. The uptake of all four anions by hydrocalumite and ettringite was high. Anion uptake by hydrocalumite was larger than that by ettringite, and hydrocalumite was able to reduce anion concentrations to below drinking water standards. Ettringite showed an anion preference in the order of B(OH)4- > SeO4(2-) > CrO4(2-) > MoO4(2-). In contrast, borate was least preferred by hydrocalumite. Coordination, size, and electronegativity are likely the factors that result in the observed differences among the oxyanions.     

Contribution to the study of avocado honeys by their mineral contents using inductively coupled plasma optical emission spectrometry

Avocado honey samples were analyzed by inductively coupled plasma optical emission spectrometric. First, the botanical origin of the honeys was confirmed by melissopalynological analysis. Twenty-four minerals were quantified for each honey sample. The elements Al, Ba, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, S, Se, Si and Zn were detected in all samples; seven elements were very abundant (Ca, K, Mg, Na, P, S and Si), six were not abundant (Al, Cu, Fe, Li and Zn) and 11 were trace elements (As, Ba, Cd, Co, Cr, Mo, Ni, Mo, Pb, Se, Sr and V).     

Aqueous solubility diagrams for cementitious waste stabilization systems. 3. Mechanism of zinc immobilizaton by calcium silicate hydrate

Zinc oxide was added during hydration of alite (C3S) as an analogue for solidification/stabilization by cement of metal-bearing hazardous waste. Curing of samples was stopped at various intervals between 8 h and 100 d, and the reaction products were analyzed by both X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS at Zn, Ca, and Si K-edges). Calcium zincate hydrate (CaZn2(OH)6 x 2H2O) initially formed together with calcium silicate hydrate (CSH) vanishes from X-ray diffractograms after 14 d, and no other crystalline Zn-bearing phase could be detected thereafter. EXAFS Zn K-edge data analysis reveals that Zn(O,OH)4 tetrahedra continue to determine the first shell coordination. However, a new Zn-Si bond appears in the second coordination shell as indicated by both Zn K-edge and Si K-edge EXAFS. Together with the Ca-Zn and Ca-Ca shells derived from the Ca K-edge EXAFS spectra, a structural model for the site occupation of Zn in CSH is proposed, whereby the Zn(O,OH)4 tetrahedra are bound in layer rather than interlayer positions substituting for the silicate bridging tetrahedra and/or at terminal silicate chain sites. This structural model enables ultimately the formulation of a thermodyamic Lippmann model to predict the aqueous solubility of Zn in solid solution with a CSH phase of a Ca/Si ratio fixed to unity.     

微波消解ICPOES法测定旱芹与西芹中的21种矿物元素

建立了微波消解-电感耦合等离子体原子发射光谱法（ICP-OES）法测定旱芹与西芹中的21种矿物元素的分析方法。利用HNO3+H2O2湿法微波消解制样,应用全谱直读ICP-OES对咸阳市售旱芹与西芹中的Na、K、Ca、S、P、Mg、Al、Si、Fe、Zn、Sr、Mn、B、V、Ba、Cu、Ga、Cr、Ti、Cd、Pb等21种矿物元素进行了测定。结果表明,各待测元素的检出限为1.0⁴40μg/L,相对标准偏差（RSD）在0.11%¹0.7%之间,标准样品回收率测定在89.0%¹09.6%之间。实验结果可为芹菜的应用研究提供基础数据。      

Assessing the origin and fate of Cr, Ni, Cu, Zn, Pb, and V in industrial polluted soil by combined microspectroscopic techniques and bulk extraction methods

