Stable isotopes in water vapor and precipitation for a coastal lagoon at mid latitudes

NASA Astrophysics Data System (ADS)

Zannoni, Daniele; Bergamasco, Andrea; Dreossi, Giuliano; Rampazzo, Giancarlo; Stenni, Barbara

2016-04-01

The stable oxygen and hydrogen isotope composition in precipitation can be used in hydrology to describe the signature of local meteoric water. The isotopic composition of water vapor is usually obtained indirectly from measurements of δD and δ18O in precipitation, assuming the isotopic equilibrium between rain and water vapor. Only few studies report isotopic data in both phases for the same area, thus providing a complete Local Meteoric Water Line (LMWL). The goal of this study is to build a complete LMWL for the lagoon of Venice (northern Italy) with observations of both water vapor and precipitation. The sampling campaign has started in March 2015 and will be carried out until the end of 2016. Water vapor is collected once a week with cold traps at low temperatures (-77°C). Precipitation is collected on event and monthly basis with a custom automatic rain sampler and a rain gauge, respectively. Liquid samples are analyzed with a Picarro L1102-i and results are reported vs VSMOW. The main meteorological parameters are continuously recorded in the same area by the campus automatic weather station. Preliminary data show an LMWL close to the Global Meteoric Water Line (GMWL) with lower slope and intercept. An evaporation line is clearly recognizable, considering samples that evaporated between the cloud base and the ground. The deviation from the GMWL parameters, especially intercept, can be attributed to evaporated rain or to the humidity conditions of the water vapor source. Water vapor collected during rainfall shows that rain and vapor are near the isotopic equilibrium, just considering air temperature measured at ground level. Temperature is one of the main factor that controls the isotopic composition of the atmospheric water vapor. Nevertheless, the circulation of air masses is a crucial parameter which has to be considered. Water vapor samples collected in different days but with the same meteorological conditions (air temperature and relative humidity

Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.

Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotopemore » observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ 18O v ranged from –40.2 to –15.9 ‰ and δ 2H v ranged from –278.7 to –113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess ( d v) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in d v, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol –1) indicate that

Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

DOE PAGES

Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.; ...

2016-04-25

Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotopemore » observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ 18O v ranged from –40.2 to –15.9 ‰ and δ 2H v ranged from –278.7 to –113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess ( d v) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in d v, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol –1) indicate that

Vapor hydrogen and oxygen isotopes reflect water of combustion in the urban atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gorski, Galen; Strong, Courtenay; Good, Stephen P.

Anthropogenic modification of the water cycle involves a diversity of processes, many of which have been studied intensively using models and observations. Some effective tools for measuring the contribution and fate of combustion-derived water vapor in the atmosphere are lacking, however, and this flux has received relatively little attention. We provide theoretical estimates and a first set of measurements demonstrating that water of combustion is characterized by a distinctive combination of H and O isotope ratios. Furthermore, we show that during periods of relatively low humidity and/or atmospheric stagnation, this isotopic signature can be used to quantify the concentration ofmore » water of combustion in the atmospheric boundary layer over Salt Lake City. Combustion-derived vapor concentrations vary between periods of atmospheric stratification and mixing, both on multiday and diurnal timescales, and respond over periods of hours to variations in surface emissions. Our estimates suggest that up to 13% of the boundary layer vapor during the period of study was derived from combustion sources, and both the temporal pattern and magnitude of this contribution were closely reproduced by an independent atmospheric model forced with a fossil fuel emissions data product. These findings suggest potential for water vapor isotope ratio measurements to be used in conjunction with other tracers to refine the apportionment of urban emissions, and imply that water vapor emissions associated with combustion may be a significant component of the water budget of the urban boundary layer, with potential implications for urban climate, ecohydrology, and photochemistry.« less

Vapor hydrogen and oxygen isotopes reflect water of combustion in the urban atmosphere

DOE PAGES

Gorski, Galen; Strong, Courtenay; Good, Stephen P.; ...

2015-03-02

Anthropogenic modification of the water cycle involves a diversity of processes, many of which have been studied intensively using models and observations. Some effective tools for measuring the contribution and fate of combustion-derived water vapor in the atmosphere are lacking, however, and this flux has received relatively little attention. We provide theoretical estimates and a first set of measurements demonstrating that water of combustion is characterized by a distinctive combination of H and O isotope ratios. Furthermore, we show that during periods of relatively low humidity and/or atmospheric stagnation, this isotopic signature can be used to quantify the concentration ofmore » water of combustion in the atmospheric boundary layer over Salt Lake City. Combustion-derived vapor concentrations vary between periods of atmospheric stratification and mixing, both on multiday and diurnal timescales, and respond over periods of hours to variations in surface emissions. Our estimates suggest that up to 13% of the boundary layer vapor during the period of study was derived from combustion sources, and both the temporal pattern and magnitude of this contribution were closely reproduced by an independent atmospheric model forced with a fossil fuel emissions data product. These findings suggest potential for water vapor isotope ratio measurements to be used in conjunction with other tracers to refine the apportionment of urban emissions, and imply that water vapor emissions associated with combustion may be a significant component of the water budget of the urban boundary layer, with potential implications for urban climate, ecohydrology, and photochemistry.« less

Vapor hydrogen and oxygen isotopes reflect water of combustion in the urban atmosphere

PubMed Central

Gorski, Galen; Strong, Courtenay; Good, Stephen P.; Bares, Ryan; Ehleringer, James R.; Bowen, Gabriel J.

