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 (δ18O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18O) 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. 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 δ18O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios (δ18O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ18O 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 δ18O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ18O and δ2H 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.

Liquid-hydrogen rocket engine development at Aerojet, 1944 - 1950

This program demonstrated the feasibility of virtually all the components in present-day, high-energy, liquid-rocket engines. Transpiration and film-cooled thrust chambers were successfully operated. The first liquid-hydrogen tests of the coaxial injector was conducted and the first pump to successfully produce high pressures in pumping liquid hydrogen was tested. A 1,000-lb-thrust gaseous propellant and a 3,000-lb-thrust liquid-propellant thrust chamber were operated satisfactorily. Also, the first tests were conducted to evaluate the effects of jet overexpansion and separation on performance of rocket thrust chambers with hydrogen-oxygen propellants

Carotenoids are the likely precursor of a significant fraction of marine dissolved organic matter.

The ocean's biota sequester atmospheric carbon dioxide (CO2) in part by producing dissolved organic matter (DOM) that persists in the ocean for millennia. This long-term accumulation of carbon may be facilitated by abiotic and biotic production of chemical structures that resist degradation, consequently contributing disproportionately to refractory DOM. Compounds that are selectively preserved in seawater were identified in solid-phase extracted DOM (PPL-DOM) using comprehensive gas chromatography (GC) coupled to mass spectrometry (MS). These molecules contained cyclic head groups that were linked to isoprenoid tails, and their overall structures closely resembled carotenoid degradation products (CDP). The origin of these compounds in PPL-DOM was further confirmed with an in vitro β-carotene photooxidation experiment that generated water-soluble CDP with similar structural characteristics. The molecular-level identification linked at least 10% of PPL-DOM carbon, and thus 4% of total DOM carbon, to CDP. Nuclear magnetic resonance spectra of experimental CDP and environmental PPL-DOM overlapped considerably, which indicated that even a greater proportion of PPL-DOM was likely composed of CDP. The CDP-rich DOM fraction was depleted in radiocarbon (14C age > 1500 years), a finding that supports the possible long-term accumulation of CDP in seawater. By linking a specific class of widespread biochemicals to refractory DOM, this work provides a foundation for future studies that aim to examine how persistent DOM forms in the ocean

Boron isotope ratio (delta B-11) measurements in water framework directive monitoring programs: comparison between double focusing sector field ICP and thermal ionization mass spectrometry

International audienceThe aim of our research was to compare delta B-11 measurements performed with thermal ionization mass spectrometry (TIMS) and sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS) and evaluate the feasibility of implementing stable isotope methods in European water framework directive (WFD) monitoring programs. The comparison was based on delta B-11 measurements of 192 ground-and surface water samples and 15 leachates of nitrate pollution source materials (organic and mineral fertilisers). The precision of delta B-11 measurements attainable with SF-ICP-MS, 2 sigma= +/- 2.6 parts per thousand; (n = 192), is as expected lower than the precision achieved by TIMS, 2 sigma= +/- 0.3 parts per thousand (n=183). However the ease of use, rapidity and availability of SF-ICP-MS on one hand and the observed variability in delta B-11 in ground-and surface water on the other (from -3.4 to +37 parts per thousand), demonstrates that using SF-ICP-MS as an isotopic screening method would promote the use of isotopic methodology for WFD monitoring. Based on the results of the different case studies it is shown that retrieving precise information on the identification of pollution sources from delta B-11 values requires reaching the best analytical precision and accuracy possible. Hence, the superior precision of TIMS advantages tracing of nitrate pollution sources. However for some cases, e. g. trying to decipher contributions between sources with really distinct delta B-11 signatures (e.g. manure and sewage effluent), SF-ICP-MS results lead to the same conclusions and can therefore be used as a first approachable screening method for the determination of delta B-11 in WFD monitoring programs

Development of an advanced on-line position-specific stable carbon isotope system and application to methyl tert-butyl ether

We present an advanced system for on-line position-specific carbon isotope analysis. The main limitation of on-line intramolecular isotope ratio measurements has been that optimal pyrolytic fragments are obtained mostly at temperatures where the analyte has not completely reacted. As a result of undetermined isotopic fractionation, the isotopic signatures of the pyrolysis products are not strictly equal to these of the equivalent moieties in the parent molecule. We designed a pyrolytic unit in which both temperature and reaction time are variable parameters, enabling determination of the enrichment factor of the pyrolysis at optimal temperature by construction of a Rayleigh plot. In the case of methyl tert-butyl ether (MTBE) presented here, a 'pre-pyrolysis' fractionation of MTBE leading to a depletion of 0.9 parts per thousand was discovered and the enrichment factor of the optimal pyrolysis reaction was determined at -1.7 parts per thousand. Absolute delta C-13 values of two functional groups of MTBE - the methoxy group and the 2-methylpropane group - could be determined with 95% confidence intervals of 0.4 parts per thousand and 0.5 parts per thousand, respectively

Effectiveness of Gloves and Infection Control in Dentistry: Student and Provider Perspectives

