Adsorption of REE(III)-humate complexes onto MnO2: Experimental evidence for cerium anomaly and lanthanide tetrad effect suppression

Experiments were conducted to evaluate the impact of organic complexation on the development of Ce anomalies and the lanthanide tetrad effect during the adsorption of rare-earth elements (REE) onto MnO₂. Two types of aqueous solutions—NaCl and NaNO₃—were tested at pH 5 and 7.5. Time-series experiments indicate that a steady-state is reached within less than 10 h when REE occur as free inorganic species, whereas steady state is not reached before 10 d when REE occur as REE-humate complexes. The distribution coefficients (K_d^REE) between suspended MnO₂ and solution show no or only very weak positive Ce anomaly or lanthanide tetrad effect when REE occur as humate complexes, unlike the results obtained in experiments with REE occurring as free inorganic species. Monitoring of dissolved organic carbon (DOC) concentrations show that log K_d^REE_organic/K_d^DOC ratios are close to 1.0, implying that the REE and humate remain bound to each other upon adsorption. Most likely, the Ce anomaly reduction/suppression in the organic experiments arises from a combination of two processes: (i) inability of MnO₂ to oxidize Ce(III) because of shielding of MnO₂ surfaces by humate molecules and (ii) Ce(IV) cannot be preferentially removed from solution due to quantitative complexation of the REE by organic matter. We suggest that the lack of lanthanide tetrad effect arises because the adsorption of REE-humate complexes onto MnO₂ occurs dominantly via the humate side of the complexes (anionic adsorption), thereby preventing expression of the differences in Racah parameters for 4f electron repulsion between REE and the oxide surface. The results presented here explain why, despite the development of strongly oxidizing conditions and the presence of MnO₂ in the aquifer, no (or insignificant) negative Ce anomalies are observed in organic-rich waters. The present study demonstrates experimentally that the Ce anomaly cannot be used as a reliable proxy of redox conditions in organic-rich waters or in precipitates formed at equilibrium with organic-rich waters.     

Glacial flood pulse effects on benthic fauna in equatorial high‐Andean streams

Equatorial glacier‐fed streams present unique hydraulic patterns when compared to glacier‐fed observed in temperate regions as the main variability in discharge occurs on a daily basis. To assess how benthic fauna respond to these specific hydraulic conditions, we investigated the relationships between flow regime, hydraulic conditions (boundary Reynolds number, Re*), and macroinvertebrate communities (taxon richness and abundance) in a tropical glacier‐fed stream located in the high Ecuadorian Andes (> 4000 m). Both physical and biotic variables were measured under four discharge conditions (base‐flow and glacial flood pulses of various intensities), at 30 random points, in two sites whose hydraulic conditions were representative to those found in other streams of the study catchment. While daily glacial flood pulses significantly increased hydraulic stress in the benthic habitats (appearance of Re* > 2000), low stress areas still persisted even during extreme flood events (Re* < 500). In contrast to previous research in temperate glacier‐fed streams, taxon richness and abundance were not significantly affected by changes in hydraulic conditions induced by daily glacial flood pulses. However, we found that a few rare taxa, in particular rare ones, preferentially occurred in highly stressed hydraulic habitats. Monte‐Carlo simulations of benthic communities under glacial flood reduction scenarios predicted that taxon richness would be significantly reduced by the loss of high hydraulic stress habitats following glacier shrinking. This pioneer study on the relationship between hydraulic conditions and benthic diversity in an equatorial glacial stream evidenced unknown effects of climate change on singular yet endangered aquatic systems. Copyright © 2013 John Wiley & Sons, Ltd.     

Does stress transmission in forelands depend on structural style? Distinctive stress magnitudes during Sevier thin‐skinned and Laramide thick‐skinned layer‐parallel shortening in the Bighorn Basin (USA) revealed by stylolite and calcite twinning paleopiezometry

The Sheep Mountain‐Little Sheep Mountain Anticlines, Bighorn Basin (USA) formed as basement‐cored Laramide structures in the formerly undeformed foreland of the thin‐skinned Sevier orogen. We take advantage of the well‐constrained microstructural network there to reconstruct differential stress magnitudes that prevailed during both Sevier and Laramide layer‐parallel shortening (LPS), before the onset of large‐scale folding. Differential stress magnitudes determined from tectonic stylolites are compared and combined to previous stress estimates from calcite twinning paleopiezometry in the same formations. During stress loading related to LPS, differential stress magnitudes transmitted from the distant Sevier thin‐skinned orogen into the sedimentary cover of the Bighorn basin (11–43 MPa) are higher than the differential stress magnitudes accompanying the early stage of LPS related to the thick‐skinned Laramide deformation (2–19 MPa). This study illustrates that the tectonic style of an orogen affects the transmission of early orogenic stress into the stable continental interior.     

