Cycles, Atmosphere, Climates

Résumé : Silicate weathering of basaltic rocks constitutes a non-negligible sink of atmospheric CO2 but the role it plays in the regulation of past and future global climate is still matter of debate. In this study, silicate weathering rates for various sub-basins of the Ethiopian Traps, emplaced 30 million years ago, and the corresponding atmospheric CO2 consumption rates are evaluated. For this, major and trace elements were measured in the dissolved phases and in the sedimentary particles carried and deposited by the main rivers flowing through this steep region. Lithium isotopes and major elements were also measured in the extracted clay fractions in order to infer complementary information on weathering processes in this region. Clay δ7Li values correlate positively with Mg/Ti ratios, and are best explained by varying ratios of leaching versus clay formation rate.
Although located in a region annually submitted to monsoon, average silicate weathering rate (16.1 tons/km2/year) and CO2 consumption rate (0.65 × 1012 mol/year) are estimated to be low when compared to other basaltic regions such as the Deccan Traps, and volcanically active islands of the tropical zone. This is surprising since the concentrations of Total Dissolved Solids of the Ethiopian rivers are among the highest ones. With a 2D rainfall model that takes into account the detailed topography of the region, annual occurrence of the Monsoon, and monitoring station data, we show that runoff intensity is a key parameter that explains this difference. We determine that, at present, the weathering of the Ethiopian Traps plays a negligible role in the carbon cycle. However, simple calculations, which integrate recent knowledge on African climate variations and on weathering controls, illustrate that during the African Humid Period (14–8 kyr), a significant increase of Monsoon precipitation may have resulted in much higher weathering rates and related CO2 consumption (0.91–1.5 × 1012 mol/year). This study therefore evidences the potential importance of this region in the past, and the need to quantify more precisely the variations of the monsoon intensity and its impact on tropical watersheds for reconstructing past CO2 levels.

Résumé : The application of lead isotope-based provenance analysis in Southeast Asia over the last decade has strongly suggested a central role was played by the Lao PDR in regional copper production exchange networks for approximately 1500 years. The Vilabouly Complex, in central Lao’s Savannakhet Province, has revealed major copper mining and smelting sites dated to the regional Iron Age (c. 400 BC – AD 500) and possibly Bronze Age (c.1000 – 400 BC). Metallurgical practices at the Vilabouly Complex, and indeed for all of the Lao PDR, are unknown, and the propose of this paper is to provide a comprehensive analytical study of the Vilabouly Complex metal assemblage, including 60 copper-base artefacts of multiple typologies. Cut samples of these were subjected to morpho-stylistic, metallographic (OM), elemental (XRF, SEM-EDS) and lead isotope analyses (MC-ICP-MS) in order to reconstruct the range of forms, metalworking materials, techniques (alloying, casting and post-casting treatments) used at the Vilabouly Complex. The results revealed an assemblage composed of copper, bronze and leaded bronze alloys, with a majority consistent with the lead isotopic signature for the Vilabouly Complex copper. The consistent geochemical and technological signature of the majority of artefacts strongly corroborates the extensive onsite production evidence, and fits with the burgeoning regional copper-base metals database for copper metal demand being sated in large part by Lao PDR supply.