The objectives of this study were to explore dental and dental hygiene students’, graduate students’, and dental professionals’ preferences for certain types of gloves and the reasons for these preferences (Aim 1), as well as determining their knowledge, attitudes, and behavior concerning the use of dental gloves as a means of barrier protection (Aim 2). Data were collected from 198 dental and forty-six dental hygiene students, thirty-five graduate students, and seventy-nine dental professionals (twenty-eight dentists and fifty-one dental hygienists in private practice). The subjects responded to a self-administered anonymous survey. Professionals (dentists: 96.4 percent and dental hygienists: 92.2 percent) were found to be more likely to have a preference for certain types of gloves than students (dental students: 79.2 percent and dental hygiene students: 76 percent) and graduate students (77.1 percent; p=.033). “Comfort” was most frequently reported as a reason for glove preference. Large percentages of respondents wrongly believed that gloves provide full protection (students: 50.8 percent; graduate students: 25.7 percent; professionals: 30.4 percent), thought that gloves provide protection as long as there is no visible tear (students: 39.7 percent; graduate students: 28.6 percent; professionals: 18.2 percent), and reported that they would not change gloves during an uninterrupted three-hour long procedure (students: 32.2 percent; graduate students: 23.5 percent; professionals: 22.7 percent). These findings should alert dental educators about the importance of educating their students as well as practicing professionals clearly and comprehensively about infection control and the science and rationale supporting recommended guidelines

Long-Term Vegetation Dynamics in a Megadiverse Hotspot: The Ice-Age Record of a Pre-montane Forest of Central Ecuador.

Tropical ecosystems play a key role in many aspects of Earth system dynamics currently of global concern, including carbon sequestration and biodiversity. To accurately understand complex tropical systems it is necessary to parameterise key ecological aspects, such as rates of change (RoC), species turnover, dynamism, resilience, or stability. To obtain a long-term (>50 years) perspective on these ecological aspects we must turn to the fossil record. However, compared to temperate zones, collecting continuous sedimentary archives in the lowland tropics is often difficult due to the active landscape processes, with potentially frequent volcanic, tectonic, and/or fluvial events confounding sediment deposition, preservation, and recovery. Consequently, the nature, and drivers, of vegetation dynamics during the last glacial are barely known from many non-montane tropical landscapes. One of the first lowland Amazonian locations from which palaeoecological data were obtained was an outcrop near Mera (Ecuador). Mera was discovered, and analysed, by Paul Colinvaux in the 1980s, but his interpretation of the data as indicative of a forested glacial period were criticised based on the ecology and age control. Here we present new palaeoecological data from a lake located less than 10 km away from Mera. Sediment cores raised from Laguna Pindo (1250 masl; 1°27'S, 78°05'W) have been shown to span the late last glacial period [50-13 cal kyr BP (calibrated kiloyears before present)]. The palaeoecological information obtained from Laguna Pindo indicate that the region was characterised by a relatively stable plant community, formed by taxa nowadays common at both mid and high elevations. was the dominant taxon until around 30 cal kyr BP, when it was replaced by , Asteraceae and among other taxa. Heat intolerant taxa including , , and peaked around the onset of the Last Glacial Maximum (c. 21 cal kyr BP). The results obtained from Laguna Pindo support Colinvaux's hypothesis that glacial cooling resulted in a reshuffling of taxa in the region but did not lead to a loss of the forest structure. Wide tolerances of the plant species occurring to glacial temperature range and cloud formation have been suggested to explain Pindo forest stability. This scenario is radically different than the present situation, so vulnerability of the tropical pre-montane forest is highlighted to be increased in the next decades

Negotiating power: examining the role of procedural elements in international peace talks

Peace agreements don’t write themselves. They are negotiated — in complex, iterative sessions with highly contingent results. Diplomats take pains to establish a negotiation’s procedural elements (e.g., timing, venue, and rules of engagement) in advance; they often contest or adapt these elements throughout the negotiation process. This area of diplomatic practice is under-examined in International Relations (IR). Accordingly, this research explores the following questions: Do the procedural elements of negotiation impact the dynamics and outcomes of international peace processes? If so, how? This thesis argues that procedural elements have meaningful effects on negotiation dynamics and subsequent foreign policy outcomes; understanding these mechanisms is key to understanding ‘power’ in the international system. After critically examining existing theories of power in IR and identifying a crucial area of underdevelopment in the field’s construction of ‘agenda-setting power,’ this thesis advances the novel ‘Cubist concept of power.’ Inspired by the Cubist art movement, this conceptual framework highlights the multi-dimensionality, fragmentation, and perceptual relativity of power in negotiation contexts. This article-based thesis presents three discrete studies of illustrative procedural elements, adopting a pragmatic approach to research aims and methodologies. The first article leverages historical sources to assess US mediators’ use of time pressure tactics; the second uses a web-based survey to investigate the impact of ‘virtual venue’ selection during the COVID-19 pandemic; and the third draws on interviews with seasoned practitioners to explore the effects of notetaking practices. All three studies validate the influence of procedural elements in shaping negotiation dynamics and outcomes. Cross-cutting findings highlight the role of technological affordances, perceptions of procedural justice, and interpersonal relationship-building. This thesis complicates existing theories of power in IR while offering policy-relevant findings to support practitioners in designing more effective peace negotiations in the future