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Adsorption of Co2+ and Cd2+ on Wyoming montmorillonite was studied by the batch equilibration technique, as a function of salt concentration (0.01–4 M NaCl and NaNO3), pH (5.0–6.5), adsorbate concentration (trace-10−2 moles/liter), and presence of complexing ions. Comparison was made with the adsorbability of Sr2+, known to follow simple ion-exchange equations. The distribution coefficients for Co and Cd in noncomplexing media varied with salt concentration (from ∼500 liters/kg in 0.01 M Na+ to ∼10 liters/kg in 1 M Na+; pH = 5), but to a lesser extent than that of Sr. Adsorbability varied also with pH (∼1 order of magnitude/pH unit), especially at high ionic strength, compared to a negligible pH effect on Sr. The distribution coefficients of Cd and Co decreased with increasing loading on the clay at a very low percentage (0.2%) of the ion-exchange capacity compared to Sr (20%). These data suggest two classes of sites participating in the adsorption of Cd and Co.
The adsorbability of Cd in highly concentrated chloride solution (>1 M) was less than 1 liter/kg, presumably because of the chloride complex formation. This effect increased with increasing pH. The low adsorbability of Cd on montmorillonite from concentrated NaCl solution is promising with respect to its use as a tracer for monitoring flow through formations containing montmorillonite.
Clay minerals and zeolites, candidate backfill minerals for nuclear waste repositories, were treated with saturated NaCl brine and Mg-rich (Mg-Ca-Na-K) brine at 200°C and 300°C for 4 weeks under a confining pressure of 30 MPa. The Al concentrations released in NaCl brine were lower than those in Mg-rich brine at both temperatures indicating that the Mg-rich brine is more acidic than the NaCl brine under these hydrothermal conditions. The Si concentrations in both brines were low because of the relatively acidic conditions developed during the hydrothermal treatment. As determined by X-ray powder diffraction or by specific Cs and Sr sorption measurements, no alteration could be detected in clay minerals treated with NaCl brine at 200°C. Among the zeolites tested, only phillipsite and erionite altered to analcime in NaCl brine at 200°C. Zeolites and most of the clay minerals tested did not alter in the Mg-rich brine treated at 200°C. Vermiculite altered to randomly interstratified vermiculite/K-vermiculite (mica-like) by selective K uptake from the Mg-rich brine.
At 300°C, the clay minerals did not greatly alter, whereas the zeolites altered to analcime and/or albite in the presence of the NaCl brine. In the Mg-rich brine, Al-rich montmorillonite from Wyoming did not alter, whereas Al-poor montmorillonite from Texas altered to randomly interstratified montmorillonite/ illite at 300°C. Vermiculite collapsed to form K-vermiculite (~ 10.2 Å) by the selective uptake of K from the Mg-rich brine at 300°C. Most of the zeolites altered to smectites in the Mg-rich brine at 300°C because of the acidic conditions generated by the hydrolysis of Mg. The selective Cs-sorption Kd decreased from 11,700 for untreated phillipsite to 240 and 15 for the hydrothermally produced analcime/albite mixtures from the phillipsite at 200° and 300°C, respectively, in NaCl brine. These results suggest that montmorillonites and mordenites are relatively more resistant than vermiculite or other zeolites at elevated temperatures and pressures in concentrated hydrothermal brines expected in a salt repository.