2015-01-01

Anthropogenic modification of the water cycle involves a diversity of processes, many of which have been studied intensively using models and observations. Effective tools for measuring the contribution and fate of combustion-derived water vapor in the atmosphere are lacking, however, and this flux has received relatively little attention. We provide theoretical estimates and a first set of measurements demonstrating that water of combustion is characterized by a distinctive combination of H and O isotope ratios. We show that during periods of relatively low humidity and/or atmospheric stagnation, this isotopic signature can be used to quantify the concentration of water of combustion in the atmospheric boundary layer over Salt Lake City. Combustion-derived vapor concentrations vary between periods of atmospheric stratification and mixing, both on multiday and diurnal timescales, and respond over periods of hours to variations in surface emissions. Our estimates suggest that up to 13% of the boundary layer vapor during the period of study was derived from combustion sources, and both the temporal pattern and magnitude of this contribution were closely reproduced by an independent atmospheric model forced with a fossil fuel emissions data product. Our findings suggest potential for water vapor isotope ratio measurements to be used in conjunction with other tracers to refine the apportionment of urban emissions, and imply that water vapor emissions associated with combustion may be a significant component of the water budget of the urban boundary layer, with potential implications for urban climate, ecohydrology, and photochemistry. PMID:25733906

A Plant-Based Proxy for the Oxygen Isotope Ratio of Atmospheric Water Vapor

NASA Astrophysics Data System (ADS)

Helliker, B.

2007-12-01

Atmospheric water vapor is a major component of the global hydrological cycle, but the isotopic balance of vapor is largely unknown. It is shown here that the oxygen isotope ratio of leaf water in the epiphytic Crassulacean acid metabolism (CAM) plant Tillandsia usneoides (Spanish Moss) is controlled by the oxygen isotope ratio of atmospheric water vapor in both field and lab studies. Assuming that the leaf-water isotopic signature (and hence the atmospheric water vapor signature) is recorded in plant organic material, the atmospheric water vapor oxygen isotope ratios for Miami, Florida (USA) were reconstructed for several years from 1878 to 2005 using contemporary and herbarium specimens. T. usneoides ranges from Virginia, USA southwards through the tropics to Argentina, and the CAM epiphytic lifeform is widespread in other species. Therefore, epiphytes may be used to reconstruct the isotope ratio of atmospheric water for spatial scales that span over 60° of latitude and temporal scales that cover the last century of global temperature increase.

Using in-situ observations of atmospheric water vapor isotopes to benchmark and isotope-enabled General Circulation Models and improve ice core paleo-climate reconstruction

NASA Astrophysics Data System (ADS)

Steen-Larsen, Hans Christian; Sveinbjörnsdottir, Arny; Masson-Delmotte, Valerie; Werner, Martin; Risi, Camille; Yoshimura, Kei

2016-04-01

We have since 2010 carried out in-situ continuous water vapor isotope observations on top of the Greenland Ice Sheet (3 seasons at NEEM), in Svalbard (1 year), in Iceland (4 years), in Bermuda (4 years). The expansive dataset containing high accuracy and precision measurements of δ18O, δD, and the d-excess allow us to validate and benchmark the treatment of the atmospheric hydrological cycle's processes in General Circulation Models using simulations nudged to reanalysis products. Recent findings from both Antarctica and Greenland have documented strong interaction between the snow surface isotopes and the near surface atmospheric water vapor isotopes on diurnal to synoptic time scales. In fact, it has been shown that the snow surface isotopes take up the synoptic driven atmospheric water vapor isotopic signal in-between precipitation events, erasing the precipitation isotope signal in the surface snow. This highlights the importance of using General or Regional Climate Models, which accurately are able to simulate the atmospheric water vapor isotopic composition, to understand and interpret the ice core isotope signal. With this in mind we have used three isotope-enabled General Circulation Models (isoGSM, ECHAM5-wiso, and LMDZiso) nudged to reanalysis products. We have compared the simulations of daily mean isotope values directly with our in-situ observations. This has allowed us to characterize the variability of the isotopic composition in the models and compared it to our observations. We have specifically focused on the d-excess in order to characterize why both the mean and the variability is significantly lower than our observations. We argue that using water vapor isotopes to benchmark General Circulation Models offers an excellent tool for improving the treatment and parameterization of the atmospheric hydrological cycle. Recent studies have documented a very large inter-model dispersion in the treatment of the Arctic water cycle under a future global

Evapotranspiration partitioning in a semi-arid African savanna using stable isotopes of water vapor

NASA Astrophysics Data System (ADS)

Soderberg, K.; Good, S. P.; O'Connor, M.; King, E. G.; Caylor, K. K.

