Desorption kinetics of radiocesium from subsurface sediments at Hanford Site, USA

The desorption of ¹³⁷Cs⁺ was investigated on sediments from the United States Hanford site. Pristine sediments and ones that were contaminated by the accidental release of alkaline ¹³⁷Cs⁺-containing high level nuclear wastes (HLW, 2 × 10⁶ to 6 × 10⁷ pCi ¹³⁷Cs⁺/g) were studied. The desorption of ¹³⁷Cs⁺ was measured in Na⁺, K⁺, Rb⁺, and NH₄⁺electrolytes of variable concentration and pH, and in presence of a strong Cs⁺-specific sorbent (self-assembled monolayer on a mesoporous support, SAMMS). ¹³⁷Cs⁺ desorption from the HLW-contaminated Hanford sediments exhibited two distinct phases: an initial instantaneous release followed by a slow kinetic process. The extent of ¹³⁷Cs⁺ desorption increased with increasing electrolyte concentration and followed a trend of Rb⁺ ≥ K⁺ > Na⁺ at circumneutral pH. This trend followed the respective selectivities of these cations for the sediment. The extent and rate of ¹³⁷Cs⁺ desorption was influenced by surface armoring, intraparticle diffusion, and the collapse of edge-interlayer sites in solutions containing K⁺, Rb⁺, or NH₄⁺. Scanning electron microscopic analysis revealed HLW-induced precipitation of secondary aluminosilicates on the edges and basal planes of micaceous minerals that were primary Cs⁺ sorbents. The removal of these precipitates by acidified ammonium oxalate extraction significantly increased the long-term desorption rate and extent. X-ray microprobe analyses of Cs⁺-sorbed micas showed that the ¹³⁷Cs⁺ distributed not only on mica edges, but also within internal channels parallel to the basal plane, implying intraparticle diffusive migration of ¹³⁷Cs⁺. Controlled desorption experiments using Cs⁺-spiked pristine sediment indicated that the ¹³⁷Cs⁺ diffusion rate was fast in Na⁺-electrolyte, but much slower in the presence of K⁺ or Rb⁺, suggesting an effect of edge-interlayer collapse. An intraparticle diffusion model coupled with a two-site cation exchange model was used to interpret the experimental results. Model simulations suggested that about 40% of total sorbed ¹³⁷Cs⁺ was exchangeable, including equilibrium and kinetic desorbable pools. At pH 3, this ratio increased to 60-80%. The remainder of the sorbed ¹³⁷Cs⁺ was fixed or desorbed at much slower rate than our experiments could detect.     

Paleohydrology of arid southeastern maui, hawaiian islands, and its implications for prehistoric human settlement

Arid slopes on the southeastern side of Maui are densely covered with archaeological remains of Hawaiian settlement from the late prehistoric to early postcontact period (ca. A.D. 1500-1860). Permanent habitation sites, agricultural features, and religious structures indicate perennial occupation and farming in a subregion called Kahikinui, yet there is presently no year-round water source. We explore the possibility that postcontact deforestation led to the loss of either (1) perennial channel flow or (2) perennial springs or seeps. To investigate the first possibility, we estimated ancient peak flows on 11 ephemeral channels in Kahikinui using field measurements and paleohydrology. Peak-flow estimates (3-230 m³/s) for a given drainage area are smaller than those for current perennial Maui streams, but are equivalent to gauged peak flows from ephemeral and intermittent streams in the driest regions of Hawai’i and Maui islands. This is consistent with the long-term absence of perennial channel flow in Kahikinui. On the other hand, others have shown that canopy fog-drip in Hawai’i can be greater than rainfall and thus a large part of groundwater recharge. Using isolated live remnants and snags, we estimate the former extent of the forest upstream from archaeological sites. We use rough estimates of the loss of fog-drip recharge caused by deforestation and apply a simple, steady-state hydrologic model to calculate potential groundwater table fall. These order-of-magnitude estimates indicate that groundwater could have fallen by a minimum of several meters, abandoning perennial seeps. This is consistent with archaeological evidence for former perennial seeps, such as stonewalls enclosing potential seeps to protect them. Although longer-term reductions in rainfall cannot be ruled out as a factor, deforestation and loss of fog-drip recharge are obvious and more immediate reasons for a recent loss of perennial water in Kahikinui, Maui.     