Reactions of Sr, La, and Nd (the latter two elements simulating Am and Cm) with potential backfill minerals for radioactive waste storage and with repository wall rocks, such as shale, were investigated under simulated repository conditions of 200° and 300°C for 12 weeks under a confining pressure of 30 MPa. The solid and solution reaction products were characterized to determine the nature and extent of reaction. Chlorite, illite, kaolinite, montmorillonite, mordenite, and clinoptilolite and four shales removed as much as 61.2 and 98.5% of the added SrCl2 and Sr(OH)2 from solution, respectively, by ion exchange and/or by forming new strontium compounds such as SrAl2Si2O8, Sr2MgSi2O7, SrCO3 (strontianite), and SrAl2Si4O12·2H2O (Sr-wairakite). The formation of these sparingly soluble Sr phases by the reaction of the soluble Sr compounds with such backfill materials indicates that the backfill may serve as a barrier during the thermal period of the waste in the life of a repository. These same minerals and shales removed as much as 99.99% of the added La or Nd from solution at 300°C by forming new phases such as LaOHCO3, NdOHCO3, and possibly La or Nd oxides and hydroxides. Zeolites reacted with La and Nd to form smectite. Thus, if La and Nd truly simulate the reactivity of Am and Cm, properly designed backfills can serve as a barrier to the migration of transuranic elements of nuclear wastes.
Cation exchange experiments were carried out on phlogopite, biotite, and muscovite using cryptand [222] as a complexing agent, dioxane as solvent, and Li as the exchanging cation. The results indicate greater than 90% exchange of the analyzed cations K+, Rb+, and Sr++ in phlogopite and biotite after two days. Similar results for the exchange in muscovite are observed but it is apparently slower. The amount of exchange observed for mica depends mainly on pH, time and the exchanging cation at a constant temperature. Residues of the mineral phase were also investigated by X-ray diffraction and a significant change of the interlayer spacing was detected. Some samples of the residue were analyzed for Li content. The compositions of the treated samples were in good agreement with the determined exchange of K+.
The high fission yield and long half life of cesium and strontium make them the two most high-risk products from nuclear fission, so their separation from radioactive wastes is an important step in mitigating their harmful effects. Clinoptilolite, because of its thermal stability, high radiation resistance, and selectivity, was considered as the adsorbent for this purpose. In order to then separate the adsorbent-adsorbate complex from aqueous solution, the clinoptilolite was prepared as a magnetized composite with nanomagnetite. This magnetically modified zeolite enabled the efficient and quick separation of the adsorbent from solution using magnetic separation. The ability of this composite to remove Cs+ and Sr2+ from aqueous solutions was assessed and characterized using X-ray diffraction, X-ray fluorescence, Fourier-transform infrared spectroscopy, differential thermogravimetric analysis, and vibrating-sample magnetometry. Variables such as initial ion concentration, pH, contact time, and temperature in the sorption process were studied and optimized. The maximum adsorption capacities of the composite were 188.7 and 36.63 mg g-1 for Cs+ and Sr2+, respectively. Investigation of the kinetics revealed that the adsorption process onto the composite was quicker than in the case of the zeolite alone. The equilibrium data were analyzed using the Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm models. The mean free energy of sorption (E) for both ions was in the range 8–16 kJ mol-1, confirming that an ion-exchange mechanism had occurred. Positive ΔH° and negative ΔG° values were indicative of the endothermic and spontaneous nature of the removal of Cs+ and Sr2+. The saturation magnetization of the composite was measured (17.46 Am2/kg), implying fast magnetic separation of the sample after adsorption. The results obtained revealed that the natural Iranian zeolite nanomagnetite composite was a good ion exchanger in the removal of Cs+ and Sr2+.
The ultimate origin or provenance of the masses of orthopyroxene primocrysts is of paramount interest. Many lines of reasoning lead to the conclusion that these were entrained in magma ascending from deeper in the mantle, generated by the continental breakup of Gondwana, somewhere below the local continental crust. The crystals themselves look old, showing signs of long-term annealing, and the crystals are in strong isotopic contrast (Sr 87/86 and O-18) with the basaltic magma itself, with the Opx assemblage being much more radiogenic that the basalt. This is especially marked in the dais rocks in going from Opx dominated layers to more basaltic layers. Moreover, the basaltic magma itself, even when it carries no large primocrysts, is highly heterogeneous isotopically. A profile through the Peneplain Sill at Solitary Rocks, near Pandora’s Spire, in an otherwise thick (330 m) featureless sill, shows strong variations in Sr-87/86. This reflects what others previous show, that the Ferrar are isotopically "noisy" and, remarkably, exhibit isotope patterns similar to the local crust. The obvious answer that this is all from local contamination and weather cannot be true, but instead this comes from the uppermost mantle underlying local crust that has had a long physical association.