2012-04-01

Evapotranspiration (ET) represents a major flux of water out of semi-arid ecosystems. Thus, understanding ET dynamics is central to the study of African savanna health and productivity. At our study site in central Kenya (Mpala Research Centre), we have been using stable isotopes of water vapor to partition ET into its constituent parts of plant transpiration (T) and soil evaporation (E). This effort includes continuous measurement (1 Hz) of δ2H and δ18O in water vapor using a portable water vapor isotope analyzer mounted on a 22.5 m eddy covariance flux tower. The flux tower has been collecting data since early 2010. The isotopic end-member of δET is calculated using a Keeling Plot approach, whereas δT and δE are measured directly via a leaf chamber and tubing buried in the soil, respectively. Here we report on a two recent sets of measurements for partitioning ET in the Kenya Long-term Exclosure Experiment (KLEE) and a nearby grassland. We combine leaf level measurements of photosynthesis and water use with canopy-scale isotope measurements for ET partitioning. In the KLEE experiment we compare ET partitioning in a 4 ha plot that has only seen cattle grazing for the past 15 years with an adjacent plot that has undergone grazing by both cattle and wild herbivores (antelope, elephants, giraffe). These results are compared with a detailed study of ET in an artificially watered grassland.

Stable isotopic variations of water vapor on the winter coastal area in Korea

NASA Astrophysics Data System (ADS)

Lee, Jeonghoon; Lee, Songyi; Han, Yeongcheol; Do Hur, Soon

2017-04-01

Studies of isotopic compositions of precipitation in Korea have been conducted for groundwater mixing and sources and residence time of water. Unravelling of water vapor isotopes will be very helpful in explaining the sources of moisture. In this work, we first present isotopic compositions of water vapor over western part of Korea in winter between December 2015 and February 2016. We collected the samples of water vapor isotopes by a cryogenic method with impingers and liquid nitrogen. We captured the water vapor for 4 to 6 hours, depending on humidity and collected 54 samples in total. The samples were analyzed by a Picarro L2130-i and the precisions were 0.06‰ and 0.7‰ for oxygen and hydrogen, respectively. The isotopic compositions of water vapor ranged from -34.04‰ to -15.27‰ for oxygen and from -221.9‰ to -100.2‰ for hydrogen. The deuterium excess (d=δD-8*δ18O) was between 17.4 and 44.0 in permil. Both air temperature (T, δ18O=0.57*T-25.5, R2=0.46) and relative humidity (RH, δ18O=0.18*RH-35.9, R2=0.38) were positively correlated with the water vapor isotopes. This is not consistent with the fact that precipitation isotopes are correlated with only temperate in winter Eastern Asia. We expect that the water vapor isotopes will be an important role to understand the origin and pathway of moistures over the Eastern Asia.

Investigating understory flora species as an isotope proxy for atmospheric water vapor

NASA Astrophysics Data System (ADS)

Rambo, J. P.; Lai, C.; Farlin, J. P.

2011-12-01

An understanding of stable isotope variation in leaf water is useful in quantifying water fluxes through different pathways. Little is known about species specific variations of leaf water 18O and 2H enrichment and their interactions with atmospheric water vapor in understory flora. Toward this end, we measured stable 18O and 2H signatures of leaf water and atmospheric water vapor in an old growth forest in the Pacific Northwest. A LGR off-axis cavity-enhanced absorption spectroscopy analyzer was used to measure hourly 18O/16O and 2H/1H ratios of atmospheric water vapor (δ18Ov and δ2Hv) at 3 canopy heights (1m aboveground, mid- and above-canopy). By employing a routine, in-situ calibration, we were able to account for the concentration and temperature dependency from the instrument-reported δ18Ov and δ2Hv values using a single reference water. By using a 3-point calibration procedure we were able to produce accurate (±0.2% for δ18Ov, ±0.5% for δ2Hv) and precise (±0.3% for δ18Ov, ±3.0% for δ2Hv) measurements on the VSMOW scale. During our sampling campaign we observed large variations ranging from -175.0% to -125.1% for δ2Hv and -23.9% to -13.5% for δ18Ov. Leaf tissue of four dominant understory plant species were sampled every 2 hours over a three day period. Previous studies showed that leaf water becomes isotopically enriched from evaporative fractionation during the day, and then returns to an isotopic equilibrium with atmospheric water vapor during nighttime, reaching a complete equilibrium at pre-dawn in wet environments (i.e. Amazon forests). This diurnal pattern in leaf water isotope ratios was ubiquitous in terrestrial ecosystems, however, leading to the potential of using this plant-based signature as a proxy to infer δ18Ov and δ2Hv in remote locations. In the present study we investigate how leaf water of understory flora and atmospheric water vapor interact in a temperate forest.

