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.     

Wintertime rates of net primary production and nitrate and ammonium uptake in the southern Benguela upwelling system

The elevated levels of primary productivity associated with eastern boundary currents are driven by nutrient- rich waters upwelled from depth, such that these regions are typically characterised by high rates of nitrate-fuelled phytoplankton growth. Production studies from the southern Benguela upwelling system (SBUS) tend to be biased towards the summer upwelling season, yet winter data are required to compute annual budgets and understand seasonal variability. Net primary production (NPP) and nitrate and ammonium uptake were measured concurrently at six stations in the SBUS in early winter. While euphotic zone NPP was highest at the stations nearest to the coast and declined with distance from the shore, a greater proportion was potentially exportable from open-ocean surface waters, as indicated by the higher specific nitrate uptake rates and f-ratios (ratio of nitrate uptake to total nitrogen consumption) at the stations located off the continental shelf. Near the coast, phytoplankton growth was predominantly supported by ammonium despite the high ambient nitrate concentrations. Along with ammonium concentrations as high as 3.6 µmol l^–1, this strongly suggests that nitrate uptake in the inshore SBUS, and by extension carbon drawdown, is inhibited by ammonium, at least in winter, although this has also been hypothesised for the summer.     

Ferrous phosphate surface precipitates resulting from the reduction of intragrain 6-line ferrihydrite by Shewanella oneidensis MR-1

The reductive biotransformation of 6-line ferrihydrite located within porous silica (intragrain ferrihydrite) by Shewanella oneidensis MR-1 was investigated and compared to the behavior of 6-line ferrihydrite in suspension (free ferrihydrite). The effect of buffer type (PIPES and NaHCO₃), phosphate (P), and an electron shuttle (AQDS) on the extent of reduction and formation of Fe(II) secondary phases was investigated under anoxic conditions. Electron microscopy and micro X-ray diffraction were applied to evaluate the morphology and mineralogy of the biogenic precipitates and to study the distribution of microorganisms on the surface of porous silica after bioreduction. Kinetic reduction experiments with free and intragrain ferrihydrite revealed contrasting behavior with respect to the buffer and presence of P. The overall amount of intragrain ferrihydrite reduction was less than that of free ferrihydrite [at 5 mmol L⁻¹ Fe(III)_T]. Reductive mineralization was not observed in the intragrain ferrihydrite incubations without P, and all biogenic Fe(II) concentrated in the aqueous phase. Irrespective of buffer and AQDS addition, rosettes of Fe(II) phosphate of approximate 20-30 μm size were observed on porous silica when P was present. The rosettes grew not only on the silica surface but also within it, forming a coherent spherical structure. These precipitates were well colonized by microorganisms and contained extracellular materials at the end of incubation. Microbial extracellular polymeric substances may have adsorbed Fe(II) promoting Fe(II) phosphate nucleation with subsequent crystal growth proceeding in different directions from a common center.     

The dissolution of synthetic Na-boltwoodite in sodium carbonate solutions

Uranyl silicates such as uranophane and Na-boltwoodite appear to control the solubility of uranium in certain contaminated sediments at the US Department of Energy Hanford site [Liu, C., Zachara, J.M., Qafoku, O., McKinley, J.P., Heald, S.M., Wang, Z. 2004. Dissolution of uranyl microprecipitates in subsurface sediments at Hanford Site, USA. Geochim. Cosmochim. Acta68, 4519-4537.]. Consequently, the solubility of synthetic Na-boltwoodite, Na(UO₂)(SiO₃OH) · 1.5H₂O, was determined over a wide range of bicarbonate concentrations, from circumneutral to alkaline pH, that are representative of porewater and groundwater compositions at the Hanford site and calcareous environments generally. Experiments were open to air. Results show that Na-boltwoodite dissolution was nearly congruent and its solubility and dissolution kinetics increased with increasing bicarbonate concentration and pH. A consistent set of solubility constants were determined from circumneutral pH (0 added bicarbonate) to alkaline pH (50 mM added bicarbonate). Average or 5.85 ± 0.0.26; using the Pitzer ion-interaction model or Davies equation, respectively. These values are close to the one determined by [Nguyen, S.N., Silva, R.J., Weed, H.C., Andrews, Jr., J.E., 1992. Standard Gibbs free energies of formation at the temperature 303.15 K of four uranyl silicates: soddyite, uranophane, sodium boltwoodite, and sodium weeksite. J. Chem. Thermodynamics24, 359-376.] under very different conditions (pH 4.5, Ar atmosphere).     