Metal isotope tracers (e.g., 87Sr/86Sr, 7Li/6Li; 138Ba/134Ba) are being employed worldwide to understand downhole processes and assess the environmental impact of hydraulic fracturing. These isotope signatures can be much more sensitive than geochemical tracers alone in discriminating between contaminant sources. This can be particularly useful when time has elapsed after an event and a contaminant has been substantially diluted, or in being able to quickly detect the intrusion of a brine with high total dissolved solids (TDS) into a protected water resource. In some cases, such as areas with multiple sources of water contaminants and overlapping chemical signatures, a multi-proxy approach is recommended. The combination of element ratio and isotopic tracers (e.g. Sr/Ca and 87Sr/86Sr) or multi-isotope tracers (e.g., 87Sr/86Sr and d7Li) can be used to discriminate between multiple contaminant sources and provide important information about the processes involved in concentrating, mobilizing or retaining a contaminant.
Dental hard tissues contain periodic incremental markings that can be used as an absolute temporal archive to reconstruct their growth and can incorporate trace elements into their chemical structure during formation that reflect diet, the environment, metabolism, and health. The growth history can be recovered from teeth using virtual tooth histology to resolve a continuous record of trace element composition within each of the mineralized dental tissues, to further our understanding of past life history events in extant and extinct taxa. While acellular cementum forms slowly and regularly and is ideal for recording annual increments, compensatory cellular cementum can mirror this regular growth through gradual physiological changes in anterior tooth inclination. Here, we document this growth through microstructural elemental mapping using non-destructive synchrotron x-ray fluorescence on chimpanzee dental thin sections. We evidence clear seasonal mineral fluctuations, and match the narrower, brighter incremental markings visible in TLM with peaks in mineral concentration in zinc and strontium.
En los Andes surandinos, las prácticas funerarias incluyeron una diversidad de actos rituales en torno a los restos de los difuntos que iban más allá de la preparación del cuerpo y el lugar de depósito. El desarrollo y las características de estos actos dependían principalmente de la condición social que tenían los muertos en vida. En el Pucará de Tilcara, definido como capital de la provincia incaica de Omaguaca, se detectan una amplia variedad de formas de inhumación, pero en este trabajo abordamos el caso de un contexto mortuorio de una mujer, cuya muerte se estima ocurrió hacia el final del período Incaico o inicios de la época Hispano-Indígena. Análisis interdisciplinarios del contexto arqueológico y, particularmente, los estudios entomológicos de la fauna cadavérica y bioantropológicos permitieron determinar que esta mujer estuvo expuesta antes de quedar sepultada por procesos naturales. Proponemos que esta exposición ocurrió en el marco del culto a los ancestros difundido por todo el imperio, y sirvió para remarcar su estatus social. El acompañamiento mortuorio y los análisis de estroncio sugieren que la mujer formó parte de un grupo de elite oriundo de otra región del Tawantinsuyu, que pudo trasladarse y asentarse en la Quebrada durante la caída del Imperio inca, buscando refugio ante la inminente envestida española.
The crystal structure of strontium hydrogen citrate monohydrate has been solved using laboratory X-ray powder diffraction data, refined using both laboratory and synchrotron data, and optimized using density functional techniques. Strontium hydrogen citrate monohydrate crystallizes in space group C2/c (#15) with a = 25.15601(17), b = 10.90724(6), c = 6.37341(4) Å, β = 91.9846(6)°, V = 1747.704(12) Å3, and Z = 8. The Sr coordination and the hydrogen bonding result in a layered structure. The SrO8 coordination polyhedra share edges to form corrugated layers parallel to the bc-plane. Hydrogen bonds between the carboxylic acid groups and water molecules link the layers. Intermolecular hydroxyl–carboxyl hydrogen bonds also link the layers in a ring pattern with a graph set symbol R2,2(12). After storage for 2 years, partial re-crystallization occurred, to an as-yet unknown compound with a triclinic unit cell.