The major geochemical forms of Cr, Ni, Cu, Zn, Pb, and V in a soil from an industrial polluted site in the south of Italy were determined by means of synchrotron X-ray microanalytical techniques such as coupled micro-X-ray fluorescence/micro-X-ray diffraction and micro-X-ray absorption near edge structure spectroscopy in combination with bulk extraction methods (sequential extraction procedures, EDTA extractions, and toxicity leaching characteristic procedure tests). Cr, Ni, Zn, and Cu were found in spinel-type geochemical forms (chromite, trevorite, franklinite, zincochromite, and cuprospinel) and often in association with magnetite and hematite. Vwas mainly present as V(V) associated with iron-oxides or in the form of volborthite [Cu3(OH)2V2O7.2H2O]. Pb was speciated as minium (Pb3O4), lanarkite [Pb2O(SO4)], and, in association with Cr(VI), as crocoite (PbCrO4). In general, despite a high total concentration, metals appear to be speciated for the most part as rather insoluble geochemical forms. However, particular attention should be paid to Zn, Cu, V, and Pb that show non-negligible mobilizable fractions. On the basis of the geochemical forms identified, among others, two major former industrial activities were tentatively ascribed as being responsible for the observed major pollution: polyvinyl chloride and cement-asbestos productions.     

Structure and properties of noncrystalline nano-Al(OH)₃ reclaimed from carbonized residual wastewater treatment sludge

Performance of wastewater treatement sludge-carbon (SC) can be evidently improved by removing the inorganic fractions. A novel investigation for recovery of Al from acid leaching of SC and synthesis of nano-Al(OH)(3) has been conducted. Results show that the sodium aluminates with high purity can be obtained by effectively dissolving the inorganic fractions from SC and by further removing the impurities (Fe(3+), Ca(2+), Mg(2+), S(4+), and P(3+)). Highly dispersed Al(OH)(3) with high S(BET) is obtained at pH = 6. The peaks of -CH(2)- vibration and the C1s peaks (binding energies of 284.6 eV) imply that polyethylene glycol 1000 (PEG-1000) is chemically adsorbed on the surface of Al(OH)(3) samples, which is propitious to reduce the hydrogen bonds between water molecules and surface -OH groups to prevent hard agglomeration. The stretching vibration peaks of [AlO(2)](-) and the Na1s peaks confirm that a trace of sodium aluminate (NaAl(OH)(4), Na(+)(H(2)O)(4)[Al(OH)(4)(-)], or the dehydrated monomers) is retained in the prepared Al(OH)(3). The main phase transformation for calcination (≤800 °C) of the SC-derived Al(OH)(3) is from amorphous Al(OH)(3) to amorphous A1(2)O(3). Here we highlight that production of Al(OH)(3) and SC from sludge provides the potential application in significant quantities that can revolutionize the handling of such kinds of harmful waste.     

Relative solubility of cations in Class F fly ash

Coal utilization byproducts (CUB), such as fly ash, contain cations that may be released during exposure to fluids such as acid rain or acid mine drainage. Researchers at the Department of Energy's National Energy Technology Laboratory (DOE/NETL) have conducted a long-term column leaching study of 32 Class F fly ash samples from pulverized coal (PC) combustion, and quantified the release of 19 cations in four leachants with a pH between 1.2 and 12. The relative solubility (M(L/T)) of each cation was defined as the total mass leached (M(L)) relative to the concentration (M(T)) of that element in the fly ash sample. A frequency distribution of relative solubility values was computed with ranges defined as insoluble, slightly soluble, moderately soluble, and very soluble. On the basis of this sample set, Ba, Cd, Fe, Pb, Sb, and Se in PC fly ash are insoluble. The elements Al, Be, Ca, Co, Cr, Cu, K, Mg, Mn, Na, Ni, and Zn are slightly to moderately acid soluble. Only Ca and Na are water soluble; As and Ca are soluble in the basic solution, The results of this study indicate that the extent to which cations in Class F PC fly ash can be leached by naturally occurring fluids is very limited.     

Treatment of hexavalent chromium in chromite ore processing solid waste using a mixed reductant solution of ferrous sulfate and sodium dithionite

