Development of a sample preparation procedure for Sr isotope analysis of Portland cements

The 87Sr/86Sr isotope ratio can, in principle, be used for provenancing of cement. However, while commercial cements consist of multiple components, no detailed investigation into their individual 87Sr/86Sr isotope ratios or their influence on the integral 87Sr/86Sr isotope ratio of the resulting cement was conducted previously. Therefore, the present study aimed at determining and comparing the conventional 87Sr/86Sr isotope ratios of a diverse set of Portland cements and their corresponding Portland clinkers, the major component of these cements. Two approaches to remove the additives from the cements, i.e. to measure the conventional 87Sr/86Sr isotopic fingerprint of the clinker only, were tested, namely, treatment with a potassium hydroxide/sucrose solution and sieving on a 11-µm sieve. Dissolution in concentrated hydrochloric acid/nitric acid and in diluted nitric acid was employed to determine the 87Sr/86Sr isotope ratios of the cements and the individual clinkers. The aim was to find the most appropriate sample preparation procedure for cement provenancing, and the selection was realised by comparing the 87Sr/86Sr isotope ratios of differently treated cements with those of the corresponding clinkers. None of the methods to separate the clinkers from the cements proved to be satisfactory. However, it was found that the 87Sr/86Sr isotope ratios of clinker and cement generally corresponded, meaning that the latter can be used as a proxy for the clinker 87Sr/86Sr isotope ratio. Finally, the concentrated hydrochloric acid/nitric acid dissolution method was found to be the most suitable sample preparation method for the cements; it is thus recommended for 87Sr/86Sr isotope analyses for cement provenancing. Graphical abstract

Stable Cu Isotope Ratios Show Changes in Cu Uptake and Transport Mechanisms in Vitis vinifera Due to High Cu Exposure

Even though copper (Cu) is an essential plant nutrient, it can become toxic under certain conditions. Toxic effects do not only depend on soil Cu content, but also on environmental and physiological factors, that are not well understood. In this study, the mechanisms of Cu bioavailability and the homeostasis of Vitis vinifera L. cv. Tannat were investigated under controlled conditions, using stable Cu isotope analysis. We measured Cu concentrations and δ65Cu isotope ratios in soils, soil solutions, roots, and leaves of grapevine plants grown on six different vineyard soils, in a 16-week greenhouse experiment. The mobility of Cu in the soil solutions was controlled by the solubility of soil organic matter. No direct relationship between Cu contents in soils or soil solutions and Cu contents in roots could be established, indicating a partly homeostatic control of Cu uptake. Isotope fractionation between soil solutions and roots shifted from light to heavy with increasing Cu exposure, in line with a shift from active to passive uptake. Passive uptake appears to exceed active uptake for soil solution concentrations higher than 270 μg L–1. Isotope fractionation between roots and leaves was increasingly negative with increasing root Cu contents, even though the leaf Cu contents did not differ significantly. Our results suggest that Cu isotope analysis is a sensitive tool to monitor differences in Cu uptake and translocation pathways even before differences in tissue contents can be observed.

Isotopic Characterization of Gaseous Mercury and Particulate Water-Soluble Organic Carbon Emitted from Open Grass Field Burning in Aso, Japan

Biomass burning is one of the major emitters of airborne particulate matter (PM) and gaseous mercury. In order to apply the isotopic fingerprinting method to process identification and source apportionment studies, isotopic characterizations of targeted substances at emission are indispensable. Here, we report the stable isotopic composition of total gaseous mercury (TGM) and the stable and radiocarbon isotopic composition of low-volatile water-soluble nitrogen (LV-WSN) and organic carbon (LV-WSOC) in PM emitted from open grass field burning in the Aso region of Japan. The measurement results showed that TGM concentrations in the air increased during the open field burning events, indicating the presence of TGM emissions. The results of LV-WSN analysis showed very low concentrations; therefore, the stable nitrogen isotope ratios could not be measured. The stable mercury isotope ratios exhibited lighter composition than those observed during non-biomass-burning days. The analysis of LV-WSOC revealed heavy stable carbon isotope ratios (average ± SD, −18 ± 2‰), suggesting a substantial contribution from C4 plant carbon. The 14C analysis showed that more than 98% of the LV-WSOC was modern carbon, indicating the contribution of plant carbon to PM emitted from biomass burning. The findings here provide reference isotope compositions of TGM and particulate LV-WSOC from biomass burning in this region.