Isotope ratios of tooth enamel from ten Early Neolithic individuals buried in a long cairn at Whitwell in central England were measured to determine where they sourced their childhood diet. Five individuals have low Sr concentrations (11–66 ppm) and high 87Sr/86Sr ratios (0.7164–0.7212). Three individuals have relatively low 87Sr/86Sr ratios (0.712–0.711) and Sr concentrations ranging between 54 and 109 ppm. Two individuals have strontium isotope values that bridge the gap between the isotope compositions of these two groups. The high 87Sr/86Sr values are rare in human enamel and exclude sources within the biosphere of central England. Oxygen isotope values are comparable to those found within human archaeological populations buried in temperate regions of Europe. The strontium isotope results should be interpreted in the context of other evidence for migration from northern France to Britain during the Early Neolithic.
Bioarchaeologists often are faced with the challenge of managing field excavations and lab analyses of skeletal remains at the same time—along with student and staff training and curation of osteological remains—and cannot be in two places at once. This article presents strategies for the recovery of human remains useful for large projects where multiple burials must be recovered simultaneously, remains are poorly preserved, and complex burial practices such as seated body positions and commingled remains are present. The excavation and curation strategies are presented in the context of the seated burial practice in the Maya region, a funerary tradition that requires detailed documentation of the burial as well as the body in order to understand its meaning. Classic period (AD 250-900) seated burials do not fit a single biological profile; in fact, the taphonomic profile of one seated individual at Actuncan, Belize, suggests a closer relationship to body processing and/or context than to status. Tropical and semitropical environmental conditions also require modified curation procedures, which present ethical challenges as well as physical ones.
In this study, Sr-incorporated nano-assembled hydroxyapatite structures (HASr) on 316L stainless steel bone plates were prepared by a biomimetic method induced by 10× simulated body fluid (SBF). First, HASr was coated on bone plates by the interaction of ions with 10× SBF containing different concentration of strontium ions. Then, silver coating is achieved as a second layer on bone plates. The cumulative release of strontium ions (Sr2+) and silver ions (Ag+) from multilayered HASr-Ag bone plates at the end of 15 days was in the range of 0.016–0.085 mM and 0.064–0.135 mM, respectively. The release mechanism for the bone plates was evaluated by several mathematical models that best fit the release data. The results showed that Sr2+ and Ag+ are released from multilayered bone plates by diffusion, whereas the release of Ag+ is not occurred by diffusion, instead the mechanism is dissolution, when silver is coated alone on bone plates.
The nature of landscape use and residence patterns during the British earlier Neolithic has often been debated. Here we use strontium and oxygen isotope analysis of tooth enamel, from individuals buried at the Hambledon Hill causewayed enclosure monument complex in Dorset, England to evaluate patterns of landscape use during the earlier Neolithic. Previous analysis suggests that a significant proportion of the artefacts found at the site may originate from lithology of Eocene and Upper to Middle Jurassic age that the enclosures overlook to the immediate west and south. The excavators therefore argued that the sector of landscape visible from Hambledon Hill provides an approximate index for the catchment occupied by the communities that it served. Most of the burial population exhibit isotope ratios that could be consistent with this argument. Connections between Hambledon Hill and regions much further afield are also hypothesised, based on the presence of artefacts within the assemblage that could have been sourced from lithology in Somerset, Devon, and Cornwall in south-west England. However, few of the sampled individuals have strontium isotope ratios consistent with having obtained the majority of their diet from such areas during childhood. The individuals who exhibit the highest strontium isotope ratios are all adult males, whom the excavators suggest to have died during one or more episodes of conflict, following the burning and destruction of surrounding defensive outworks built during the 36th century bc. At least one of these individuals, who was found with an arrowhead amongst his ribs, did not obtain his childhood diet locally and has 87Sr/86Sr values that could be comparable to those bioavailable in the south-west peninsula.