Partitioning the effects of Global Warming on the Hydrological Cycle with Stable Isotopes in Water Vapor

NASA Astrophysics Data System (ADS)

Dee, S. G.; Russell, J. M.; Nusbaumer, J. M.; Konecky, B. L.; Buenning, N. H.; Lee, J. E.; Noone, D.

2016-12-01

General circulation models (GCMs) suggest that much of the global hydrological cycle's response to anthropogenic warming will be caused by increased lower-tropospheric water vapor concentrations and associated feedbacks. However, fingerprinting changes in the global hydrological cycle due to anthropogenic warming remains challenging. Held and Soden (2006) predicted that as lower-tropospheric water vapor increases, atmospheric circulation will weaken as climate warms to maintain the surface energy budget. Unfortunately, the strength of this feedback and the fallout for other branches of the hydrological cycle is difficult to constrain in situ or with GCMs alone. We demonstrate the utility of stable hydrogen isotope ratios in atmospheric water vapor to quantitatively trace changes in atmospheric circulation and convective mass flux in a warming world. We compare water isotope-enabled GCM experiments for control (present-day) CO2 vs. high CO2(2x, 4x) atmospheres in two GCMs, IsoGSM and iCAM5. We evaluate changes in the distribution of water vapor, vertical velocity (omega), and the stream function between these experiments in order to identify spatial patterns of circulation change over the tropical Pacific (where vertical motion is strong) and map the δD of water vapor associated with atmospheric warming. We also probe the simulations to isolate isotopic signatures associated with water vapor residence time, precipitation efficiency, divergence, and cloud physics. We show that there are robust mechanisms that moisten the troposphere and weaken convective mass flux, and that these mechanisms can be tracked using the δD of water vapor. Further, we find that these responses are most pronounced in the upper troposphere. These findings provide a framework to develop new metrics for the detection of global warming impacts to the hydrological cycle. Further, currently available satellite missions measure δD in the atmospheric boundary layer, the free atmosphere, or the

Stable isotope composition of water vapor in the atmospheric boundary layer above the forests of New England

NASA Astrophysics Data System (ADS)

He, Hui; Smith, Ronald B.

1999-05-01

Water vapor at multiple levels was sampled from a light aircraft in the summertime atmospheric boundary layer (ABL) over forested terrain at altitudes up to 3 km. Three sampling flights were carried out under similar weather conditions during the summer to earlier fall period of 1996. The deuterium and oxygen 18 isotope ratios, δD and δ18O, of 24 water vapor and 30 surface water samples were analyzed on a mass spectrometer. The water vapor mixing ratio, Q, at each sampling level was estimated from the amount of the sample collected. The results show constant δD and δ18O in the mixed region of the ABL and sharply decreasing values near the top. Measurement of the ratio of the vertical atmospheric flux of HD16O or H218O to the flux of H216O is of particular interest in hydrology and paleoclimatology studies. This quantity, however, cannot be measured directly at the surface due to the instantaneous turbulent mixing of the evaporating water vapor with the overlying ABL. Using a δ - 1/Q mixing line method, we are able to determine such isotope flux ratios characterizing the two-way exchange between the Earth's surface and the free atmosphere. The varying isotope flux ratios are lighter than expected, but fall into the ranges of the isotope ratios of the winter precipitation in the area. Based on the hypothesis of no fractionation between the soil water and the water vapor transpired by plants, our measurements suggest that late summer transpiration releases soil water which comes from the precipitation that fell during the previous winter. Other explanations are also discussed.

Importance of depth and intensity of convection on the isotopic composition of water vapor as seen from IASI and TES δD observations

NASA Astrophysics Data System (ADS)

Lacour, Jean-Lionel; Risi, Camille; Worden, John; Clerbaux, Cathy; Coheur, Pierre-François

2018-01-01

We use tropical observations of the water vapor isotopic composition, derived from IASI and TES spaceborne measurements, to show that the isotopic composition of water vapor in the free troposphere is sensitive to both the depth and the intensity of convection. We find that for any given precipitation intensity, vapor associated with deep convection is isotopically depleted relative to vapor associated with shallow convection. The intensity of precipitation also plays a role as for any given depth of convection, the relative enrichment of water vapor decreases as the intensity of precipitation increases. Shallow convection, via the uplifting of enriched boundary layer air into the free troposphere and the convective detrainment, enriches the free troposphere. In contrast, deep convection is associated with processes that deplete the water vapor in the free troposphere, such as rain re-evaporation. The results of this study allow for a better identification of the parameters controlling the isotopic composition of the free troposphere and indicate that the isotopic composition of water vapor can be used to evaluate the relative contributions of shallow and deep convection in global models.

