Transport of Sr2+ and SrEDTA2- in partially-saturated and heterogeneous sediments

Strontium-90 has migrated deep into the unsaturated subsurface beneath leaking storage tanks in the Waste Management Areas (WMA) at the U.S. Department of Energy's (DOE) Hanford Reservation. Faster than expected transport of contaminants in the vadose zone is typically attributed to either physical hydrologic processes such as development of preferential flow pathways, or to geochemical processes such as the formation of stable, anionic complexes with organic chelates, e.g., ethylenediaminetetraacetic acid (EDTA). The goal of this paper is to determine whether hydrological processes in the Hanford sediments can influence the geochemistry of the system and hence control transport of Sr(2+) and SrEDTA(2-). The study used batch isotherms, saturated packed column experiments, and an unsaturated transport experiment in an undisturbed core. Isotherms and repacked column experiments suggested that the SrEDTA(2-) complex was unstable in the presence of Hanford sediments, resulting in dissociation and transport of Sr(2+) as a divalent cation. A decrease in sorption with increasing solid:solution ratio for Sr(2+) and SrEDTA(2-) suggested mineral dissolution resulted in competition for sorption sites and the formation of stable aqueous complexes. This was confirmed by detection of MgEDTA(2-), MnEDTA(2-), PbEDTA(2-), and unidentified Sr and Ca complexes. Displacement of Sr(2+) through a partially-saturated undisturbed core resulted in less retardation and more irreversible sorption than was observed in the saturated repacked columns, and model results suggested a significant reservoir (49%) of immobile water was present during transport through the heterogeneous layered sediments. The undisturbed core was subsequently disassembled along distinct bedding planes and subjected to sequential extractions. Strontium was unequally distributed between carbonates (49%), ion exchange sites (37%), and the oxide (14%) fraction. An inverse relationship between mass wetness and Sr suggested that sandy sediments of low water content constituted the immobile flow regime. Our results suggested that the sequestration of Sr(2+) in partially-saturated, heterogeneous sediments was most likely due to the formation of immobile water in drier regions having low hydraulic conductivities.     

Scaling the quality of teammates' mental models: equifinality and normative comparisons

We tested the impact of teammates' team and task mental model sharedness on team processes and performance using 70 undergraduate teams that completed a series of missions on a PC‐based flight simulator. Moreover, we considered how the quality of mental models might moderate such relationships. Team processes were found to partially mediate the relationship between task mental model sharedness and team performance. Although team mental model sharedness failed to exhibit a significant linear relationship with team processes or performance, it did evidence a multiplicative relationship as moderated by the quality of those models. Team processes and performance were better among teams sharing higher‐quality team mental models than among teams evidencing less sharedness or who had lower‐quality models. Again, team processes partially mediated these relationships. Results are discussed in terms of the equifinality of mental model quality and applications to various team environments. Copyright © 2005 John Wiley & Sons, Ltd.     

Distribution of uranium contamination in weathered fractured saprolite/shale and ground water

The objective of this study was to determine how structure, stratigraphy, and weathering influence fate and transport of contaminants (particularly U) in the ground water and geologic material at the Department of Energy (DOE) Environmental Remediation Sciences Department (ERSD) Field Research Center (FRC). Several cores were collected near four former unlined adjoining waste disposal ponds. The cores were collected, described, analyzed for U, and compared with ground water geochemistry from surrounding multilevel wells. At some locations, acidic U-contaminated ground water was found to preferentially flow in small remnant fractures weathering the surrounding shale (nitric acid extractable U [U(NA)] usually < 50 mg kg(-1)) into thin (<25 cm) Fe oxide-rich clayey seams that retain U (U(NA) 239 to 375 mg kg(-1)). However, greatest contaminant transport occurs in a 2 to 3 m thick more permeable stratigraphic transition zone located between two less permeable, and generally less contaminated zones consisting of (i) overlying unconsolidated saprolite (U(NA) < 0.01 to 200 mg kg(-1)) and (ii) underlying less-weathered bedrock (U(NA) generally < 0.01 to 7 mg kg(-1)). In this transition zone, acidic (pH < 4) U-enriched ground water (U of 38 mg L(-1)) has weathered away calcite veins resulting in greater porosity, higher hydraulic conductivity, and higher U contamination (U(NA) 106 to 745 mg kg(-1)) of the weathered interbedded shale and sandstone. These characteristics of the transition zone produce an interval with a high flux of contaminants that could be targeted for remediation.     

