Tracer Applications of Noble Gas Radionuclides in the Geosciences

The noble gas radionuclides, including 81Kr (half-life = 229,000 yr), 85Kr (11 yr), and 39Ar (269 yr), possess nearly ideal chemical and physical properties for studies of earth and environmental processes. Recent advances in Atom Trap Trace Analysis (ATTA), a laser-based atom counting method, have enabled routine measurements of the radiokrypton isotopes, as well as the demonstration of the ability to measure 39Ar in environmental samples. Here we provide an overview of the ATTA technique, and a survey of recent progress made in several laboratories worldwide. We review the application of noble gas radionuclides in the geosciences and discuss how ATTA can help advance these fields, specifically determination of groundwater residence times using 81Kr, 85Kr, and 39Ar; dating old glacial ice using 81Kr; and an 39Ar survey of the main water masses of the oceans, to study circulation pathways and estimate mean residence times. Other scientific questions involving deeper circulation of fluids in the Earth's crust and mantle also are within the scope of future applications. We conclude that the geoscience community would greatly benefit from an ATTA facility dedicated to this field, with instrumentation for routine measurements, as well as for research on further development of ATTA methods

A 60 yr record of atmospheric carbon monoxide reconstructed from Greenland firn air

We present the first reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO in 1950 was 140–150 nmol mol-1, which is higher than today's values. CO mole fractions rose by 10–15 nmol mol-1 from 1950 to the 1970s and peaked in the 1970s or early 1980s, followed by a ˜ 30 nmol mol-1 decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radicals (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless unrealistically large changes in OH are assumed. We argue that the available CO emission inventories strongly underestimate historical NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe

Facility for testing ice drills

The Rapid Access Ice Drill (RAID) is designed for subsurface scientific investigations in Antarctica. Its objectives are to drill rapidly through ice, to core samples of the transition zone and bedrock, and to leave behind a borehole observatory. These objectives required the engineering and fabrication of an entirely new drilling system that included a modified mining-style coring rig, a unique fluid circulation system, a rod skid, a power unit, and a workshop with areas for the storage of supplies and consumables. An important milestone in fabrication of the RAID was the construction of a North American Test (NAT) facility where we were able to test drilling and fluid processing functions in an environment that is as close as possible to that expected in Antarctica. Our criteria for site selection was that the area should be cold during the winter months, be located in an area of low heat flow, and be at relatively high elevation. We selected a site for the facility near Bear Lake, Utah, USA. The general design of the NAT well (NAT-1) started with a 27.3 cm (10.75 in.) outer casing cemented in a 152 m deep hole. Within that casing, we hung a 14 cm (5.5 in.) casing string, and, within that casing, a column of ice was formed. The annulus between the 14 and 27.3 cm casings provided the path for circulation of a refrigerant. After in-depth study, we chose to use liquid CO2 to cool the hole. In order to minimize the likelihood of the casing splitting due to the volume increase associated with freezing water, the hole was first cooled and then ice was formed in increments from the bottom upward. First, ice cubes were placed in the inner liner and then water was added. Using this method, a column of ice was incrementally prepared for drilling tests. The drilling tests successfully demonstrated the functioning of the RAID system. Reproducing such a facility for testing of other ice drilling systems could be advantageous to other research programs in the future

Pulse oximetry in the oesophagus

Pulse oximetry has been one of the most significant technological advances in clinical monitoring in the last two decades. Pulse oximetry is a non-invasive photometric technique that provides information about the arterial blood oxygen saturation (SpO(2)) and heart rate, and has widespread clinical applications. When peripheral perfusion is poor, as in states of hypovolaemia, hypothermia and vasoconstriction, oxygenation readings become unreliable or cease. The problem arises because conventional pulse oximetry sensors must be attached to the most peripheral parts of the body, such as finger, ear or toe, where pulsatile flow is most easily compromised. Since central blood flow may be preferentially preserved, this review explores a new alternative site, the oesophagus, for monitoring blood oxygen saturation by pulse oximetry. This review article presents the basic physics, technology and applications of pulse oximetry including photoplethysmography. The limitations of this technique are also discussed leading to the proposed development of the oesophageal pulse oximeter. In the majority, the report will be focused on the description of a new oesophageal photoplethysmographic/SpO(2) probe, which was developed to investigate the suitability of the oesophagus as an alternative monitoring site for the continuous measurement of SpO(2) in cases of poor peripheral circulation. The article concludes with a review of reported clinical investigations of the oesophageal pulse oximeter

Venous Admixture in COPD: Pathophysiology and Therapeutic Approaches

Chronic obstructive and interstitial lung diseases impair pulmonary gas exchange leading to wasted ventilation (alveolar dead space) and wasted perfusion (venous admixture). These two fundamental types of abnormality represent opposite ends of the spectrum of ventilation-perfusion mismatch with V˙/Q˙ ratios of infinity and zero. Treatment approaches that improve airway function, reduce air trapping and hyperinflation have received much attention and might be successful at ameliorating the problems associated with high V˙/Q˙. However, in patients with low V˙/Q˙ abnormality in whom venous admixture leads to hypoxemia, there are few therapeutic options. Indeed, some patients are refractory to treatment with supplemental oxygen particularly during exercise. Theoretically these patients could benefit from an intervention that increased mixed venous oxygen content thereby ameliorating the deleterious effects of venous admixture. In this perspective article we discuss the mechanisms whereby venous admixture contributes to hypoxemia and reduced oxygen delivery to tissues. We explore methods which could potentially increase mixed venous oxygen content thus ameliorating the deleterious effects of venous admixture. One such intervention that warrants further investigation is the therapeutic creation of an arterio-venous fistula. Such an approach would be novel, simple and minimally invasive. There is reason to believe that complications would be minor leading to a favorable risk-benefit analysis. This approach to treatment could have significant impact for patients with COPD but should also benefit any patient with chronic hypoxemia that impairs exercise performance

