A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Genesis of Kanggur Gold Deposit in Eastern Tianshan Orogenic Belt, NW China: Fluid Inclusion and Oxygen and Hydrogen Isotope Constraints

Abstract. Primary fluid inclusions in quartz and carbonates from the Kanggur gold deposit are dominated by aqueous inclusions, with subsidiary CO₂-H₂O inclusions that have a constant range in CO₂ content (10–20 vol %). Microthermometric results indicate that total homogenization temperatures have a wide but similar range for both aqueous inclusions (120 to 310C) and CO₂-H₂O inclusions (140 to 340C). Estimates of fluid salinity for CO₂-H₂O inclusions are quite restricted (5.9∼10.3 equiv. wt% NaCl), whereas aqueous inclusions show much wider salinity ranging from 2.2 to 15.6 equivalent wt %NaCl.
The 6D values of fluid inclusions in carbonates vary from -45 to -61 %, in well accord with the published δD values of fluid inclusions in quartz (-46 to -66 %). Most of the δ¹⁸O and δD values of the ore-forming fluids can be achieved by exchanged meteoric water after isotopic equilibration with wall rock by fluid/rock interaction at a low water/rock ratio. However, the exchanged meteoric water alone cannot explain the full range of δ¹⁸O and δD values, magmatic and/or meta-morphic water should also be involved. The wide salinity in aqueous inclusions may also result from mixing of meteoric water and magmatic and/or metamorphic water.     

Late-glacial and Holocene vegetation and climatic history of the Cass Basin, central South Island, New Zealand

Lithology, pollen, macrofossils, and stable carbon isotopes from an intermontane basin bog site in southern New Zealand provide a detailed late-glacial and early Holocene vegetation and climate record. Glacial retreat occurred before 17,000 cal yr B.P., and tundra-like grassland–shrubland occupied the basin shortly after. Between 16,500 and 14,600 cal yr B.P., a minor regional expansion of forest patches occurred in response to warming, but the basin remained in shrubland. Forest retreated between 14,600 and 13,600 cal yr B.P., at about the time of the Antarctic Cold Reversal. At 13,600 cal yr B.P., a steady progression from shrubland to tall podocarp forest began as the climate ameliorated. Tall, temperate podocarp trees replaced stress-tolerant shrubs and trees between 12,800 and 11,300 cal yr B.P., indicating sustained warming during the Younger Dryas Chronozone (YDC). Stable isotopes suggest increasing atmospheric humidity from 11,800 to 9300 cal yr B.P. Mild (annual temperatures at least 1°C higher than present), and moist conditions prevailed from 11,000 to 10,350 cal yr B.P. Cooler, more variable conditions followed, and podocarp forest was completely replaced by montane Nothofagus forest at around 7500 cal yr B.P. with the onset of the modern climate regime. The Cass Basin late-glacial climate record closely matches the Antarctic ice core records and is in approximate antiphase with the North Atlantic.     

Time-Frequency Variations of Plio-Pleistocene Foraminiferal Isotopes： A Case Study from Southern South China Sea

The continuous wavelet transform (CWT) analysis reveals the instantaneous variability of the foraminiferal δ18O and δ13C of Site 1143 for the past 5 Ma at the eccentricity, obliquity and precession bands. The cross CWT analysis further demonstrates nonstationary phases of the benthic -δ18O relative to ETP at the three primary Milankovitch bands in the last 5 Ma. The instantaneous phases between benthic -δ18O and δ13C at the precession band display a prominent 128 ka period, probably the cyclicity of the nonstationary climate close to the eccentricity. To explain these nonstationary phases, it is desirable to introduce a nonlinear response model to the global climate system, in which the output has a prominent cycle around 100 ka to match the 128 ka cycle of the instantaneous phase of the δ13C and -δ18O on the precession band.     

L'archivage des activités humaines par les neiges et glaces polaires : le cas du plomb

The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).     

Particularités de la contamination crustale des phonolites : exemple du Velay oriental (Massif central)

Sr and Nd isotopic compositions of one trachyte, eight phonolites and five basalts have been measured. The isotopic characteristics of the trachyte can be explained by a combined assimilation–fractional crystallization process within an upper crustal magmatic chamber. Some phonolites display isotopic signatures identical to basalts, suggesting that they have been protected against any crustal assimilation during their formation. Some others have low Sr contents, whereas they are enriched in radiogenic Sr (0.70451<⁸⁷Sr/⁸⁶Sr_i<0.71192), and display basaltic ¹⁴³Nd/¹⁴⁴Nd ratios. Both observations could be explained by very strong alkali feldspar fractionation and by subsequent very low assimilation of surrounding rocks (between 0.3 and 4%) during intrusion. To cite this article: J.-M. Dautria et al., C. R. Geoscience 336 (2004).     

Holocene hydrographical changes of the eastern Laptev Sea (Siberian Arctic) recorded in δO profiles of bivalve shells

Oxygen isotope profiles along the growth axis of fossil bivalve shells of Macoma calcarea were established to reconstruct hydrographical changes in the eastern Laptev Sea since 8400 cal yr B.P.. The variability of the oxygen isotopes (δ¹⁸O) in the individual records is mainly attributed to variations in the salinity of bottom waters in the Laptev Sea with a modern ratio of 0.50‰/salinity. The high-resolution δ¹⁸O profiles exhibit distinct and annual cycles from which the seasonal and annual salinity variations at the investigated site can be reconstructed. Based on the modern analogue approach oxygen isotope profiles of radiocarbon-dated bivalve shells from a sediment core located northeast of the Lena Delta provide seasonal and subdecadal insights into past hydrological conditions and their relation to the Holocene transgressional history of the Laptev Sea shelf. Under the assumption that the modern relationship between δ¹⁸O_w and salinity has been constant throughout the time, the δ¹⁸O of an 8400-cal-yr-old bivalves would suggest that bottom-water salinity was reduced and the temperature was slightly warmer, both suggesting a stronger mixture of riverine water to the bottom water. Reconstruction of the inundation history of the Laptev Sea shelf indicates local sea level ∼27 m below present at this time and a closer proximity of the site to the coastline and the Lena River mouth. Due to continuing sea level rise and a southward retreat of the river mouth, bottom-water salinity increased at 7200 cal yr B.P. along with an increase in seasonal variability. Conditions comparable to the modern hydrography were achieved by 3800 cal yr B.P.     

