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Dietzel, Martin

Publications and source records attributed to Dietzel, Martin.

Comparative clumped isotope temperature relationships in freshwater carbonates

Lacustrine, riverine and spring carbonates represent archives of terrestrial climates and their geochemistry has been used to study palaeoenvironments. Clumped isotope thermometry is an emerging tool that has been applied to freshwater carbonates. Limited work has been done to evaluate comparative relationships between clumped isotopes and temperature in different types of modern freshwater carbonates. This study assembles an extensive calibration data set with 135 samples of modern freshwater carbonates from 96 sites and constrains the relationship between independent observations of water temperature and the clumped isotopic composition of carbonates (denoted by Δ 47 ), including new measurements, and recalculates published data in accordance with current community-defined standard values. For temperature reconstruction, the study reports a composite freshwater calibration and material-specific calibrations for biogenic carbonates (freshwater gastropods and bivalves), fine-grained carbonate (e.g. micrites), biologically mediated carbonates (microbialites and tufas) and travertines. Material-specific calibration trends show a convergence of slopes that are in agreement with recently published syntheses, but statistically significant differences in intercepts occur between some materials (e.g. some biogenics, fine-grained carbonates). These differences may arise due to unresolved seasonal biases, kinetic isotope effects and/or varying degrees of biological influence. The impact of different calibrations is shown through application to new data for glacial and deglacial age travertines from Austria and published data sets. While material-specific calibrations may yield more accurate results for biogenic and fine-grained carbonate samples, the use of material-specific and the composite freshwater calibrations generally produces values within 1.0–1.5°C of each other, and typically fall within calibration uncertainty given limitations of precision.

54 ENVIRONMENTAL SCIENCES↗

Continuous optical in-situ pH monitoring during early hydration of cementitious materials

A luminescent sensor technique for pH analyses has been tested in cementitious media. The optical sensors monitor in-situ pH every 5 s during early hydration reactions over a period of 100 h from initial fluid up to consolidated stage. The pH development was analysed in calcium aluminate, calcium sulfoaluminate and OPC/slag cements up to a pH level of 13.3 and directly correlated with the heat of hydration. Thus tracing the dissolution and formation processes of solid phases via pH sensor monitoring is possible. This measurement technique enables the recording of continuous and highly reproducible pH data sets from slurries, pastes, and hardening materials leading to new vistas for individual (trans)formation pathways of solids, hydration and consolidation reactions in high alkaline cementitious systems.

36 MATERIALS SCIENCE↗

Uptake of aqueous heavy metal ions (Co2+, Cu2+ and Zn2+) by calcium-aluminium-silicate-hydrate gels

Highlights: • C-A-S-H gels containing metal ions (Co{sup 2+}, Cu{sup 2+} or Zn{sup 2+}) were precipitated by a sol-gel technique. • Uptake mechanism and immobilization capacity of divalent metal ions by C-A-S-H are elucidated. • Up to ~55–60 mol% of Zn can be incorporated in defective tobermorite-type C-A-S-H. • Metal uptake by C-A-S-H is controlled mainly by isomorphous substitution for Ca ions. • Crystal-chemical features of C-A-S-H gels and implications for practical application are discussed. Calcium-aluminium-silicate-hydrate (C-A-S-H) gels containing heavy metal ions (Me: Co{sup 2+}, Cu{sup 2+} or Zn{sup 2+}) were precipitated at different Me/Si molar ratios to study the uptake mechanism and immobilization capacity. Aqueous solution chemistry and solid-phase characterization using XRD, FTIR, ESEM-EDX, TEM-HAADF and TG-DSC methods reveal threshold values for ion substitution of ~55–60 mol% for Zn, ~30–40 mol% for Co and ~25–30 mol% for Cu in defective tobermorite-type C-A-S-H with (Ca + Me)/(Si + Al) molar ratios from 0.86 to 1.04. At higher aqueous Me concentrations, Me (chloride) hydroxides start to co-precipitate. The uptake mechanism of Me ions by C-A-S-H is based on (i) isomorphous substitution of Me for Ca in the CaO layer, (ii) ion exchange in the interlayer, (iii) tetrahedral substitution (Zn) within the dreierketten chains and (iv) surface adsorption onto the C-A-S-H gel structure. Systematics in crystal-chemistry of Me-bearing C-A-S-H and implications for application and performance in natural and man-made settings are discussed.

