Sorption of Cs+ to Micaceous Subsurface Sediments from the Hanford Site, USA
The sorption of Cs{sup +} was investigated over a large concentration range (10{sup -9}-10{sup -2} mol/L) on subsurface sediments from a United States nuclear materials site (Hanford) where high-level nuclear wastes (HLW) have been accidentally released to the vadose zone. The sediment sorbs large amounts of radiocesium, but expedited migration has been observed when HLW (a NaNO{sub 3} brine) is the carrier. Cs{sup +} sorption was measured on homoionic sediments (Na{sup +}, K{sup +}, Ca{sup 2+}) with electrolyte concentrations ranging from 0.01 to 1.0 mol/L. In Na{sup +} electrolyte, concentrations were extended to near saturation with NaNO{sub 3(s)} (7.0 mol/L). The sediment contained nonexpansible (biotite, muscovite) and expansible (vermiculite, smectite) phyllosilicates. The sorption data were interpreted according to the frayed edge-planar site conceptual model. A four-parameter, two-site (high- and low-affinity) numeric ion exchange model was effective in describing the sorption data. The high-affinity sites were ascribed to wedge zones on the micas where particle edges have partially expanded due to the removal of interlayer cations during weathering, and the low-affinity ones to planar sites on the expansible clays. The electrolyte cations competed with Cs{sup +} for both high- and low-affinity sites according to the trend K{sup +} >> Na{sup +} {ge} Ca{sup 2+}. At high salt concentration, Cs{sup +} adsorption occurred only on high-affinity sites. Na{sup +} was an effective competitor for the high-affinity sites at high salt concentrations. In select experiments, silver-thiourea (AgTU) was used as a blocking agent to further isolate and characterize the high-affinity sites, but the method was found to be problematic. Mica particles were handpicked from the sediment, contacted with Cs{sub eq}{sup +}, and analyzed by electron microprobe to identify phases and features important to Cs{sup +} sorption. The microprobe study implied that biotite was the primary contributor of high-affinity sites because of its weathered periphery. The poly-phase sediment exhibited close similarity in ion selectivity to illite, which has been well studied, although its proportion of high-affinity sites relative to the cation exchange capacity (CEC) was lower than that of illite. Important insights are provided on how Na{sup +} in HLW and indigenous K{sup +} displaced from the sediments may act to expedite the migration of strongly sorbing Cs{sup +} in subsurface environments.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1033470
- Report Number(s):
- PNNL-SA-33718; GCACAK; KP1301020; TRN: US201202%%769
- Journal Information:
- Geochimica et Cosmochimica Acta, Vol. 66, Issue 2; ISSN 0016-7037
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ADSORPTION
BIOTITE
CATIONS
CLAYS
ELECTROLYTES
ELECTRONS
ILLITE
ION EXCHANGE
MICA
MUSCOVITE
RADIOACTIVE WASTES
REMOVAL
SATURATION
SEDIMENTS
SMECTITE
SORPTION
VERMICULITE
WEATHERING
Cs adsorption
ion exchange
high ionic strength
AgTU
adsorption modeling