Résumé : Rationale
High‐precision determination of magnesium (Mg) isotopes can now be routinely achieved by multi‐collector inductively coupled plasma mass spectrometry (MC‐ICP‐MS). The analytical sensitivity and instrumental mass discrimination behavior of this method are, however, sensitive to the types of sample and skimmer cones used in these measurements, so it is important that these parameters should be investigated.
Methods
Using the sample‐standard‐bracketing method in the wet‐plasma mode, four available combinations of sample and skimmer cones [Jet sample cone + H skimmer cone (Jet + H), standard sample cone + H skimmer cone (Standard + H), standard sample cone + X skimmer cone (Standard + X), and Jet sample cone + X skimmer cone (Jet + X)] were systematically investigated for peak shape, sensitivity, mass discrimination, accuracy, and precision in Mg‐isotopic ratio determination using a Neptune plus MC‐ICP mass spectrometer.
Results
The results showed that different cone combinations do not affect peak shapes but would significantly change the sensitivities for Mg‐isotopic determinations. Compared with using the Standard + H, the sensitivities of Mg‐isotopic determinations were enhanced by approximately a factor of 1.3, 1.4, and 1.9 by using the Standard + X, the Jet + H, and the Jet + X combinations, with the most stable mass discrimination behaviors obtained by the Jet + H. The instrumental mass fractionation slope for any combination of a modified cone geometry (i.e. Standard + X, Jet + X, and Jet + H) is 0.500, while it is 0.510 for the Standard + H. In addition, the mass discrimination behavior is related to Mg concentrations once the combination is set, indicating the necessity of concentration match during Mg‐isotopic determination.
Conclusions
The precision and accuracy of the Jet + H combination are better than those of the other combinations, and this is further supported by the validation of the Mg‐isotope data for four international reference materials: Cambridge‐1, NASS‐6, AGV‐2, and BHVO‐2. As the Jet + H combination also provides a high signal, this combination gives the most robust strategy for the highly precise and accurate determination of Mg isotopes.

Résumé : The levels and speciation of dissolved, particulate and gaseous Se have been measured in five thermokarst ponds in a sporadic and discontinuous permafrost region of northern Que´bec (Canada) during summer oxygen stratification. Evolution of Se concentrations with depth was investigated in sediment cores collected in three different ponds. The potential for inorganic Se transformation in natural pond waters was investigated by experimental incubations of isotopic species-specific tracers of selenite and selenate. Experimental and monitoring observation revealed that high dissolved carbon concentration, suspended particle matter concentration, heterotrophic activity and periphytic biofilms have a significant role in the formation of gaseous selenium species. In sediment, Se is mainly associated with organic matter in the concentration range 0.14–1.6 mg kg-1. Despite low outgassing rates of volatile Se toward the atmosphere (1–97 ng Se m-2 day-1), the large surface occupied by ponds in northern Canada may lead to important exchange rates (ca. 1 ton year-1) at the global scale. Detailed measurements of Se speciation, including volatile compounds, and its reactivity toward heterotrophic activity in selected thaw ponds from the Canadian Subarctic provides new insight to better constrain the biogeochemical pathways leading to Se removal from the water column via atmospheric gas exchange and sediment accumulation.

Résumé : Marine sedimentary archives are well dated and often span several glacial cycles ; cosmogenic 10Be concentrations in their detrital quartz grains could thus offer the opportunity to reconstruct a wealth of past denudation rates. However, these archives often comprise sediments much finer (<250 µm) than typically analyzed in 10Be studies, and few studies have measured 10Be concentrations in quartz grains smaller than 100 µm or assessed the impacts of mixing, grain size, and interannual variability on the 10Be concentrations of such fine-grained sediments. Here, we analyzed the in situ cosmogenic 10Be concentrations of quartz grains in the 50–100 and 100–250 µm size fractions of sediments from the Var basin (southern French Alps) to test the reliability of denudation rates derived from 10Be analyses of fine sands. The Var basin has a short transfer zone and highly variable morphology, climate, and geology, and we test the impact of these parameters on the observed 10Be concentrations. Both analyzed size fractions returned similar 10Be concentrations in downstream locations, notably at the Var’s outlet, where concentrations ranged from (4.02±0.78)×104 to (4.40±0.64)×104 atoms g−1 of quartz. By comparing expected and observed 10Be concentrations at three major river junctions, we interpret that sediment mixing is efficient throughout the Var basin. We resampled four key locations 1 year later, and despite variable climatic parameters during that period, interannual 10Be concentrations were in agreement within uncertainties, except for one upper subbasin. The 10Be-derived denudation rates of Var subbasins range from 0.10±0.01 to 0.57±0.09 mm yr−1, and spatial variations are primarily controlled by the average subbasin slope. The integrated denudation rate of the entire Var basin is 0.24±0.04 mm yr−1, in agreement with other methods. Our results demonstrate that fine-grained sediments (50–250 µm) may return accurate denudation rates and are thus potentially suitable targets for future 10Be applications, such as studies of paleo-denudation rates using offshore sediments.