Toward a simple, repeatable, non-destructive approach to measuring stable-isotope ratios of water within tree stems

NASA Astrophysics Data System (ADS)

Raulerson, S.; Volkmann, T.; Pangle, L. A.

2017-12-01

Traditional methodologies for measuring ratios of stable isotopes within the xylem water of trees involve destructive coring of the stem. A recent approach involves permanently installed probes within the stem, and an on-site assembly of pumps, switching valves, gas lines, and climate-controlled structure for field deployment of a laser spectrometer. The former method limits the possible temporal resolution of sampling, and sample size, while the latter may not be feasible for many research groups. We present results from initial laboratory efforts towards developing a non-destructive, temporally-resolved technique for measuring stable isotope ratios within the xylem flow of trees. Researchers have used direct liquid-vapor equilibration as a method to measure isotope ratios of the water in soil pores. Typically, this is done by placing soil samples in a fixed container, and allowing the liquid water within the soil to come into isotopic equilibrium with the headspace of the container. Water can also be removed via cryogenic distillation or azeotropic distillation, with the resulting liquid tested for isotope ratios. Alternatively, the isotope ratios of the water vapor can be directly measured using a laser-based water vapor isotope analyzer. Well-established fractionation factors and the isotope ratios in the vapor phase are then used to calculate the isotope ratios in the liquid phase. We propose a setup which would install a single, removable chamber onto a tree, where vapor samples could non-destructively and repeatedly be taken. These vapor samples will be injected into a laser-based isotope analyzer by a recirculating gas conveyance system. A major part of what is presented here is in the procedure of taking vapor samples at 100% relative humidity, appropriately diluting them with completely dry N2 calibration gas, and injecting them into the gas conveyance system without inducing fractionation in the process. This methodology will be helpful in making

Continuous field measurements of δD in water vapor by open-path Fourier transform infrared spectrometry

NASA Astrophysics Data System (ADS)

Wang, Wei; Liu, Wenqing; Zhang, Tianshu

2012-12-01

The stable isotopes in atmospheric water vapor contain rich information on the hydrologic cycles and gaseous exchange processes between biosphere and atmosphere. About one-week field experiment was conducted to continuously measure the isotope composition of water vapor in ambient air using an open-path FTIR system. Mixing ratios of H2 16O and HD16O were measured simultaneously. Analysis of water vapor isotopes revealed that the variations of H2 16O and HD16O were highly related. Mixing ratios of both isotopes varied considerably on a daily timescale or between days, with no obvious diurnal cycle, whereas the deuterium isotopic [delta]D showed clear diel cycle. The results illustrated that the correlation between [delta]D and H2O mixing ratio was relatively weak, which was also demonstrated by the Keeling plot analysis with the whole data. Yet the further Keeling analysis on a daily timescale displayed more obvious linear relationship between [delta]D and the total H2O concentration. All daily isotopic values of evapotranspiration source were obtained, with the range between -113.93±10.25‰ and -245.63±17.61‰ over the observation period.

Stable isotope measurements of evapotranspiration partitioning in a maize field

NASA Astrophysics Data System (ADS)

Hogan, Patrick; Parajka, Juraj; Oismüller, Markus; Strauss, Peter; Heng, Lee; Blöschl, Günter

2017-04-01

Evapotranspiration (ET) is one of the most important processes in describing land surface - atmosphere interactions as it connects the energy and water balances. Furthermore knowledge of the individual components of evapotranspiration is important for ecohydrological modelling and agriculture, particularly for irrigation efficiency and crop productivity. In this study, we tested the application of the stable isotope method for evapotranspiration partitioning to a maize crop during the vegetative stage, using sap flow sensors as a comparison technique. Field scale ET was measured using an eddy covariance device and then partitioned using high frequency in-situ measurements of the isotopic signal of the canopy water vapor. The fraction of transpiration (Ft) calculated with the stable isotope method showed good agreement with the sap flow method. High correlation coefficient values were found between the two techniques, indicating the stable isotope method can successfully be applied in maize. The results show the changes in transpiration as a fraction of evapotranspiration after rain events and during the subsequent drying conditions as well as the relationship between transpiration and solar radiation and vapor pressure deficit.

Continuous-flow water sampler for real-time isotopic water measurements

NASA Astrophysics Data System (ADS)

Carter, J.; Dennis, K.

