Geology topics

Roland A. Werner

Publications and source records attributed to Roland A. Werner.

4 recordsLinked to original sources

USGS2016

New organic reference materials for hydrogen, carbon, and nitrogen stable isotope-ratio measurements: caffeines, n-alkanes, fatty acid methyl esters, glycines, L-valines, polyethylenes, and oils

An international project developed, quality-tested, and determined isotope−δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope−δ scales. The RMs span a range of δ 2 H VSMOW-SLAP values from −210.8 to +397.0 mUr or ‰, for δ 13 C VPDB-LSVEC from −40.81 to +0.49 mUr and for δ 15 N Air from −5.21 to +61.53 mUr. Many of the new RMs are amenable to gas and liquid chromatography. The RMs include triads of isotopically contrasting caffeines, C 16 n -alkanes, n -C 20 -fatty acid methyl esters (FAMEs), glycines, and l -valines, together with polyethylene powder and string, one n -C 17 -FAME, a vacuum oil (NBS 22a) to replace NBS 22 oil, and a 2 H-enriched vacuum oil. A total of 11 laboratories from 7 countries used multiple analytical approaches and instrumentation for 2-point isotopic normalization against international primary measurement standards. The use of reference waters in silver tubes allowed direct normalization of δ 2 H values of organic materials against isotopic reference waters following the principle of identical treatment. Bayesian statistical analysis yielded the mean values reported here. New RMs are numbered from USGS61 through USGS78, in addition to NBS 22a. Because of exchangeable hydrogen, amino acid RMs currently are recommended only for carbon- and nitrogen-isotope measurements. Some amino acids contain 13 C and carbon-bound organic 2 H-enrichments at different molecular sites to provide RMs for potential site-specific isotopic analysis in future studies.

Analytical Chemistry↗

USGS2012

Temporal evolution of stable water isotopologues in cloud droplets in a hill cap cloud in central Europe (HCCT-2010)

In this work, we present the first study resolving the temporal evolution of δ 2 H and δ 18 O values in cloud droplets during 13 different cloud events. The cloud events were probed on a 937 m high mountain chain in Germany in the framework of the Hill Cap Cloud Thuringia 2010 campaign (HCCT-2010) in September and October 2010. The δ values of cloud droplets ranged from −77‰ to −15‰ (δ 2 H) and from −12.1‰ to −3.9‰ (δ 18 O) over the whole campaign. The cloud water line of the measured δ values was δ 2 H=7.8×δ 18 O+13×10−3, which is of similar slope, but with higher deuterium excess than other Central European Meteoric Water Lines. Decreasing δ values in the course of the campaign agree with seasonal trends observed in rain in central Europe. The deuterium excess was higher in clouds developing after recent precipitation revealing episodes of regional moisture recycling. The variations in δ values during one cloud event could either result from changes in meteorological conditions during condensation or from variations in the δ values of the water vapor feeding the cloud. To test which of both aspects dominated during the investigated cloud events, we modeled the variation in δ values in cloud water using a closed box model. We could show that the variation in δ values of two cloud events was mainly due to changes in local temperature conditions. For the other eleven cloud events, the variation was most likely caused by changes in the isotopic composition of the advected and entrained vapor. Frontal passages during two of the latter cloud events led to the strongest temporal changes in both δ 2 H (≈ 6‰ per hour) and δ 18 O (≈ 0.6‰ per hour). Moreover, a detailed trajectory analysis for the two longest cloud events revealed that variations in the entrained vapor were most likely related to rain out or changes in relative humidity and temperature at the moisture source region or both. This study illustrates the sensitivity of stable isotope composition of cloud water to changes in large scale air mass properties and regional recycling of moisture.

Atmospheric Chemistry and Physics↗

USGS2012

Stable water isotopologue ratios in fog and cloud droplets of liquid clouds are not size-dependent

In this work, we present the first observations of stable water isotopologue ratios in cloud droplets of different sizes collected simultaneously. We address the question whether the isotope ratio of droplets in a liquid cloud varies as a function of droplet size. Samples were collected from a ground intercepted cloud (= fog) during the Hill Cap Cloud Thuringia 2010 campaign (HCCT-2010) using a three-stage Caltech Active Strand Cloud water Collector (CASCC). An instrument test revealed that no artificial isotopic fractionation occurs during sample collection with the CASCC. Furthermore, we could experimentally confirm the hypothesis that the δ values of cloud droplets of the relevant droplet sizes (μm-range) were not significantly different and thus can be assumed to be in isotopic equilibrium immediately with the surrounding water vapor. However, during the dissolution period of the cloud, when the supersaturation inside the cloud decreased and the cloud began to clear, differences in isotope ratios of the different droplet sizes tended to be larger. This is likely to result from the cloud's heterogeneity, implying that larger and smaller cloud droplets have been collected at different moments in time, delivering isotope ratios from different collection times.

Atmospheric Chemistry and Physics↗

USGS2009

Comprehensive inter-laboratory calibration of reference materials for δ18O versus VSMOW using various on-line high-temperature conversion techniques

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC) in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125‰, an artificially enriched reference water ( δ 18 O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18 O) were prepared and calibrated relative to VSMOW2 and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material δ 18 O and estimated combined uncertainty IAEA-602 benzoic acid +71.28 ± 0.36‰ USGS35 sodium nitrate +56.81 ± 0.31‰ IAEA-NO-3 potassium nitrate +25.32 ± 0.29‰ IAEA-601 benzoic acid +23.14 ± 0.19‰ IAEA-SO-5 barium sulfate +12.13 ± 0.33‰ NBS 127 barium sulfate +8.59 ± 0.26‰ VSMOW2 water 0‰ IAEA-600 caffeine −3.48 ± 0.53‰ IAEA-SO-6 barium sulfate −11.35 ± 0.31‰ USGS34 potassium nitrate −27.78 ± 0.37‰ SLAP water −55.5‰ The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for δ 18 O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios ( δ 18 O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ 18 O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the δ 18 O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ 18 O and δ 2 H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible.

Rapid Communications in Mass Spectrometry↗