Variability of the Intertropical Convergence Zone recorded in coral isotopic records from the central Indian Ocean (Chagos Archipelago)

We have analyzed the stable oxygen isotopic composition of two Porites corals from the Chagos Archipelago, which is situated in the geographical center of the Indian Ocean. Coral δ¹⁸O at this site reliably records temporal variations in precipitation associated with the Intertropical Convergence Zone (ITCZ). Precipitation maxima occur in boreal winter, when the ITCZ forms a narrow band across the Indian Ocean. The Chagos then lies within the center of the ITCZ, and rainfall is strongly depleted in δ¹⁸O. A 120-yr coral isotopic record indicates an alternation of wet and dry intervals lasting 15 to 20 yr. The most recent 2 decades are dominated by interannual variability, which is tightly coupled to the El Niño-Southern Oscillation (ENSO). This is unprecedented in the 120 yr of coral record. As the ITCZ is governed by atmospheric dynamics, this provides evidence of a major change in the coupled ENSO-monsoon system.     

Vegetation dynamics during the late Pleistocene in the Barreirinhas region, Maranhão State, northeastern Brazil, based on carbon isotopes in soil organic matter

The study place is in the Barreirinhas region, Maranhão State, northeastern Brazil. A vegetation transect of 78 km was studied among four vegetation types: Restinga (coastal vegetation), Cerrado (woody savanna), Cerradão (dense woody savanna), and Forest, as well as three forested sites around Lagoa do Caçó, located approximately 10 km of the transect. Soil profiles in this transect were sampled for δ¹³C analysis, as well as buried charcoal fragments were used for ¹⁴C dating. The data interpretation indicated that approximately between 15,000 and ∼9000 ¹⁴C yr B.P., arboreal vegetation prevailed in the whole transect, probably due to the presence of a humid climate. Approximately between ∼9000 and 4000-3000 ¹⁴C yr B.P., there was the expansion of the savanna, probably related to the presence of drier climate. From ∼4000-3000 ¹⁴C yr B.P. to the present, the results indicated an increase in the arboreal density in the area, due to the return to a more humid and probably similar climate to the present. The presence of buried charcoal fragments in several soil depths suggested the occurrence of palaeofires during the Holocene. The vegetation dynamic inferred in this study for northeastern Brazil is in agreement with the results obtained in areas of Amazon region, based on pollen analysis of lake sediments and carbon isotope analysis of soil organic matter (SOM), implying than similar climatic conditions have affected these areas during the late Pleistocene until the present.     

Hydrothermal alteration and tectonic evolution of an intermediate- to fast-spreading back-arc oceanic crust: Late Ordovician Solund-Stavfjord ophiolite, western Norway

Abstract The Solund‐Stavfjord ophiolite complex (SSOC) in western Norway represents a remnant of the Late Ordovician oceanic lithosphere, which developed in an intermediate‐ to fast‐spreading Caledonian back‐arc basin. The internal architecture and magmatic features of its crustal component suggest that the SSOC has a complex, multistage sea floor spreading history in a supra‐subduction zone environment. The youngest crustal section associated with the propagating rift tectonics consists of a relatively complete ophiolite pseudostratigraphy, including basaltic volcanic rocks, a transition zone between the sheeted dyke complex and the extrusive sequence, sheeted dykes, and high‐level isotropic gabbros. Large‐scale variations in major and trace element distributions indicate significant remobilization far beyond that which would result from magmatic processes, as a result of the hydrothermal alteration of crustal rocks. Whereas K₂O is strongly enriched in volcanic rocks of the extrusive sequence, Cu and Zn show the largest enrichment in the dyke complex near the dyke–volcanic transition zone or within this transition zone. The δ¹⁸O values of the whole‐rock samples show a general depletion structurally downwards in the ophiolite, with the largest and smallest variations observed in volcanic rocks and the transition zone, respectively. δ¹⁸O values of epidote–quartz mineral pairs indicate 260–290°C for volcanic rocks, 420°C for the transition zone, 280–345°C for the sheeted dyke complex and 290–475°C for the gabbros. The ⁸⁷Sr/⁸⁶Sr isotope ratios show the widest range and highest values in the extrusive rocks (0.70316–0.70495), and generally the lowest values and the narrowest range in the sheeted dyke complex (0.70338–0.70377). The minimum water/rock ratios calculated show the largest variations in volcanic rocks and gabbros (approximately 0–14), and generally the lowest values and range in the sheeted dyke complex (approximately 1–3). The δD values of epidote (?1 to ?12‰), together with the δ¹⁸O calculated for Ordovician seawater, are similar to those of present‐day seawater. Volcanic rocks experienced both cold and warm water circulation, resulting in the observed K₂O‐enrichment and the largest scatter in the δ¹⁸O values. As a result of metal leaching in the hot reaction zone above a magma chamber, Zn is strongly depleted in the gabbros but enriched in the sheeted dyke complex because of precipitation from upwelling of discharged hydrothermal fluids. The present study demonstrates that the near intact effect of ocean floor hydrothermal activity is preserved in the upper part of the SSOC crust, despite the influence of regional lower greenschist facies metamorphism.