2013-12-01

Measuring the stable isotopes of liquid water (δ18O and δD) is a tool familiar to many Earth scientists, but most current techniques require discrete sampling. For example, isotope ratio mass spectrometry requires the collection of aliquots of water that are then converted to CO2, CO or H2 for analysis. Similarly, laser-based techniques, such as Cavity Ring-Down Spectroscopy (CRDS) convert discrete samples (typically < 2μL) of liquid water to water vapor using a flash vaporization process. By requiring the use of discrete samples fine-scale spatial and temporal studies of changes in δ18O and δD are limited. Here we present a continuous-flow water sampler that will enable scientists to probe isotopic changes in real-time, with applications including, but not limited to, quantification of the 'amount effect' (Dansgaard, 1964) during an individual precipitation event or storm track, real-time mixing of water in river systems, and shipboard continuous water measurements (Munksgaard et al., 2012). Due to the inherent ability of CRDS to measure a continuous flow of water vapor it is an ideal candidate for interfacing with a continuous water sampling system. Here we present results from the first commercially available continuous-flow water sampler, developed by engineers at Picarro. This peripheral device is compatible with Picarro CRDS isotopic water analyzers, allowing real-time, continuous isotopic measurements of liquid water. The new device, which expands upon the design of Munskgaard et al. (2011), utilizes expanded polytetrafluoroethylene (ePTFE) membrane technology to continuously generate gas-phase water, while liquid water is pumped through the system. The water vapor subsequently travels to the CRDS analyzer where the isotopic ratios are measured and recorded. The generation of water vapor using membrane technology is sensitive to environmental conditions, which if not actively control, lead to sustainable experimental noise and drift. Consequently, our

Controls on water vapor isotopes over Roorkee, India: Impact of convective activities and depression systems

NASA Astrophysics Data System (ADS)

Saranya, P.; Krishan, Gopal; Rao, M. S.; Kumar, Sudhir; Kumar, Bhishm

2018-02-01

The study evaluates the water vapor isotopic compositions and its controls with special reference to Indian Summer Monsoon (ISM) season at Roorkee, India. Precipitation is usually a discrete event spatially and temporally in this part of the country, therefore, the information provided is limited, while, the vapors have all time availability and have a significant contribution in the hydrological cycle locally or over a regional scale. Hence for understanding the processes altering the various sources, its isotopic signatures were studied. The Isotope Water Vapour Line (Iso Val) was drawn together with the Global Meteoric Water Line (GMWL) and the best fit line was δD = 5.42 * δ18O + 27.86. The precipitation samples were also collected during the study period and were best fitted with δD = 8.20(±0.18) * δ18O + 9.04(±1.16) in the Local Meteoric Water Line (LMWL). From the back trajectory analysis of respective vapor samples, it is unambiguous that three major sources viz; local vapor, western disturbance and monsoon vapor are controlling the fate of moisture over Roorkee. The d-excess in ground-level vapor (GLV) reveals the supply of recycled moisture from continental water bodies and evapo-transpiration as additional moisture sources to the study area. The intensive depletion in isotopic ratios was associated with the large-scale convective activity and low-pressure/cyclonic/depression systems formed over Bay of Bengal.

Variations in stable hydrogen and oxygen isotopes in atmospheric water vapor in the marine boundary layer across a wide latitude range.

PubMed

Liu, Jingfeng; Xiao, Cunde; Ding, Minghu; Ren, Jiawen

2014-11-01

The newly-developed cavity ring-down laser absorption spectroscopy analyzer with special calibration protocols has enabled the direct measurement of atmospheric vapor isotopes at high spatial and temporal resolution. This paper presents real-time hydrogen and oxygen stable isotope data for atmospheric water vapor above the sea surface, over a wide range of latitudes spanning from 38°N to 69°S. Our results showed relatively higher values of δ(18)O and δ(2)H in the subtropical regions than those in the tropical and high latitude regions, and also a notable decreasing trend in the Antarctic coastal region. By combining the hydrogen and oxygen isotope data with meteoric water line and backward trajectory model analysis, we explored the kinetic fractionation caused by subsiding air masses and related saturated vapor pressure in the subtropics, and the evaporation-driven kinetic fractionation in the Antarctic region. Simultaneous observations of meteorological and marine variables were used to interpret the isotopic composition characteristics and influential factors, indicating that d-excess is negatively correlated with humidity across a wide range of latitudes and weather conditions worldwide. Coincident with previous studies, d-excess is also positively correlated with sea surface temperature and air temperature (Tair), with greater sensitivity to Tair. Thus, atmospheric vapor isotopes measured with high accuracy and good spatial-temporal resolution could act as informative tracers for exploring the water cycle at different regional scales. Such monitoring efforts should be undertaken over a longer time period and in different regions of the world. Copyright © 2014. Published by Elsevier B.V.

[Monitoring and Analysis of Stable Isotopes of the Near Surface Water Vapor in Changsha].