Investigating influences on the Pb pseudo-isochron using three-dimensional mantle convection models with a continental reservoir

For mid-ocean ridge basalts (MORBs) and ocean island basalts (OIBs), measurements of Pb isotope ratios show broad linear correlations with a certain degree of scatter. In 207Pb/204Pb - 206Pb/204Pb space, the best fit line defines a pseudo-isochron age (τPb) of ~1.9 Gyr.Previous modelling suggests a relative change in the behaviours of U and Pb between 2.25-2.5 Ga, resulting in net recycling of HIMU (high U/Pb) material in the latter part of Earth's history, to explain the observed τPb. However, simulations in which fractionation is controlled by a single set of partition coefficients throughout the model runs fail to reproduce τPb and the observed scatter in Pb isotope ratios. We build on these models with 3D mantle convection simulations including parameterisations for melting, U recycling from the continents and preferential removal of Pb from subducted oceanic crust.We find that both U recycling after the great oxygenation event (GOE) and Pb extraction after the onset of plate tectonics, are required in order to fit the observed gradient and scatter of both the 207Pb/204Pb - 206Pb/204Pb and 208Pb/204Pb - 206Pb/204Pb arrays. Unlike much previous work, our model does not require accumulations of subducted oceanic crust to persist at the CMB for long periods of time in order to match geochemical observations.

Untersuchung des Einflusses von Biomasseverbrennung auf die Atmosphäre mit Hilfe der Verhältnisse stabiler Kohlenstoffisotope in VOC

<p>Im August/September 2018 fand die Messkampagne CAFE-Africa (Chemistry of the Atmosphere – Field Experiment in Africa) mit dem Forschungsflugzeug HALO statt. Stützpunkt des Flugzeugs war die kapverdische Insel Sal. Basierend auf CAMS-Vorhersagen wurden von dort aus Messflüge in ausgewählte Gebiete über dem Atlantik und über den Westen Afrikas durchgeführt. Ziel der Kampagne war die Untersuchung des Einflusses der Emissionen von Biomasseverbrennung auf die regionale und globale Atmosphäre mit einem Fokus auf die Biomasseverbrennung in Afrika. Mit dem Luftprobensammler MIRAH (Measurements of Isotope Ratios in the Atmosphere on HALO) wurden Gesamtluftproben gesammelt, die anschließend im Labor auf die Verhältnisse stabiler Kohlenstoffisotope in ausgewählten flüchtigen organischen Verbindungen (VOC) sowie auf deren Mischungsverhältnisse untersucht wurden. Die Isotopenverhältnisse bieten zusammen mit CAMS Re-Analysen, Rückwärtstrajektorien, Satellitendaten und weiteren Stützmessungen die Möglichkeit, die Herkunft, Transportzeiten und die Umsetzung von VOC zu bestimmen. Wir zeigen als Fallstudie die Ergebnisse des 10. Messfluges, bei dem über dem Atlantik nordwestlich der Kapverden zwei deutlich unterscheidbare Luftmassen aufeinandertrafen. Während eine Luftmasse von Emissionen aus dem nördlichen Afrika geprägt war und mit dem westafrikanischen Monsoon-System auf den Atlantik transportiert wurde, konnte die andere Luftmasse eindeutig Biomasseverbrennung im Norden des amerikanischen Kontinents zugeordnet werden. Der Vergleich der genannten Datensätze gibt einen guten Überblick über den globalen Transport von Spurenstoffen, auch wenn nicht alle Details konsistent zu sein scheinen.</p>