We investigated a method for delivering ferrous iron into the subsurface to enhance chemical reduction of Cr(VI) in chromite ore processing solid waste (COPSW) derived from the production of ferrochrome alloy. The COPSW is characterized by high pH (8.5-11.5) and high Cr(VI) concentrations in the solid phase (up to 550 mg kg(-1)) and dissolved phase (3-57 mg L(-1)). The dominant solid-phase minerals are forsterite (Mg2SiO4), brucite (Mg-(OH)2), and hydrocalumite [Ca4(Al, Fe)2(OH)12X x 6H2O), X = (OH)2(2-), SO4(2-), CrO4(2-)]. The method utilizes FeSO4 in combination with Na2S2O4 to inhibit oxidation and precipitation of the ferrous iron, thereby preventing well and formation clogging. Laboratory batch tests using a 0.05 M FeSO4 + 0.05 M Na2S2O4 solution indicated effective treatment of both dissolved and solid-phase Cr(VI). Contrary to treatments with FeSO4 and FeCl2 alone, the combination resulted in both complete removal of Cr(VI) from solution and sustained Fe(ll) concentrations in solution after a 24 h period. A field test involving injection of 5700 L of a 0.07 M FeSO4 + 0.07 M Na2S2O4 solution into a COPSW saturated zone (pH 11.5) indicated no well and formation clogging during injection. Examination of a core collected 0.46 m from the injection well following injection indicated effective treatment of the solid phase Cr(VI) based on analysis of water, phosphate solution, and high temperature alkaline extracts. The combined reductant solution also imparted a residual treatment capacity to the COPSW allowing for subsequent treatment of dissolved phase Cr(VI); however, dissemination of the iron in the highly alkaline environment appeared to be impeded by the inability to sufficiently lower the pH with distance from the injection well to avoid precipitation of Fe(OH)2 and likely also FeCO3. Injection of a 0.2 M FeSO4 + 0.2 M Na2S2O4 solution into another COPSW saturated zone (pH 9) indicated much more effective dissemination of the injected iron.     

Chromium release from waste incineration air-pollution-control residues

Cr release overtime was investigated in batch experiments for eleven air-pollution-control residues from eight different municipal solid waste incinerators covering all majorflue gas cleaning technologies. Cr released during 168 h of contact with water showed significant variations among the residues studied. Also for the individual residue, large variations were observed depending on the liquid-to-solid ratio used in the leaching test and the degree of carbonation. It is argued that Al(0) present in the residues can control Cr leaching by reducing Cr(VI) released from the solid phase by dissolution and that exposure to oxygen-either prior to or during the leaching test-depletes the reduction capacity of Al(0) leading to increased Cr leaching. A dynamic model is shown to describe Cr release from all investigated residues by accounting for Al(0) oxidation with Cr(VI), O2, and water as well as Cr(VI) dissolution. The paper reveals that Al-O2-Cr(VI) interactions must be considered very carefully when interpreting Cr leaching data.     

Vitrification of chromium electroplating sludge

This work investigated the vitrification of hazardous electroplating sludge containing 140 mg/g Cr with/without bottom ash or cullet conditioning to lower specimens' basicities to 0.97-1.17 or 0.18-0.23, respectively. The conditioning was found to enhance the smooth/glassy appearance of slags but no ingot was obtained. Cr was >98% retained in the vitrified slags. Cr2O3 dominated in crystalline structure for the slag vitrified from the sludge, but this domination gradually shifted to Fe2SiO4/Fe3O4/SiO2 or SiO2 crystalline with increasing addition of bottom ash or cullet into the sludge, respectively. Compared to the raw sludge, the sludge-vitrified slag displayed lower leaching concentrations for most metals (particularly Cr (2.54 mg/L)), and smaller leaching ratios for Ag, Cr, and Cu (1.35, 0.02, and <0.01%, respectively) but greater ones for Cd, Pb, and Zn (3.83, 2.46, and 0.36%, respectively). The Cr leaching ratios were approximately 0.01% for the slags vitrified from the conditioned sludge. Independent of the slag basicity and crystalline structure, metal leaching quantity increased but leaching ratio decreased with increasing slag metal content. The slag compressive strengths were improved to >14.7 MPa at the mixing ratios > or = 2/1 and 1/1 for bottom ash/sludge and cullet/sludge, respectively. Fulfilling the criteria of Toxicity Characteristic Leaching Procedure (TCLP), all the slags were recyclable.     