PubMed

Xie, Yu-long; Zhang, Xin-ping; Yao, Tian-ci; Huang, Huang

2016-02-15

Based on the monitored atmospheric water vapor stable isotopes and observed meteorological elements at Changsha during the period from November 12, 2014 to April 13, 2015, the variations of water vapor stable isotopes and the relationships between isotope ratios and temperature, absolute humidity, precipitation amount were analyzed in this paper. The results indicated that: (1) Seasonal variations of delta18O and 82H in atmospheric water vapor at Changsha were remarkable, with high values in winter. delta18O and delta2H in atmospheric water vapor were positively correlated with absolute humidity in winter. There were some fluctuations of the delta18O and delta2H in atmospheric water vapor, especially when the precipitation events occurred. Precipitation events had a significant effect on the variations of delta18O and delta2H in atmospheric water vapor, and low values were often accompanied with precipitation events; (2) Diurnal Variations of delta18O and delta2H in atmospheric water vapor had a close correlation with the atmospheric water vapor content, whereas the absolute humidity was mainly controlled by the strength of the local evapotranspiration and atmospheric turbulence. The "precipitation amount effect" was observed during the process of a single precipitation event; (3) Values of delta18O and delta2H in atmospheric water vapor were always lower than those of precipitation in Changsha, but he variation trends were completely consistent, the average difference values were 8.6% per hundred and 66.82% per hundred, respectively; (4) The meteoric vapor line (MVL) in cold months was delta2H =7.18 delta18O + 10.58, the slope and intercept of MVL were always lower than those of MWL, and the slope and intercept of MVL in spring were significantly higher than those of winter.

Partitioning of sublimation and evaporation from Lake Bonney using water vapor isotope and latent heat fluxes

NASA Astrophysics Data System (ADS)

Bellagamba, A. W.; Berkelhammer, M. B.; Winslow, L.; Peter, D.; Myers, K. F.

2017-12-01

The landscapes of the McMurdo Dry Valleys in Antarctica are characterized by a series of frozen lakes. Although the conditions in this region are severe, the lakes share common characteristics with lakes at glacial termini elsewhere. Geochemical and geomorphological evidence suggest these lakes have experienced large historical changes indicative of changes water balances. While part of these shifts in lake volume arise from changes in glacial inflow, they likely also reflect changes in the latent heat flux from the lake surfaces. Here we present a joint analysis of the stable isotopic ratio of surface ice/water and the water vapor flux over Dry Valley frozen lakes to ascertain the processes controlling water losses from the lake surfaces. We compare the isotopic ratio of the latent heat flux with the surface water isotopes to derive a fractionation factor associated with latent flux. This data is then used to provide insight into how much of the water vapor flux is sublimated versus evaporated, as well as how the sublimation and evaporative components of the flux change with synoptic weather. We used a Picarro L2130-I isotopic water analyzer to measure humidity and the isotopic ratio of water vapor at three heights over Lake Bonney in Taylor Valley, Antarctica and used the flux-gradient approach to convert the isotopic ratio of the vapor to an "isoflux". An on-site meteorological station recorded temperature, relative humidity and wind direction/intensity at two different heights above the lake and an infrared radiometer recorded lake skin temperature. These data were used to calculate the sensible and latent heat fluxes. The fractionation factor was close to 0, which indicates that sublimation was the primary component of the flux although evaporation became increasingly prominent following a katabatic wind event. The results suggest this technique could be an effective tool to study the sensitivity of latent heat fluxes to weather here and in other similar

Partitioning evapotranspiration via continuous sampling of water vapor isotopes over common row crops and candidate biofuel crops.

NASA Astrophysics Data System (ADS)

Miller, J. N.; Black, C. K.; Bernacchi, C.

2014-12-01

Global demand for renewable energy is accelerating land conversion from common row crops such as maize and soybean to cellulosic biofuel crops such as miscanthus and switchgrass. This land conversion is expected to alter ecohydrology via changes in evapotranspiration (ET). However, the direction in which evapotranspiration will shift, either partitioning more moisture through soil evaporation (E) or through plant transpiration (T) is uncertain. To investigate how land conversion from maize to miscanthus affects ET partitioning we measured the isotopic composition of water vapor via continuous air sampling. We obtained continuous diurnal measurements of δ2H and δ18O for miscanthus and maize on multiple days over the course of the growing season. Water vapor isotopes drawn from two heights were measured at 2 Hz using a cavity ringdown spectrometer and partitioned into components of E and T using a simple mixing equation. A second approach to partitioning was accomplished by subtracting transpiration measurements, obtained through sap flow sensors, from total ET, measured via eddy covariance. Preliminary results reveal that both methods compare favorably and that transpiration dominates variations in ET in miscanthus fields more so than in fields of maize.

Oxygen isotope anomaly observed in water vapor from Alert, Canada and the implication for the stratosphere

PubMed Central

Lin, Ying; Clayton, Robert N.; Huang, Lin; Nakamura, Noboru; Lyons, James R.