Heterogeneous reduction of Tc(VII) by Fe(II) at the solid-water interface

Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to hematite and goethite, and by Fe(II) associated with a dithionite-citrate-bicarbonate (DCB) reduced natural phyllosilicate mixture [structural, ion-exchangeable, and edge-complexed Fe(II)] containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by DCB-reduced phyllosilicates were not sensitive to pH or to added that adsorbed to the clay. The reduction kinetics were orders of magnitude slower than observed for the Fe(III) oxides, and appeared to be controlled by structural Fe(II). The following affinity series for heterogeneous Tc(VII) reduction by Fe(II) was suggested by the experimental results: aqueous Fe(II) ∼ adsorbed Fe(II) in phyllosilicates [ion-exchangeable and some edge-complexed Fe(II)] ? structural Fe(II) in phyllosilicates ? Fe(II) adsorbed on Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO₂ monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mössbauer spectroscopy applied to an experiment with ⁵⁶Fe-goethite with adsorbed ⁵⁷Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB-reduced phyllosilicates was different from the Fe(III) oxides, and was more similar to Tc(IV) oxyhydroxide in its second coordination shell. The heterogeneous reduction of Tc(VII) to less soluble forms by Fe(III) oxide-adsorbed Fe(II) and structural Fe(II) in phyllosilicates may be an important geochemical process that will proceed at very different rates and that will yield different surface species depending on subsurface pH and mineralogy.     

内蒙古西拉沐伦成矿带碾子沟钼矿床成矿流体地球化学特征

碾子沟钼矿床是内蒙古西拉沐伦钼多金属成矿带中石英脉型钼矿床的典型代表,矿体以石英大脉形式产于燕山期中粗粒黑云母二长花岗岩内,受断裂构造控制。流体包裹体研究发现包裹体均为气液两相,按照相比不同,可进一步分为WL型(5%～20%)和WV型(20%～50%)。Ⅰ阶段流体为低温(89.3～245.2℃)、中低盐度(2.07%～17.96%NaCleqv)流体;Ⅱ阶段流体具有中低温(134.4～458.8℃,峰值170℃～240℃)、中低盐度(0.53%～19.92%NaCleqv)特征;Ⅲ阶段流体为低温(134.9～202.4℃)、中低盐度(4.96%～14.97%NaCleqv)流体。流体成分均以H2O为主(96.1mol%),含少量挥发份CO2、N2、CH4、C2H6、Ar、H2S,阳离子以Na+为主,阴离子以SO42-、Cl-为主,属NaCl-H2O体系。各阶段成矿热液氢、氧同位素特征为:δ18OH2O介于-5.75‰～-1.90‰、δD介于-128.821‰～-109.234‰,说明成矿流体是岩浆热液与古大气降水混合而成。开放的断裂体系为流体混合创造了条件,流体的混合作用是造成碾子沟辉钼矿沉淀成矿的主要原因。这与斑岩型钼矿床的高盐度流体以及以沸腾为主的矿石沉淀机制具有显著区别。     

Influence of hydrolysis on the sorption of metal cations by smectites: Importance of edge coordination reactions

A comparison was made between the adsorptive behaviors of Cd²⁺ and UO ₂ ²⁺ relative to two smectites that differed in their ratio of edge sites to fixed-charge sites. Adsorption varied with both pH and ionic strength, consistent with sorptive contributions of ion exchange and coordination reactions to edge hydroxyls. Both clay minerals exhibited a greater affinity for UO ₂ ²⁺ than for Cd²⁺, and the clay with a higher proportion of edge sites retained both ions more strongly. A computational model including fixed-charge sites and edge hydroxyls resulted in a good prediction of overall UO ₂ ²⁺ and Cd²⁺ uptake to both smectites.     