Anatomy of a Dansgaard-Oeschger warming transition: High-resolution analysis of the North Greenland Ice Core Project ice core

Large and abrupt temperature oscillations during the last glacial period, known as Dansgaard‐Oeschger (DO) events, are clearly observed in the Greenland ice core record. Here we present a new high‐resolution chemical (2 mm) and stable isotope (20 mm) record from the North Greenland Ice Core Project (NGRIP) ice core at the onset of one of the most prominent DO events of the last glacial, DO‐8, observed ∼38,000 years ago. The unique, subannual‐resolution NGRIP record provides a true sequence of change during a DO warming with detailed annual layer counting of very high depth resolution geochemical measurements used to determine the exact duration of the transition. The continental ions, indicative of long‐range atmospheric loading and dustiness from East Asia, are the first to change, followed by the snow accumulation, the moisture source conditions, and finally the atmospheric temperature in Greenland. The sequence of events shows that atmospheric and oceanic source and circulation changes preceded the DO warming by several years

Opera and poison : a secret and enjoyable approach to teaching and learning chemistry

The storyline of operas, with historical or fictional characters, often include potions and poisons. This has prompted a study of the chemistry behind some operatic plots. The results were originally presented as a lecture given at the University of Minho in Portugal, within the context of the International Year of Chemistry. The same lecture was subsequently repeated at other universities as an invited lecture for science students and in public theaters for wider audiences. The lecture included a multimedia and interactive content that allowed the audience to listen to arias and to watch video clips with selected scenes extracted from operas. The present article, based on the lecture, demonstrates how chemistry and opera can be related and may also serve as a source of motivation and inspiration for chemistry teachers looking for alternative pedagogical approaches. Moreover, the lecture constitutes a vehicle that transports chemistry knowledge to wider audiences through examples of everyday molecules, with particular emphasis on natural products.The author is pleased to express his gratitude to Jorge Calado and Michael John Smith for useful discussions. The author also thanks the reviewers of the manuscript for their helpful comments and suggestions. Thanks are due to the Foundation for Science and Technology (FCT,Portugal), QREN and FEDER/EU for financial support through the research centers, CQ/UM PEst-C/QUI/UI0686/2011. Ciencia Viva, Portugal, is also acknowledged for financial support of the activities organized by the University of Minho during the International Year of Chemistry. The author also expresses his gratitude to Ana Paula Ferreira and Andre Cunha Leal from RTP Antena 2 who contributed immensely to the popularization of the lecture on which this paper is based on

Chemistry courses as the turning point for premedical students

Previous research has documented that negative experiences in chemistry courses are a major factor that discourages many students from continuing in premedical studies. This adverse impact affects women and students from under-represented minority (URM) groups disproportionately. To determine if chemistry courses have a similar effect at a large public university, we surveyed 1,036 students from three entering cohorts at the University of California, Berkeley. We surveyed students at the beginning of their first year at the university and again at the end of their second year. All subjects had indicated an interest in premedical studies at the time they entered the university. We conducted follow-up interviews with a stratified sub-set of 63 survey respondents to explore the factors that affected their level of interest in premedical studies. Using a 10-point scale, we found that the strength of interest in premedical studies declined for all racial/ethnic groups. In the follow-up interviews, students identified chemistry courses as the principal factor contributing to their reported loss of interest. URM students especially often stated that chemistry courses caused them to abandon their hopes of becoming a physician. Consistent with reports over more than 50 years, it appears that undergraduate courses in chemistry have the effect of discouraging otherwise qualified students, as reflected in their admission to one of the most highly selective public universities in the US, from continuing in premedical studies, especially in the case of URM students. Reassessment of this role for chemistry courses may be overdue

Rising atmospheric methane: 2007-2014 growth and isotopic shift

From 2007 to 2013, the globally averaged mole fraction of methane in the atmosphere increased by 5.7±1.2ppb yr$^{-1}$. Simultaneously, $\delta^{13}$C$_\text{CH4}$ (a measure of the $^{13}$C/$^{12}$C isotope ratio in methane) has shifted to significantly more negative values since 2007. Growth was extreme in 2014, at 12.5±0.4ppb, with a further shift to more negative values being observed at most latitudes. The isotopic evidence presented here suggests that the methane rise was dominated by significant increases in biogenic methane emissions, particularly in the tropics, for example, from expansion of tropical wetlands in years with strongly positive rainfall anomalies or emissions from increased agricultural sources such as ruminants and rice paddies. Changes in the removal rate of methane by the OH radical have not been seen in other tracers of atmospheric chemistry and do not appear to explain short-term variations in methane. Fossil fuel emissions may also have grown, but the sustained shift to more $^{13}$C-depleted values and its significant interannual variability, and the tropical and Southern Hemisphere loci of post-2007 growth, both indicate that fossil fuel emissions have not been the dominant factor driving the increase. A major cause of increased tropical wetland and tropical agricultural methane emissions, the likely major contributors to growth, may be their responses to meteorological change.This work was supported by the UK Natural Environment Research Council projects NE/N016211/1 The Global Methane Budget, NE/M005836/1 Methane at the edge, NE/K006045/1 The Southern Methane Anomaly and NE/I028874/1 MAMM. We thank the UK Meteorological Office for flask collection and hosting the continuous measurement at Ascension, the Ascension Island Government for essential support, and Thumeka Mkololo for flask collection in Cape Tow