Deposition of uranium precipitates in dolomitic gravel fill

Uranium-containing precipitates have been observed in a dolomitic gravel fill near the Department of Energy (DOE) S-3 Ponds former waste disposal site as a result of exposure to acidic (pH 3.4) groundwater contaminated with U (33 mg L(-1)), Al3+ (900 mg L(-1)), and NO3- (14 000 mg L(-1)). The U containing precipitates fluoresce a bright green under ultraviolet (UV) short-wave light which identify U-rich coatings on the gravel. Scanning electron microscopy (SEM) microprobe analysis show U concentration ranges from 1.6-19.8% (average of 7%) within the coatings with higher concentrations at the interface of the dolomite fragments. X-ray absorption near edge structure spectroscopy (XANES) indicate that the U is hexavalent and extended X-ray absorption fine structure spectroscopy (EXAFS) shows that the uranyl is coordinated by carbonate. The exact nature of the uranyl carbonates are difficult to determine, but some are best described by a split K(+)-like shell similar to grimselite [K4Na(UO2)(CO3)3 x H2O] and other regions are better described by a single Ca(2+)-like shell similar to liebigite [Ca2(UO2)(CO3)3 x 11(H2O)] or andersonite [Na2CaUO2(CO3)3 x 6H2O]. The U precipitates are found in the form of white to light yellow cracked-formations as coatings on the dolomite gravel and as detached individual precipitates, and are associated with amorphous basalumnite [Al4(SO4)(OH)10 x 4H2O].     

微波消解ICP-OES测定牛蒡茶中的矿质元素

采用HNO3/H2O2微波消解的制样方法,利用全谱直读电感耦合等离子原子发射光谱仪（ICP-OES）对牛蒡茶中的Al、As、Ba、Ca、Cd、Cr、Cu、Fe、K、Mg、Mn、Na、Ni、P、Pb、Sr、Ti、Zn等18种矿质元素进行了测定。结果表明,牛蒡茶中含有人体必需常量元素K、Na、Ca、Mg、P和人体必需微量元素Cu、Fe、Mn、Ni、Ti、Zn,以及人体非必需的微量元素Al、Ba、Sr,而有害元素As、Pb、Cr、Cd均未检出。并建立了一种牛蒡茶中矿质元素的分析测试方法,各元素的回收率均在93.7%¹07%,相对标准偏差在1.31%².31%,检出限低且满足各元素分析要求,此方法具有简捷、快速、准确的特点。      

Ettringite-induced heave in chromite ore processing residue (COPR) upon ferrous sulfate treatment

A pilot-scale treatment study was implemented at a deposition site of chromite ore processing residue (COPR) in New Jersey. Ferrous sulfate heptahydrate (FeSO4 x 7H2O) was employed to reduce hexavalent chromium in two dosages with three types of soil mixing equipment. XANES analyses of treated samples cured for 240 days indicated that all treatment combinations failed to meet the Cr(VI) regulatory limit of 240 mg/kg. More importantly, the discrepancy between XANES and alkaline digestion results renders the latter unreliable for regulatory purposes when applied to ferrous-treated COPR. Regardless of Cr-(VI), the introduction of reductant containing sulfate, mechanical mixing, water, acidity, and the resulting temperature increase in treated COPR promoted dissolution of brownmillerite (Ca2FeAlO5), releasing alumina and alkalinity. The pH increase caused initially precipitated gypsum (CaSO4 x 2H2O) to progressively convert to ettringite (Ca6Al2(SO4)3 x 32H2O) and its associated volume expansion under both in situ and ex situ conditions, with a maximum of 0.8 m vertical swell within 40 days of curing. While Cr-(VI) treatment remains a challenge, the intentional exhaustion of the heave potential of COPR by transforming all Al sources to ettringite emerges as a possible solution to delayed ettringite formation, which would hamper site redevelopment.     