Reduction of TcO4 by sediment-associated biogenic Fe(II)

The potential for reduction of ⁹⁹TcO₄⁻_(aq) to poorly soluble ⁹⁹TcO₂ · nH₂O_(s) by biogenic sediment-associated Fe(II) was investigated with three Fe(III)-oxide containing subsurface materials and the dissimilatory metal-reducing subsurface bacterium Shewanella putrefaciens CN32. Two of the subsurface materials from the U.S. Department of Energy’s Hanford and Oak Ridge sites contained significant amounts of Mn(III,IV) oxides and net bioreduction of Fe(III) to Fe(II) was not observed until essentially all of the hydroxylamine HCl-extractable Mn was reduced. In anoxic, unreduced sediment or where Mn oxide bioreduction was incomplete, exogenous biogenic TcO₂ · nH₂O_(s) was slowly oxidized over a period of weeks. Subsurface materials that were bioreduced to varying degrees and then pasteurized to eliminate biological activity, reduced TcO₄⁻_(aq) at rates that generally increased with increasing concentrations of 0.5 N HCl-extractable Fe(II). Two of the sediments showed a common relationship between extractable Fe(II) concentration (in mM) and the first-order reduction rate (in h⁻¹), whereas the third demonstrated a markedly different trend. A combination of chemical extractions and ⁵⁷Fe Mössbauer spectroscopy were used to characterize the Fe(III) and Fe(II) phases. There was little evidence of the formation of secondary Fe(II) biominerals as a result of bioreduction, suggesting that the reactive forms of Fe(II) were predominantly surface complexes of different forms. The reduction rates of Tc(VII)O₄⁻ were slowest in the sediment that contained plentiful layer silicates (illite, vermiculite, and smectite), suggesting that Fe(II) sorption complexes on these phases were least reactive toward pertechnetate. These results suggest that the in situ microbial reduction of sediment-associated Fe(III), either naturally or via redox manipulation, may be effective at immobilizing TcO₄⁻_(aq) associated with groundwater contaminant plumes.     

A multimetric-index approach using fisheries data to assess fish assemblage structure in relation to salinity gradient in a tropical West African estuary

This study examines the effects of increasing salinity on fish assemblage structure in the Casamance Estuary, Senegal, using a series of indices. The study data were derived from commercial fishery surveys conducted between April and July 2005. Analysis of within-trophic-group diversity in the Casamance Estuary shows a significant drop in the diversity of apex predators in the upper, more saline reaches of the estuary. By contrast, primary consumers adapted well to salinity changes and exhibited higher taxonomic diversity in the upper reaches of the estuary than in the lower reaches. The findings also indicate decreases in average sizes of the landed species and the trophic levels among fish catches in the direction of the upper reaches. However, the catch per unit effort (CPUE) was globally higher in the upstream area of the estuary as compared with the downstream area. This increasing CPUE trend from the lower towards the upper reaches is attributed to (i) the high primary productivity in the upper Casamance Estuary; (ii) the increasing abundance of euryhaline fish species in an upstream direction; and (iii) ‘telescoping’ of the food chain through the presence of mostly herbivorous fishes in the upper reaches. Such a situation likely facilitated high fish production in the upstream area of the estuary, though multimetric indices indicated unfavourable living conditions for many fish taxa in this area.     

Classification of marine bioregions on the east coast of South Africa

Marine bioregional planning requires a meaningful classification and spatial delineation of the ocean environment using biological and physical characteristics. The relative inaccessibility of much of the ocean and the paucity of directly measured data spanning entire planning regions mean that surrogate data, such as satellite imagery, are frequently used to develop spatial classifications. However, due to a lack of appropriate biological data, these classifications often rely on abiotic variables, which act as surrogates for biodiversity. The aim of this study was to produce a fine-scale bioregional classification, using multivariate clustering, for the inshore and offshore marine environment off the east coast of South Africa, adjacent to the province of KwaZulu-Natal and out to the boundary of the exclusive economic zone (EEZ), 200 nautical miles offshore. We used remotely sensed data of sea surface temperature, chlorophyll a and turbidity, together with interpolated bathymetry and continental-slope data, as well as additional inshore data on sediments, seabed oxygen and bottom temperature. A multivariate k-means analysis was used to produce a fine-scale marine bioregionalisation, with three bioregions subdivided into 12 biozones. The offshore classification was primarily a pelagic bioregionalisation, whereas the inshore classification (on the continental shelf) was a coupled benthopelagic bioregionalisation, owing to the availability of benthic data for this area. The resulting classification was used as a base layer for a systematic conservation plan developed for the province, and provided the methods for subsequent planning conducted for the entire South African EEZ. Validation of the classification is currently being conducted in marine research programmes that are sampling benthic biota and habitats in a sampling design stratified according to the biozones delineated in this study.