A parametric transfer function methodology for analyzing reactive transport in nonuniform flow

We analyze reactive transport during in-situ bioremediation in a nonuniform flow field, involving multiple extraction and injection wells, by the method of transfer functions. Gamma distributions are used as parametric models of the transfer functions. Apparent parameters of classical transport models may be estimated from those of the gamma distributions by matching temporal moments. We demonstrate the method by application to measured data taken at a field experiment on bioremediation conducted in a multiple-well system in Oak Ridge, TN. Breakthrough curves (BTCs) of a conservative tracer (bromide) and a reactive compound (ethanol) are measured at multi-level sampling (MLS) wells and in extraction wells. The BTCs of both compounds are jointly analyzed to estimate the first-order degradation rate of ethanol. To quantify the tracer loss, we compare the approaches of using a scaling factor and a first-order decay term. Results show that by including a scaling factor both gamma distributions and inverse-Gaussian distributions (transfer functions according to the advection-dispersion equation) are suitable to approximate the transfer functions and estimate the reactive rate coefficients for both MLS and extraction wells. However, using a first-order decay term for tracer loss fails to describe the BTCs at the extraction well, which is affected by the nonuniform distribution of travel paths.     

Uranium sequestration in sediment at an iron-rich contaminated site at Oak Ridge, Tennessee via. bioreduction followed by reoxidation

This study evaluated uranium sequestration performance in iron-rich(30 g/kg) sediment via bioreduction followed by reoxidation. Field tests(1383 days) at Oak Ridge, Tennessee demonstrated that uranium contents in sediments increased after bioreduced sediments were re-exposed to nitrate and oxygen in contaminated groundwater. Bioreduction of contaminated sediments(1200 mg/kg U) with ethanol in microcosm reduced aqueous U from 0.37 to 0.023 mg/L. Aliquots of the bioreduced sediment were reoxidized with O_2, H_2O_2,and NaNO_3, respectively, over 285 days, resulting in aqueous U of 0.024, 1.58 and 14.4 mg/L at pH 6.30, 6.63 and 7.62, respectively. The source-and the three reoxidized sediments showed different desorption and adsorption behaviors of U, but all fit a Freundlich model.The adsorption capacities increased sharply at pH 4.5 to 5.5, plateaued at pH 5.5 to 7.0, then decreased sharply as pH increased from 7.0 to 8.0. The O_2-reoxidized sediment retained a lower desorption efficiency at pH over 6.0. The NO_3~--reoxidized sediment exhibited higher adsorption capacity at pH 5.5 to 6.0. The pH-dependent adsorption onto Fe(Ⅲ) oxides and formation of U coated particles and precipitates resulted in U sequestration, and bioreduction followed by reoxidation can enhance the U sequestration in sediment.     

Influence of hydrological and geochemical processes on the transport of chelated metals and chromate in fractured shale bedrock

Field-scale processes governing the transport of chelated radionuclides in groundwater remain conceptually unclear for highly structured, heterogeneous environments. The objectives of this research were to provide an improved understanding and predictive capability of the hydrological and geochemical mechanisms that control the transport behavior of chelated radionuclides and metals in anoxic subsurface environments that are complicated by fracture flow and matrix diffusion. Our approach involved a long-term, steady-state natural gradient field experiment where nonreactive Br- and reactive 57Co(II)EDTA2- 109CdEDTA2-, and 51Cr(VI) were injected into a fracture zone of a contaminated fractured shale bedrock. The spatial and temporal distribution of the tracer and solutes was monitored for 500 days using an array of groundwater sampling wells instrumented within the fast-flowing fracture regime and a slower flowing matrix regime. The tracers were preferentially transported along strike-parallel fractures coupled with the slow diffusion of significant tracer mass into the bedrock matrix. The chelated radionuclides and metals were significantly retarded by the solid phase with the mechanisms of retardation largely due to redox reactions and sorption coupled with mineral-induced chelate-radionuclide dissociation. The formation of significant Fe(III)EDTA byproduct that accompanied the dissociation of the radionuclide-chelate complexes was believed to be the result of surface interactions with biotite which was the only Fe(III)-bearing mineral phase present in these Fe-reducing environments. These results counter current conceptual models that suggest chelated contaminants move conservatively through Fe-reducing environments since they are devoid of Fe-oxyhydroxides that are known to aggressively compete for chelates in oxic regimes. Modeling results further demonstrated that chelate-radionuclide dissociation reactions were most prevalent along fractures where accelerated weathering processes are expected to expose more primary minerals than the surrounding rock matrix. The findings of this study suggest that physical retardation mechanisms (i.e. diffusion) are dominant within the matrix regime, whereas geochemical retardation mechanisms are dominant within the fracture regime.     

Neurobiology of the homing pigeon—a review

Homing pigeons are well known as good homers, and the knowledge of principal parameters determining their homing behaviour and the neurological basis for this have been elucidated in the last decades. Several orientation mechanisms and parameters—sun compass, earth’s magnetic field, olfactory cues, visual cues—are known to be involved in homing behaviour, whereas there are still controversial discussions about their detailed function and their importance. This paper attempts to review and summarise the present knowledge about pigeon homing by describing the known orientation mechanisms and factors, including their pros and cons. Additionally, behavioural features like motivation, experience, and track preferences are discussed. All behaviour has its origin in the brain and the neuronal basis of homing and the neuroanatomical particularities of homing pigeons are a main topic of this review. Homing pigeons have larger brains in comparison to other non-homing pigeon breeds and particularly show increased size of the hippocampus. This underlines our hypothesis that there is a relationship between hippocampus size and spatial ability. The role of the hippocampus in homing and its plasticity in response to navigational experience are discussed in support of this hypothesis.     