Intra-interstadial environmental changes in Last Glacial loess revealed by molluscan assemblages from the Upper Palaeolithic site of Amiens-Renancourt 1 (Somme,France)

The Amiens-Renancourt 1 site recently yielded one of the most important Upper Palaeolithic human occupations of northern France by the number of flint artefacts and especially by the presence of Venus figurines. All the material comes from a single archaeological layer located in a tundra gley bracketed by loess units. A multi-proxy study combining a detailed stratigraphy, luminescence and radiocarbon datings and high-resolution (5 cm per sample) grain size and molluscan analyses was therefore carried out to reconstruct and date the associated environmental changes and to determine the exact context of the human occupation. The chronological frame thus established supports the correlations of the archaeology-bearing tundra gley and of an underlying arctic brown soil with Greenland interstadials GI-4 and GI-3. Composition changes in the molluscan population enabled the identification of transitional and optimum phases and sub-phases within these two pedogenetic horizons. A conceptual correlation model linking molluscan phases with millennial-scale variations of Greenland ice-core and Sieben Hengste speleothem climate records is proposed. The Human occupation appears contemporaneous to the end of the stadial–interstadial transition of GI-3. Synchronous in Amiens-Renancourt 1 and Nussloch, subsequent micro-gleys may also result from a regional/global forcing. Such a level of detail is unprecedented in a loess sequence.     

Floods and livelihoods: The impact of changing water resources on wetland agro-ecological production systems in the Tana River Delta,Kenya

Wetlands are highly dynamic and productive systems that have been under increased pressure from changes in land use and water management strategies. In Eastern Africa, wetlands provide resources at multiple spatial and temporal levels through farming, fishing, livestock ownership and a host of other ecosystem services that sustain the local economy and individual livelihoods. As part of a broader effort to describe future development scenarios for East African coastal wetlands, this qualitative study focuses on understanding the processes by which river water depletion has affected local food production systems in Kenya's Tana River Delta over the past 50 years, and how this situation has impacted residents’ livelihoods and well-being. Interviews performed in six villages among various ethnic groups, geographical locations and resource profiles indicated that the agro-ecological production systems formerly in place were adapted to the river's dynamic flooding patterns. As these flooding patterns changed, the local population diversified and abandoned or adopted various farming, fishing and livestock-rearing techniques. Despite these efforts, the decrease in water availability affected each subcomponent of the production systems under study, which led to their collapse in the 1990s. Water depletion negatively impacted local human well-being through the loss of food security. The current study provides a detailed account of the dynamics of agro-ecological production systems facing the effects of river water depletion in a wetland-associated environment in Sub-Saharan Africa.     

Using radon-222 to study coastal groundwater/surface-water interaction in the Crau coastal aquifer (southeastern France)

Radon has been used to determine groundwater velocity and groundwater discharge into wetlands at the southern downstream boundary of the Crau aquifer, southeastern France. This aquifer constitutes an important high-quality freshwater resource exploited for agriculture, industry and human consumption. An increase in salinity occurs close to the sea, highlighting the need to investigate the water balance and groundwater behavior. Darcy velocity was estimated using radon activities in well waters according to the Hamada “single-well method” (involving comparison with radon in groundwater in the aquifer itself). Measurements done at three depths (7, 15 and 21 m) provided velocity ranging from a few mm/day to more than 20 cm/day, with highest velocities observed at the 15-m depth. Resulting hydraulic conductivities agree with the known geology. Waters showing high radon activity and high salinity were found near the presumed shoreline at 3,000 years BP, highlighting the presence of ancient saltwater. Radon activity has also been measured in canals, rivers and ponds, to trace groundwater discharges and evaluate water balance. A model of the radon spatial evolution explains the observed radon activities. Groundwater discharge to surface water is low in pond waters (4 % of total inputs) but significant in canals (55 l/m²/day).     

A helping hand: artificial nest site provisioning increases breeding success of a tropical seabird

Common white terns Gygis alba lay a single egg balanced on rocks or branches and consequently are at risk of low nesting success. A novel technique of hollowing out coconut husks and providing artificial nest sites was developed on Cousine Island, Seychelles. Our study aimed to critically assess whether common white tern nesting success differed between artificial and natural nest sites. For natural nest sites, nesting success and the stage of nest failure were also compared between seasons, nest heights, and tree species. Finally, we compared results from our study to those of a study conducted 10 years ago on the same island. Nesting success differed significantly between artificial nests and natural nests, with the success of artificial nests nearly double that of natural nests. Hatching success was similar for artificial and natural nests (65% and 52% respectively), suggesting coconut husks do not reduce egg losses, but rather provide secure perches for young chicks. Most natural nest failures occurred during the egg phase (70%), followed by the youngest chick phase (21%). Of the eggs that hatched in natural nests, 61% fledged successfully. Tree species and season significantly influenced nesting success for natural nests and nest height varied significantly between tree species. Higher nesting success was observed during the mixed seasonal period (50%) followed by the cooler, windier and drier South-East Monsoon season (33%). The hotter and more humid North-West Monsoon period had the lowest nesting success (20%). Comparisons of nesting success at natural and artificial nest sites with the earlier study did not differ significantly, despite a smaller population of common white terns being present on the island at that stage. Our results support the use of artificial nest sites to improve nesting success for this species and serve as a model for similar species currently under threat.