Reaction fronts in brick-sand layers: column experiments and modeling

Admixing waste materials with common raw materials in brick production is a promising treatment technology to overcome contamination problems, because organic pollutants are destroyed and inorganic contaminants are thought to be immobilized. During their use in constructions and after the use as part of the demolition masses bricks can be leached by runoff waters and seepage waters. A possible application of recycling crushed bricks consists of their use as a surface layer material on sports grounds or in road construction. To investigate the potential leaching during acidification of a brick-sand layer and the resultant leaching of heavy metals, crushed material from two bricks was examined in several column experiments. Deionized water at pH 4 percolated through the water-saturated columns at a Darcy velocity which was varied between 0.37 and 2.2 m/d. Another column was run under unsaturated conditions. A reaction front evolved in all experiments characterized by a pH increase from pH 4 to pH 8. The chemical composition of the percolating water changed at the reaction front. Several heavy metals (Cd, Co, Cu, Ni) and Al were immobilized at this front. Other parameters such as Ca, S as SO4, V, and Mo were depleted within several days. The reaction front moved forward depending on the Darcy velocity in the column and the buffer capacity of the brick sand. Thermodynamic calculations (PHREEQC 2.0) indicated that mobilization of As was influenced by Ba(AsO4)2. The solubility of Ba and Mn was controlled by barite and manganite, respectively. Reactive transport modeling was applied to describe the dissolution of the bricks with regard to their main components Ca, SO4, Al, and Si.     

First insights of Cr speciation in leached Portland cement using X-ray spectromicroscopy

X-ray spectromicroscopy has been successfully applied to determine the evolution of the Cr oxidation state in Portland cement during leaching experiments. To our knowledge, this is the first study that demonstrates the possibility to study the chromium oxidoreduction phenomena in cement materials at natural Cr concentration (approximately 60 ppm) and at the micron scale. Line scans of Cr for Cr(VI) doped (2000 ppm) and undoped samples indicate that the altered layer (0-1000 microm from the surface) is characterized by a lower amount of Cr as compared to the core part, whereas an accumulation appears in the intermediate region (1000-1300 microm). This Cr-rich interface could correspond to an accumulation of ettringite (3CaO x Al2O3 x 3CaSO4 x 32H2O) as reported by previous works. This mineral exhibits the property to incorporate Cr(III) and Cr(VI) by replacement of aluminum and sulfate, respectively, in the structure. The most surprising result concerns the evolution of the Cr(VI)/Cr(tot) ratio along the line spectra, which is constant from the altered layer to the core (both for doped and undoped samples). This means thatthe same amounts of Cr(VI) and Cr(tot) are released during leaching. Even for the undoped sample, Cr(VI) was detected in the altered layer at 40 microm from the surface. This result is not in perfect agreement with literature, which usually states that Cr(VI) is mainly leached out. Although this result must be confirmed, it clearly indicates that Cr(VI) may be less mobile than predicted by models. An attempt is made to identify potential Cr(VI) fixation phases.     

Aqueous solubility diagrams for cementitious waste stabilization systems. 4. A carbonation model for Zn-doped calcium silicate hydrate by Gibbs energy minimization

A thermodynamic Gibbs energy minimization (GEM) solid solution-aqueous solution (SSAS) equilibrium model was used to determine the solubility of Zn from calcium silicate hydrate (CSH) phases doped with 0, 0.1, 1, 5, and 10% Zn at a unity (Ca+Zn)/Si molar ratio. Both the stoichiometry and standard molar Gibbs energy (G(o)298) of the Zn-bearing end-member in the ideal ternary Zn-bearing calcium silicate hydrate (CZSH) solid solution were determined by a "dual-thermodynamic" (GEM-DT) estimation technique. The SSAS model reproduces a complex sequence of reactions suggested to occur in a long-term weathering scenario of cementitious waste forms at subsurface repository conditions. The GEM model of CZSH leaching at several Zn loadings and solid/water (s/w) ratios in a C02-free system showed that, upon complete dissolution of portlandite and calcium zincate phases at decreasing s/w < 0.01 mol x kg(H2O)(-1), the total dissolved concentrations Si(aq), Ca(aq), and Zn(aq) are controlled by a CZSH solid solution of changing composition, with a trough-like Znaq drop by 2-3 orders of magnitude. Carbonation was simulated in another GEM model run series by CO2 titration of the system with initial s/w approximately 0.9 mol/kg(H2O). Formation of (Ca,Zn)-CO3 nonideal solid solution was predicted already at early reaction stage in the presence of both portlandite and calcium zincate hydrate phases. Upon their disappearance, pH, Zn(aq), C(aq), and fCO2 were predicted to change due to the incongruent dissolution of two concurrent CZSH-I and CZSH-II solid solutions, until the total re-partitioning of Ca and Zn into a carbonate solid solution coexisting with amorphous silica at fCO2 > 0.1 bar. Along this solid-phase transition, dissolved Zn(aq) concentrations follow a highly nonlinear trend. The model results predict that at low to moderate Zn loading (< or = 1% per mole Si), CZSH-type compounds can efficiently immobilize Zn in the near field of a cement-stabilized waste repository.     