In situ migration experiments using different radiotracers have been performed in the HADES Underground Research Facility (URF), built at a depth of 225 m in the Boom Clay formation below the SCK–CEN nuclear site at Mol (Belgium). Small-scale experiments, mimicking laboratory experiments, were carried out with strongly retarded tracers (strontium, caesium, europium, americium and technetium). Contrary to europium, americium and technetium which are subjected to colloid mediated transport, the transport of strontium and caesium can be described by the classic diffusion retardation formalism. For these last two tracers, the transport parameters derived from the in situ experiments can be compared with the laboratory-derived values. For both tracers, the apparent diffusion coefficients measured in the in situ experiments agree well with the laboratory-derived values.
In the large-scale experiments (of the order of metres) performed in the URF, non-retarded or slightly retarded tracers (HTO, iodide and H14CO3–) were used. The migration behaviour of these tracers was predicted based on models applied in performance assessment calculations (classic diffusion retardation) using migration parameter values measured in laboratory experiments. These blind predictions of large-scale experiments agree well in general with the experimental measurements. Fitting the experimental in situ data leads to apparent diffusion coefficients close to those determined by the laboratory experiments. The iodide and H14CO3– data were fitted with a simple analytical expression, and the HTO data were additionally fitted numerically with COMSOL multiphysics, leading to about the same optimal values.
Understanding the environmental and biogeochemical behaviour of radionuclides is essential for managing our nuclear legacy safely. Remediation efforts and the concept of geological disposal of nuclear waste focus on immobilizing radionuclides within the subsurface. Here we review recent developments in the understanding of solid-phase capture processes of Cs, Sr, Tc, U, Pu and Np. Abiotic interactions between minerals and these radionuclides (including sorption, reductive precipitation and co-precipitation) have been studied in various conditions. Microbially driven processes are much less well characterized, for example the effects of microbial reduction on the structure and reactivity of existing minerals, or their role in the formation of new minerals. Metabolites released by bacteria can play a role in both mineral dissolution and formation, and better understanding their release and role in mineralization has great potential in the development of solid-phase capture processes for radionuclides.
With the aid of a map of the research landscape covered by this review (created using a cluster-analysis tool, a self-organizing map), we highlight the most promising sequestration processes for specific radionuclides. However, radionuclides exhibit highly species-specific behaviour in their interactions with minerals and microorganisms. More research is required to characterize the role mineral surfaces play in bioreductive immobilization of Pu and Np, the reduction products formed, and their relative stability. Further studies should concentrate on more environmentally relevant experiments that include bacteria, minerals and radionuclides.
A magmatic calcic amphibole (M4Ca≥1.50) characterized by large Sr and F contents (SrO>1 wt.%, F>2.5 wt.%) is described. According to the crystal-chemical formula, the amphibole can be classified as a strontian fluoro-magnesiohastingsite and the presence of Sr cations in the A sites is suggested. The amphibole occurs in the groundmass of ultrapotassic lavas from the Alban Hills Volcanic District (Central Italy). This peculiar chemical composition is due to the lavas' groundmass compositional trend occurring under low silica-activity conditions. We suggest that the occurrence of F amphiboles allows us to consider the Alban Hills Volcanic District magmas to be as rich in F as other ultrapotassic magmas.