36 MATERIALS SCIENCE↗

Deterioration mechanism of alkali-activated materials in sulfuric acid and the influence of Cu: A micro-to-nano structural, elemental and stable isotopic multi-proxy study

In this study, a multi-proxy approach combining {sup 29}Si, {sup 27}Al and {sup 1}H MAS-NMR, FEG-EPMA, XANES at the Cu K-edge and XRD analytics with hydrochemical tools such as ICP-OES analyses, oxygen-isotope signatures, and thermodynamic modelling was applied to K-silicate-activated metakaolin specimens - with and without CuSO{sub 4}·5H{sub 2}O addition - exposed to sulfuric acid at pH = 2 for 35 days. The results revealed a multistage deterioration mechanism governed by (i) acid diffusion, (ii) leaching of K-A-S-H, (iii) microstructural damage related to precipitation of expansive (K,Ca,Al)-sulfate-hydrate phases (iv) complete dissolution of the K-A-S-H framework, (v) and formation of silica gel in the outermost corroded regions. Copper ions were mainly located in layered spertiniite-chrysocolla-like phases in the as-cured materials. The results demonstrate an overall negative effect of Cu addition on chemical material durability, implying that the reported higher durability of Cu-doped AAM in biocorrosion environments can be best explained by bacteriostatic effects.

36 MATERIALS SCIENCE↗

Thermodynamics of the Solar Corona and Evolution of the Solar Magnetic Field as Inferred from the Total Solar Eclipse Observations of 11 July 2010

We report on multi-wavelength observations of the corona taken simultaneously in broadband white light, and in seven spectral lines, H-alpha 656.3 nm, Fe IX 435.9 nm, Fe X 637.4 nm, Fe XI 789.2 nm, Fe XIII 1074.7 nm, Fe XIV 530.3 nm and Ni XV 670.2 nm. The observations were made during the total solar eclipse of 11 July 2010 from the atoll of Tatakoto in French Polynesia. Simultaneous imaging with narrow bandpass filters in each of these spectral lines and in their corresponding underlying continua maximized the observing time during less than ideal observing conditions and yielded outstanding quality data. The application of two complementary image processing techniques revealed the finest details of coronal structures at 1" resolution in white light, and 6.5" in each of the spectral lines. This comprehensive wavelength coverage confirmed earlier eclipse findings that the solar corona has a clear two-temperature structure: The open field lines, expanding outwards from the solar surface, are characterized by electron temperatures near 1 X 10(exp 6) K, while the hottest plasma around 2X 10(exp 6) K resides in loop-like structures forming the bulges of streamers. The first images of the corona in the forbidden lines of Fe IX and Ni XV, showed that there was very little coronal plasma at temperatures below 5 X 10(exp 5) K and above 2.5X 10(exp 6) K. The data also enabled temperature differentiations as low as 0:2 X 10(exp 6) K in different density structures. These observations showed how the passage of CMEs through the corona, prior to totality, produced large scale ripples and very sharp streaks, which could be identified with distinct temperatures for the first time. The ripples were most prominent in emission from spectral lines associated with temperatures around 10(exp 6) K. The most prominent streak was associated with a conical-shaped void in the emission from the coolest line of Fe IX and from the hottest line of Ni XV. A prominence, which erupted prior to totality, appeared in the shape of a hook in the cooler lines of Fe X and Fe XI, spanning 0.5 R(solar) in extent starting at a heliocentric distance of 1.3 R(solar), with a complex trail of hot and cool twisted structures connecting it to the solar surface. Simultaneous Fe X 17.4 nm observations from space by Proba2/SWAP provided an ideal opportunity for comparing emission from a coronal forbidden line, namely Fe X 637.4 nm, with a space-based EUV allowed line. Comparison of the Fe X 17.4 nm and 637.4 nm emission provided the first textbook example of the role of radiative excitation in extending the detectability of coronal emission to much larger heliocentric distances than its collisionally excited component. These eclipse observations demonstrate the unique capabilities of coronal forbidden lines for exploring the evolution of the coronal magnetic field in the heliocentric distance range of 1 - 3 R(solar), which is currently inaccessible to any space-borne or ground-based observatory.

Habbal, Shadia Rifai↗