Recovery of uranium from mine waste by leaching with carbonate-based reagents

Waste materials, stored in inappropriate places, are one of the most significant environmental issues concerning mining activities. In Brazil, one closed uranium mine has faced such a problem. The waste, produced during the neutralization of acid drainage and containing several metals including uranium, has been disposed into the mine opening as a temporary alternative for over 20 years. The present work aimed at the recovery of the uranium present in the aforementioned waste. The effect of the following parameters on the leaching procedure was investigated: solid/liquid ratio, time, temperature, extracting agents, concentration of reagents, and the use of oxidants. The chemical characterization showed that the main constituents of the sample are Ca, S, Mn, and Al. Uranium is around 0.25%. The crystallized phases are ettringite (Ca(6)Al(2)(SO(4))(3)·(OH)(12)·26H(2)O) as the major phase followed by gypsum (CaSO(4)·2H(2)O), calcite (CaCO(3)), and bassanite (CaSO(4)·0.5H(2)O). Carbonate and bicarbonate were observed to be effective extractants for the uranium. However, a combination of both reagents proved to be a better option than their individual use, and extractions around 100% were achieved. The optimum experimental condition for attaining the maximum dissolution is 0.11 solid/liquid ratio, 0.50 mol L(-1) Na(2)CO(3), 1.00 mol L(-1) NaHCO(3), 20 h, and room temperature.     

Residual waste from Hanford tanks 241-C-203 and 241-C-204. 1. Solids characterization

Bulk X-ray diffraction (XRD), synchrotron X-ray microdiffraction (microXRD), and scanning electron microscopy/ energy-dispersive X-ray spectroscopy (SEM/EDS) were used to characterize solids in residual sludge from single-shell underground waste tanks C-203 and C-204 at the U.S. Department of Energy's Hanford Site in southeastern Washington state. Cejkaite [Na4(UO2)(CO3)3] was the dominant crystalline phase in the C-203 and C-204 sludges. This is one of the few occurrences of cejkaite reported in the literature and may be the first documented occurrence of this phase in radioactive wastes from DOE sites. Characterization of residual solids from water leach and selective extraction tests indicates that cejkaite has a high solubility and a rapid rate of dissolution in water at ambient temperature and that these sludges may also contain poorly crystalline Na2U207 [or clarkeite Na[(UO2)O(OH)](H2O)0-1] as well as nitratine (soda niter, NaNO3), goethite [alpha-FeO(OH)], and maghemite (gamma-Fe2O3). Results of the SEM/EDS analyses indicate that the C-204 sludge also contains a solid that lacks crystalline form and is composed of Na, Al, P, O, and possibly C. Other identified solids include Fe oxides that often also contain Cr and Ni and occur as individual particles, coatings on particles, and botryoidal aggregates; a porous-looking material (or an aggregate of submicrometer particles) that typically contain Al, Cr, Fe, Na, Ni, Si, U, P, O, and C; Si oxide (probably quartz); and Na-Al silicate(s). The latter two solids probably represent minerals from the Hanford sediment, which were introduced into the tank during prior sampling campaigns or other tank operation activities. The surfaces of some Fe-oxide particles in residual solids from the water leach and selective extraction tests appear to have preferential dissolution cavities. If these Fe oxides contain contaminants of concern, then the release of these contaminants into infiltrating water would be limited by the dissolution rates of these Fe oxides, which in general have lowto very low solubilities and slow dissolution rates at near neutral to basic pH values under oxic conditions.