Decreasing lead bioaccessibility in industrial and firing range soils with phosphate-based amendments

In-situ stabilization using phosphate (P) amendments, such as P-based fertilizers and rock, are a potentially cost-effective and minimally disruptive alternative for stabilizing Pb in soils. We examined the effect of time (0-365 d), in vitro extraction pH (1.5 vs. 2.3), and dosage of three P-based amendments on the bioaccessibility (as a surrogate for oral bioavailability) of Pb in 10 soils from U.S. Department of Defense facilities. Initial untreated soil bioaccessibility consistently exceeded the U.S. Environmental Protection Agency default value of 60% relative bioavailability, with higher bioaccessibility consistently observed at an in vitro extraction pH of 1.5 vs. 2.3. Although P-based amendments statistically (P < 0.05) reduced bioaccessibility in many instances, with reductions dependent on the amendment and dosage, large amendment dosages (approximately 20-25% by mass to yield 5% P by mass) were required to reduce average bioaccessibility by approximately 25%. For most amendment combinations, reductions continued to occur for periods up to 1 yr, indicating that the observed reductions were not merely experimental artifacts of the in vitro extraction procedure. Although our results indicated that reductions in Pb bioaccessibility with P amendments are technically feasible, relatively large amendment masses were required to achieve relatively modest reductions in bioaccessibility. The cost and potential environmental implications of adding such large amounts of P may limit the practicality of in situ immobilization for some Pb-contaminated soils, industrial and firing range soils in particular.     

Ancient settlement dynamics and predictive archaeological models for the Metapontum coastal area in Basilicata,southern Italy: from geomorphological survey to spatial analysis

In the ancient territory of the Greek settlement of Metaponto and its Chora (Ionian sector of Basilicata, southern Italy) geomorphological mapping, GIS-supported statistics, and landform topographic features were investigated and combined to extract settlement rules and site dynamics. Analyses of environmental dynamics as well as of spatial and temporal settlement evolution were carried through an integrated approach that, starting from a detailed geomorphological analysis, tried to extract the spatial relationships between archaeological site locations and landform/landscape features. Spatial analysis was used to investigate the relationships between environmental parameters and archaeological sites. The advantages to develop a predictive model using Archeological Spatial Evaluation (ASE) analysis lay in the possibility to deeply study the relationships between man and the environment. In the present study, the analysis was carried out in a pioneering way in the ~400 km² Metaponto territory in order to robustly validate - in the aftermath data - human and territorial dynamics. A model describing interactions between sites and parameters such as elevation, slope, aspect, landforms, land use, and distances from rivers was constructed. Sensibility maps were produced, which will help archaeologists to know how many and which are the parameters increasing the probability to find new archaeological sites as well as how the main geomorphological features of the study area, contextualized within the most likely paleoclimate scenario, affect ancient site arrangement though time. The preferential occupation of mid-altitude marine terraces, and the consequence spreading of agriculture on these territories, is likely due to the existence of well-developed soil profiles on them. Clearly colonists recognized that on these landform units there were the better conditions for the development of massive agricultural practices: since the SP age (4,1 to 2,0 Kyr B.P.) the settlers expands inland looking for most fertile territories as well as for areas sufficiently protected (being far away from the coast). The increase in farmhouses on the top of marine terraces from the FC up to EC-EE periods and the modifications of settlement distribution (gradual abandonment of alluvial) in the Metaponto area is likely related to the acceleration of alluvial processes. The progressive decrease of human occupation during the Hellenistic up to the Roman Age is clearly consequence of the Roman conquest. However, a role played by the increase in flooding occurrence in the coastal plain/floodplains of the main rivers in triggering the abandonment of these territories and marking the beginning of the decadent phases should not be neglected. Productive areas (locally associated to farmhouses) are preferential set along the fluvial incisions (sometime associated to farmhouses), thus implying that productive area setting is strongly linked to the presence of rivers, and of their lower rank tributaries, both as an intrinsic need of manufacturing and to facilitate the spreading of products. From the Classical to the Hellenistic Age until the Roman Age, Necropolis are spread in the entire area, from marine terraces to alluvial plain. On the other hand, Sacred areas - which appearance is recorded starting from the Colony Foundation Age - exhibits a settlement continuity in the study area starting from this time up to the entire Roman period, and the sacred areas setting is strictly associated to the category of Settlement.