Kinetics of Disproportionation of Inorganic Polysulfides in Undersaturated Aqueous Solutions at Environmentally Relevant Conditions

The rate of the reversible homogeneous disproportionation of polysulfides was studied by following the optical absorbance of polysulfide solutions in a continuous plug flow reactor equipped with an on-line photometric detector. In order to avoid heterogeneous slow reactions involving sulfur colloids or precipitate, the reaction was initiated by an abrupt pH change from an undersaturated solution containing predominantly tetrasulfide species to a pH where pentasulfide is the dominant species. The disproportionation was found to follow first order reversible reaction dynamics. At environmentally relevant conditions the characteristic time of the disproportionation reaction is of the order of 10 s. This characteristic time implies that necessary conditions for speciation of the different polysulfide species by chromatography or another separation and subsequent quantification scheme should be of the order of 1 s.     

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element.We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases.Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO₂, carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO₂.Thermodynamic calculations indicate that Te occurs predominantly as H₅TeO₆⁻ in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO₂ in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.     

Late Pliocene to late Pleistocene environments preserved at the Palisades Site, central Yukon River, Alaska

The Palisades Site is an extensive silt-loam bluff complex on the central Yukon River preserving a nearly continuous record of the last 2 myr. Volcanic ash deposits present include the Old Crow (OCt; 140,000 yr), Sheep Creek (SCt; 190,000 yr), PA (2.02 myr), EC (ca. 2 myr), and Mining Camp (ca. 2 myr) tephras. Two new tephras, PAL and PAU, are geochemically similar to the PA and EC tephras and appear to be comagmatic. The PA tephra occurs in ice-wedge casts and solifluction deposits, marking the oldest occurrence of permafrost in central Alaska. Three buried forest horizons are present in association with dated tephras. The uppermost forest bed occurs immediately above the OCt; the middle forest horizon occurs below the SCt. The lowest forest bed occurs between the EC and the PA tephras, and correlates with the Dawson Cut Forest Bed. Plant taxa in all three peats are common elements of moist taiga forest found in lowlands of central Alaska today. Large mammal fossils are all from common late Pleistocene taxa. Those recovered in situ came from a single horizon radiocarbon dated to ca. 27,000 ¹⁴C yr B.P. The incongruous small mammal assemblage in that horizon reflects a diverse landscape with both wet and mesic environments.     

Estuary-specific variation in the air-water gas exchange coefficient for oxygen

Oxygen air-water gas exchange was measured using floating chambers in two shallow tidal estuaries of differing bathymetry and local terrain, near Waquoit Bay, Massachusetts (United States). The specific chamber design permitted measurements of gas flux in 15 min, allowing analysis of the relationship with wind speed and tidal stage. Exchange coefficients ranged from 0.5 to 2.5 g O₂·m^?2 h^?1 atm^?1 (equivalent to piston velocities of 1.5 to 7 cm h^?1) for wind speeds of 0.3 to 9 m s^?1 at 10 m elevation. While the relationships for each estuary appear linear (significant linear regressions with wind speed were shown for each estuary, and the slopes were different at the 99.5% confidence level), the range of speeds differed at the two sites and an exponential function of wind speed was consistent with the combined data from both estuaries. A power function of wind speed was not an acceptable model. The exchange coefficients for our estuaries are from 57% to as low as 9% of that predicted by previously published generic equations. Because the atmospheric correction can be significant in shallow, metabolically active coastal waters, we suggest that empirically determined relationships for gas exchange versus wind for a specific estuary are preferable to the predictions of the general equations. While the floating chamber method should be used cautiously, at low winds speeds (below 8 m s^?1) and in slowly flowing waters, it provides a convenient approach for quantifying these site-specific differences. The differences, especially those between shallow sheltered systems and the open waters best fit by some published relationships, are ecologically important and do not appear yet to be measurable by other methods.