Search results for "Isotope fractionation"

2012

Abstract. The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g). However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate – which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl…

Coupled silicon-oxygen isotope fractionation traces Archaean silicification

2011

International audience; Silica alteration zones and cherts are a conspicuous feature of Archaean greenstone belts worldwide and provide evidence of extensive mobilisation of silica in the marine environment of the early Earth. In order to understand the process(es) of silicification we measured the silicon and oxygen isotope composition of sections of variably silicified basalts and overlying bedded cherts from the Theespruit, Hooggenoeg and Kromberg Formations of the Barberton Greenstone Belt, South Africa.The δ30Si and δ18O values of bulk rock increase with increasing amount of silicification from unsilicified basalts (-0.64‰ 30Si 18O 30Si and δ18O values as high as + 0.81‰ and + 15.6‰, r…

Iron isotope signature of magnetofossils and oceanic biogeochemical changes through the Middle Eocene Climatic Optimum.

2021

21 pages; International audience; Magnetotactic bacteria (MTB) intracellularly precipitate magnetite (Fe3O4) crystals that can be preserved in the geological record. When MTB die, the so-called magnetofossils constitute valuable proxies for paleoenvironmental reconstructions and are suspected to represent some of the oldest traces of biomineralization on Earth. Yet, the biogenicity of putative magnetofossils found in ancient terrestrial and extra-terrestrial samples is still largely debated and their significance for past climate still holds uncertainties. Here we studied a sedimentary sequence from the Indian Ocean (ODP Hole 711A) recording the Middle Eocene Climatic Optimum (MECO) through…

Reconstruction of drip-water δ<sup>18</sup>O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave…

2013

Abstract. The geochemical signature of many speleothems used for reconstruction of past continental climates is affected by kinetic isotope fractionation. This limits quantitative paleoclimate reconstruction and, in cases where the kinetic fractionation varies with time, also affects relative paleoclimate interpretations. In carbonate archive research, clumped isotope thermometry is typically used as proxy for absolute temperatures. In the case of speleothems, however, clumped isotopes provide a sensitive indicator for disequilibrium effects. The extent of kinetic fractionation co-varies in Δ47 and δ18O so that it can be used to account for disequilibrium in δ18O and to extract the past dri…

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

2011

Abstract Understanding the relationship between stable isotope signals recorded in speleothems (δ 13 C and δ 18 O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO 2 . The water entering the cave flows as a thin film towards the drip site. CO 2 degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scal…

Modelling the δ18O value of cave drip water and speleothem calcite

2010

Abstract Stable isotope signals recorded in speleothems have provided important insights about past climate variability in recent years. Quantitative reconstruction of mean annual temperature and the amount of precipitation, however, remains difficult because the stable isotope signals are influenced by various processes. Here we present a drip water model, which shows how these climate parameters affect the oxygen isotope signal of cave drip water. In the model the dependence of the δ 18 O value of drip water on mean annual temperature is established by correlation to the amount of winter precipitation and winter temperature. Application of the model to two caves in western Germany reveals…

Lithium isotopes and partition coefficients in inorganic carbonates: Proxy calibration for weathering reconstruction

2021

We report Li measurements from cave-analogue carbonate-precipitation experiments in order to: i) assess the expected isotope fractionation factors applicable to speleothem growth, and ii) contribute to the wider understanding of lithium incorporation in carbonates. The experimental setup closely mimics natural processes (e.g. precipitation driven by CO2 degassing, low ionic strength solution, thin solution film) but within a laboratory setting that allows for controlled growth conditions (temperature, pCO2, drip rate, carbonate saturation index and the composition of the initial solution). For the main batch of calcite growth experiments our average 1000lnαcalcite-solution is -8.5&plu…

Constraining speleothem oxygen isotope disequilibrium driven by rapid CO2 degassing and calcite precipitation: Insights from monitoring and modeling

2020

Abstract Oxygen isotopes are the most commonly applied speleothem proxy for reconstructing Quaternary changes in precipitation and/or temperature. These interpretations are either limited to qualitative wetting and drying trends or rely on theoretical, experimental and/or empirical equilibrium isotope fractionation factors for more quantitative constraints. These various fractionation factors have similar temperature sensitivities, but their absolute values differ, and cave calcite does not appear to generally precipitate in isotopic equilibrium with its drip water. Rapid CO2 degassing paired with calcite precipitation, both occurring under disequilibrium conditions, are a set of mechanisms…

The lithium isotope response to the variable weathering of soils in Iceland

2021

Abstract This study has analysed Li isotopes ratios from well-studied soil and pore water profiles from Iceland that have the same parent material but have experienced different degrees of chemical weathering. Thus, from least to most weathered, we have analysed vitrosols (V), gleyic andosols (GA), brown andosols (BA), Histosols (H) and Histic Andosols (HA). Although the most weathered H and HA soils have the highest content in clay-sized material, they have the least fractionated δ7Lipore water values. In contrast, the least weathered GA and BA pore waters are most fractionated for Li isotopes. Given that Li isotope ratios are fractionated by clay mineral formation, this appears counter-in…

Tracing anthropogenic thallium in soil using stable isotope compositions.

2014

Thallium stable isotope data are used in this study, for the first time, to apportion Tl contamination in soils. In the late 1970s, a cement plant near Lengerich, Germany, emitted cement kiln dust (CKD) with high Tl contents, due to cocombustion of Tl-enriched pyrite roasting waste. Locally contaminated soil profiles were obtained down to 1 m depth and the samples are in accord with a binary mixing relationship in a diagram of Tl isotope compositions (expressed as e(205)Tl, the deviation of the (205)Tl/(203)Tl ratio of a sample from the NIST SRM 997 Tl isotope standard in parts per 10(4)) versus 1/[Tl]. The inferred mixing endmembers are the geogenic background, as defined by isotopically l…