Cesium migration in Hanford sediment: a multisite cation exchange model based on laboratory transport experiments

Cs+ transport experiments carried out in columns packed with uncontaminated Hanford formation sediment from the SX tank farm provide strong support for the use of a multisite, multicomponent cation exchange model to describe Cs+ migration in the Hanford vadose zone. The experimental results indicate a strong dependence of the effective Cs+ Kd on the concentrations of other cations, including Na+ that is present at high to extremely high concentrations in fluids leaking from the Hanford SX tanks. A strong dependence of the Cs+ Kd on the aqueous Cs+ concentration is also apparent, with retardation of Cs+ increasing from a value of 41 at a Cs+ concentration of 10(-4) M in the feed solution to as much as 282 at a Cs+ concentration of 5x10(-7) M, all in a background of 1 M NaNO3. The total cation exchange capacity (CEC) of the Hanford sediment was determined using 22Na isotopic equilibrium exchange in a flow-through column experiment. The value for the CEC of 120 microeq/g determined with this method is compatible with a value of 121.9 microeq/g determined by multi-cation elution. While two distinct exchange sites were proposed by Zachara et al. [Geochim. Cosmochim. Acta 66 (2002) 193] based on binary batch exchange experiments, a third site is proposed in this study to improve the fit of the Cs+-Na+ and Cs+-Ca+ exchange data and to capture self-sharpened Cs+ breakthrough curves at low concentrations of Cs+. Two of the proposed exchange sites represent frayed edge sites (FES) on weathered micas and constitute 0.02% and 0.22% of the total CEC. Both of the FES show a very strong selectivity for Cs+ over Na+ (K(Na-Cs)=10(7.22) and 10(4.93), respectively). The third site, accounting for over 99% of the total CEC, is associated with planar sites on expansible clays and shows a smaller Na+-Cs+ selectivity coefficient of 10(1.99). Parameters derived from a fit of binary batch experiments alone tend to under predict Cs+ retardation in the column experiments. The transport experiments indicate 72-90% of the Cs+ sorbed in experiments targeting exchange on FES was desorbed over a 10- and 24-day period, respectively. At high Cs+ concentrations, where sorption is controlled primarily by exchange on planar sites, 95% of the Cs+ desorption was desorbed. Most of the difficulty in desorbing Cs+ from FES is a result of the extremely high selectivity of these sites for Cs+, although truly irreversible sorption as high as 23% was suggested in one experiment. The conclusion that Cs+ exchange is largely reversible in a thermodynamic sense is supported by the ability to match Cs+ desorption curves almost quantitatively with an equilibrium reactive transport simulation. The model for Cs+ retardation developed here qualitatively explains the behavior of Cs+ in the Hanford vadose zone underneath a variety of leaking tanks with differing salt concentrations. The high selectivity of FES for Cs+ implies that future desorption and migration is very unlikely to occur under natural recharge conditions.     

AN EXAMINATION OF RELATIVE PERMEABILITY RELATIONS FOR TWO-PHASE FLOW IN POROUS MEDIA1

ABSTRACT: A key parameter in modeling two-phase flow phenomena is relative permeability. It is important to understand which variables influence relative permeability, especially since so few measurements of relative permeability have been made for typical contaminants at hazardous waste sites. This paper focuses on the effect of five variables on relative permeability: intrinsic permeability, pore-size distribution, viscosity ratio, interfacial tension, and wettability, by critically reviewing previously published relative permeability experiments. The wide variability in the functional relationship between relative permeability and saturation should be considered in attempts to model two-phase flow.     

ASSESSMENT USING GIS AND SEDIMENT ROUTING OF THE PROPOSED REMOVAL OF BALLVILLE DAM,SANDUSKY RIVER,OHIO1

ABSTRACT: The proposed removal of Ballville Dam was assessed by (1) using a new Geographic Information Systems (GIS) based method for calculating reservoir sediment storage, (2) evaluating sediment properties and contamination from core data, and (3) assessing downstream impacts from sediment routing calculations. A 1903 (pre‐dam) map was manipulated using GIS to recreate the reservoir bathymetry at time of dam construction and used in combination with a detailed 1993 bathymetric survey to calculate sediment volumes and thickness. Reservoir sediment properties and geochemistry were determined from 14 sediment vibracores. Annual sedimentation rates varied from 1.7 to 4.3 g/cm²/yr based on Cesium‐137 (¹³⁷Cs) and Lead‐210 (²¹⁰Pb) geochronology and dated flood layers. The pore fluid geochemistry (Ba, Co, Cu, Mn) of four cores showed surficial enrichments in Cu, while Co and Mn show secondary peaks within the sediments. GIS calculations showed that a designed channel through the former reservoir able to accommodate the 10 percent Probable Maximum Flood (PMF) would require removing approximately 0.35 million m³ of sediment (27 percent of the reservoir fill), either by dredging at a cost of up to $6.3 million or by releasing fine grained sediment downstream. A sediment routing model was applied for the critical 6 km downstream using four cross sections. The sediment routing model predicts that, for flows exceeding minimum Mean Daily Flow (1924 to 1998 data), greater than 90 percent of this sediment would be transported through downstream reaches into Lake Erie (Sandusky Bay).     

Relationships between psychological climate perceptions and work outcomes: a meta‐analytic review

In this study, meta‐analytic procedures were used to examine the relationships between individual‐level (psychological) climate perceptions and work outcomes such as employee attitudes, psychological well‐being, motivation, and performance. Our review of the literature generated 121 independent samples in which climate perceptions were measured and analyzed at the individual level. These studies document considerable confusion regarding the constructs of psychological climate, organizational climate, and organizational culture and reveal a need for researchers to use terminology that is consistent with their level of measurement, theory, and analysis. Our meta‐analytic findings indicate that psychological climate, operationalized as individuals' perceptions of their work environment, does have significant relationships with individuals' work attitudes, motivation, and performance. Structural equation modeling analyses of the meta‐analytic correlation matrix indicated that the relationships of psychological climate with employee motivation and performance are fully mediated by employees' work attitudes. We also found that the James and James ( 1989 ) PC_g model could be extended to predict the impact of work environment perceptions on employee attitudes, motivation, and performance. Despite the number of published individual‐level climate studies that we found, there is a need for more research using standardized measures so as to enable analyses of the organizational and contextual factors that might moderate the effects of psychological climate perceptions. Finally, we argue for a molar theory of psychological climate that is rooted in the psychological processes by which individuals make meaning or their work experiences. Copyright © 2003 John Wiley & Sons, Ltd.     

Duplication of chromosome 2 in association with ventriculomegaly — a case report

This is a case report of the prenatal diagnosis of a de novo interstitial duplication of chromosome 2 (46,XX,dup(2)(p13p21) de novo) with an associated phenotypic abnormality. This chromosomal duplication is rare, only one has previously been described prenatally. Postnatal reports of similar duplications in this region have described associated dysmorphic features and significant neurodevelopmental delay. In our case, the only ultrasound finding was moderately severe ventriculomegaly. At post-mortem, ventriculomegaly was confirmed and there was associated macrocephaly (head circumference above the 97th centile) with no dysmorphic features seen. Copyright © 2001 John Wiley & Sons, Ltd.