Cycles, Atmosphere, Climates

Résumé : We measured concentrations of Ne isotopes in quartz in a 27.6-m sandstone core from a low-erosion-rate site at 2183m elevation at Beacon Heights in the Antarctic Dry Valleys. Surface concentrations of cosmogenic 21Ne indicate a surface exposure age of at least 4.1 Ma and an erosion rate no higher than ca. 14 cm Myr−1 21Ne concentrations in the upper few centimeters of the core show evidence for secondary spallogenic neutron escape effects at the rock surface, which is predicted by first-principles models of cosmogenic-nuclide production but is
not commonly observed in natural examples. We used a model for 21Ne production by various mechanisms fit to the observations to distinguish cosmic-ray-produced 21Ne from nucleogenic 21Ne produced by decay of trace U and Th present in quartz, and also constrain rates of subsurface 21Ne production by cosmic-ray muons. Core samples have a quartz (U-Th)/Ne closure age, reflecting cooling below approximately 95 °C, near 160 Ma, which is consistent with existing apatite fission-track data and the 183 Ma emplacement of nearby Ferrar dolerite intrusions. Constraints on 21Ne production by muons derived from model fitting are consistent with a previously proposed value of 0.79 mb at 190 GeV for the cross-section for 21Ne production by fast muon interactions, but indicate that 21Ne production by negative muon capture is likely negligible.

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 : As one of the largest dust sources on the Earth's surface, dryland in Central Asia gives rise to thick eolian deposits over East Asia (e.g., the Chinese Loess Plateau, CLP) and significantly influences the regional hydrochemistry in the downwind drainage areas. However, the formation of thick eolian dust deposits requires not only climatic prerequisites for dust emission and transport but also climatic and topographic conditions favourable for deposition and accumulation. The scarcity of widespread eolian deposition around the CLP before 7-8 Ma hinders a full understanding of the processes and mechanisms of Central Asian aridification. The deposition of eolian dust also impacts the hydrogeochemistry of fluvial systems and the precipitation of authigenic phases in continental sedimentary systems could be an archive for studying eolian dust dynamics when pure eolian deposits are scarce. Here, we present the Ca-Mg-Sr concentrations and 87Sr/86Sr isotope compositions of bulk carbonates in a new fluvial sequence (12.7-4.8 Ma) of the Xining Basin. The Mg/Ca and Sr/Ca ratios of the carbonate describe a power law relationship with a power coefficient of ∼0.8, lower than the coefficient characteristic of prior calcite precipitation (PCP). An input of eolian dust with the dissolution of Mg-rich carbonate is likely responsible for the deviation from a pure PCP process. The bulk carbonates also show a general decrease of 87Sr/86Sr ratios from 12.7 to 4.8 Ma, with a transition around 8.6 Ma revealed by lower Sr/Mg ratios. The comparison of these proxies to a previously reported fluvial section (12.2-5.1 Ma) in the Linxia Basin, ∼200 km to the southeast, shows that the 87Sr/86Sr ratios of the bulk carbonates and water-soluble salts in the Linxia Basin are around 0.7098, which is 0.0018 lower than those in the Xining Basin before 8.6 Ma, but shows a significant rise between 8.6 and 7.0 Ma. The two basins share the same range of carbonate 87Sr/86Sr ratios when sediments are younger than 7 Ma. For the last 7 Myrs, the evolution of the 87Sr/86Sr ratios in bulk carbonates of fluvial sediments and Pliocene-Quaternary eolian deposits found in the Xining Basin are similar to those in typical eolian red clays/loess-palaeosol sequences on the CLP. These results suggest a transition of the hydrochemical regime at 8.6 Ma in the Linxia Basin from a catchment only influenced by the weathering of its bedrock to one significantly impacted by eolian dust input. In the Xining Basin, the carbonate elemental and 87Sr/86Sr ratios are consistent with a hydrochemistry more impacted by the presence of the eolian dust. There, the dust input occurred earlier, at ≥12.7 Ma, though it has strengthened since 8.6 Ma. The eolian dust impact on fluvial systems in the Xining Basin was much earlier than in the Linxia Basin and also preceded the initial accumulation of widespread eolian red clays on the CLP (7-8 Ma), suggesting a temporally propagating and spatially stepwise expansion of eolian dust delivery across the Asian inland during the late Cenozoic.