Sixteen fluorapatite specimens from regional skarns in granulite terrain were associated with Al-zoned diopside ± scapolite ± actinolite ± calcite(+ rare phlogopite). Apatite was low in Ce (ave. 0.19% Ce2O3) and enriched in LREE relative to HREE (La/Yb = 31 to 74 in 4 specimens). Some specimens showed small negative Eu anomalies and some crystals were zoned in REE. SrO averaged 0.36%. The mineral contained some carbonate (ave. 0.5% CO2 in 5 specimens), appreciable silica (ave. 0.5%), and variable sulphate (0.1 to 1.2% SO3). Excess charge due to S6+ was largely compensated by Si4+. Chlorine was minor and F accounted for 75–98% of the F, Cl and OH ions. Apatite from marble lacking amphiboles and pyroxenes has a similar chemical composition, but apatite from later carbonatite and fenite contains more Ce and Sr. Apatite from Gatineau fenite, Gatineau carbonatite and world-wide siliceous igneous rock generally contains less S. Apatite from Gatineau skarns normally contains more Cl and less S than that from phosphorite. Magnesian marble was silicated to skarn by reaction with siliceous gneiss. Phosphorus, REE, and Sr were removed from nearby rocks and transported in aqueous, carbonated solutions containing minor amounts of F, Cl and S at granulite-facies conditions. Apatite and calcite precipitation took place in skarns and marble during the Grenville (Proterozoic) orogeny.
An experimental technique has been developed and applied to the problem of determining effective diffusion coefficients and partition coefficients of Sr in low permeability geological materials. This technique, the micro-reactor simulated channel method (MRSC), allows rapid determination of contaminant transport parameters with resulting values comparable to those determined by more traditional methods and also creates product surfaces that are amenable for direct chemical analysis. An attempt to further constrain mass flux was completed by detailed ion beam analysis of polished tuff surfaces (tuff is a polycrystalline polyminerallic aggregate dominated by silicate phases) that had been reacted with Sr solutions at concentrations of 10−5, 10−3 and 10−1 mol l−1. Ion beam analysis was carried out using beams of both protons (using particle induced X-ray emission and elastic backscattering spectrometry or EBS) and alpha-particles (using Rutherford backscattering spectrometry). The ion beam analyses showed that increased solution concentrations resulted in increased surface concentrations and that in the highest concentration experiment, Sr penetrated to at least 4 μm below the primary interface. The Sr surface concentrations determined by EBS were 0.06 (±0.05), 0.87 (±0.30) and 2.40 (±1.0) atomic weight % in the experiments with starting solution concentrations of 10−5, 10−3, and 10−1 mol l−1, respectively.
Strontium-rich epidote, including epidote-(Sr) and epidote with major amounts of Sr (i.e. epidote containing up to 17.3 wt.% SrO), was found in pumpellyite schist and epidote blueschist in a tectonic block in the serpentinite mélange of the Kurosegawa Zone, central Kyushu, Japan. The tectonic block is 20 m wide and made primarily of lawsonite blueschist, with subordinate amounts of pumpellyite schist and epidote blueschist. The pumpellyite schist typically occurs at the edge of the block and is composed mainly of pumpellyite with subordinate amounts of strontium-poor epidote, albite and chlorite, and thin veins of fine-grained calcite and clinopyroxene. Epidote-(Sr) forms rims around strontium-poor epidote, fills fractures in strontium-poor epidote and also occurs interstitially between pumpellyite aggregates and along the boundaries between pumpellyite and calcite-clinopyroxene veins. The epidote blueschist is found between the pumpellyite schist and lawsonite blueschist, and consists mainly of sodic amphibole, epidote and titanite, with albite veining. Strontium-rich epidote occurs as rims, replacing Sr-poor epidote near the albite vein. The bulk strontium contents of the rocks are as follows: lawsonite blueschist (200 ppm), epidote blueschist (2800 ppm) and pumpellyite schist (~10,700 ppm). The chemical and petrological characteristics of the Sr-rich epidote-bearing metabasites suggest that the infiltration of a metamorphic fluid promoted extensive Sr metasomatism during the later stages of high-pressure metamorphism.