2013-01-01

To identify the possible anomalous oxygen isotope signature in stratospheric water predicted by model studies, 25 water vapor samples were collected in 2003−2005 at Alert station, Canada (82°30′N), where there is downward transport of stratospheric air to the polar troposphere, and were analyzed for δ17O and δ18O relative to Chicago local precipitation (CLP). The latter was chosen as a reference because the relatively large evaporative moisture source should erase any possible oxygen isotope anomaly from the stratosphere. A mass-dependent fractionation coefficient for meteoric waters, λMDF(H2O) = 0.529 ± 0.003 [2σ standard error (SE)], was determined from 27 CLP samples collected in 2003−2005. An oxygen isotopic anomaly of Δ17O = 76 ± 16 ppm (2σ SE) was found in water vapor samples from Alert relative to CLP. We propose that the positive oxygen isotope anomalies observed at Alert originated from stratospheric ozone, were transferred to water in the stratosphere, and subsequently mixed with tropospheric water at high latitudes as the stratospheric air descended into the troposphere. On the basis of this ground signal, the average Δ17O in stratospheric water vapor predicted by a steady-state box model is ∼40‰. Seven ice core samples (1930−1991) from Dasuopu glacier (Himalayas, China) and Standard Light Antarctic Precipitation did not show an obvious oxygen isotope anomaly, and Vienna Standard Mean Ocean Water exhibited a negative Δ17O relative to CLP. Six Alert snow samples collected in March 2011 and measured at Laboratoire des Sciences du Climat et de l'Environnement, Gif sur Yvette, France, had 17Oexcess of 45 ± 5 ppm (2σ SE) relative to Vienna Standard Mean Ocean Water. PMID:24009339

Aerosol mass spectrometry: particle-vaporizer interactions and their consequences for the measurements

NASA Astrophysics Data System (ADS)

Drewnick, F.; Diesch, J.-M.; Faber, P.; Borrmann, S.

2015-09-01

The Aerodyne aerosol mass spectrometer (AMS) is a frequently used instrument for on-line measurement of the ambient sub-micron aerosol composition. With the help of calibrations and a number of assumptions on the flash vaporization and electron impact ionization processes, this instrument provides robust quantitative information on various non-refractory ambient aerosol components. However, when measuring close to certain anthropogenic or marine sources of semi-refractory aerosols, several of these assumptions may not be met and measurement results might easily be incorrectly interpreted if not carefully analyzed for unique ions, isotope patterns, and potential slow vaporization associated with semi-refractory species. Here we discuss various aspects of the interaction of aerosol particles with the AMS tungsten vaporizer and the consequences for the measurement results: semi-refractory components - i.e., components that vaporize but do not flash-vaporize at the vaporizer and ionizer temperatures, like metal halides (e.g., chlorides, bromides or iodides of Al, Ba, Cd, Cu, Fe, Hg, K, Na, Pb, Sr, Zn) - can be measured semi-quantitatively despite their relatively slow vaporization from the vaporizer. Even though non-refractory components (e.g., NH4NO3 or (NH4)2SO4) vaporize quickly, under certain conditions their differences in vaporization kinetics can result in undesired biases in ion collection efficiency in thresholded measurements. Chemical reactions with oxygen from the aerosol flow can have an influence on the mass spectra for certain components (e.g., organic species). Finally, chemical reactions of the aerosol with the vaporizer surface can result in additional signals in the mass spectra (e.g., WO2Cl2-related signals from particulate Cl) and in conditioning or contamination of the vaporizer, with potential memory effects influencing the mass spectra of subsequent measurements. Laboratory experiments that investigate these particle-vaporizer interactions are

Aircraft profile measurements of 18O/16O and D/H isotope ratios of cloud condensate and water vapor constrain precipitation efficiency and entrainment rates in tropical clouds

NASA Astrophysics Data System (ADS)

Noone, D. C.; Raudzens Bailey, A.; Toohey, D. W.; Twohy, C. H.; Heymsfield, A.; Rella, C.; Van Pelt, A. D.

2011-12-01

Convective clouds play a significant role in the moisture and heat balance of the tropics. The dynamics of organized and isolated convection are a function of the background thermodynamic profile and wind shear, buoyancy sources near the surface and the latent heating inside convective updrafts. The stable oxygen and hydrogen isotope ratios in water vapor and condensate can be used to identify dominant moisture exchanges and aspects of the cloud microphysics that are otherwise difficult to observe. Both the precipitation efficiency and the dilution of cloud updrafts by entrainment can be estimated since the isotopic composition outside the plume is distinct from inside. Measurements of the 18O/16O and D/H isotope ratios were made in July 2011 on 13 research flights of the NCAR C130 aircraft during the ICE-T (Ice in Clouds Experiment - Tropical) field campaign near St Croix. Measurements were made using an instrument based on the Picarro Wave-Length Scanning Cavity Ring Down platform that includes a number of optical, hardware and software modifications to allow measurements to be made at 5 Hz for deployment on aircraft. The measurement system was optimized to make precise measurements of the isotope ratio of liquid and ice cloud condensate by coupling the gas analyzer to the NCAR Counter flow Virtual Impactor inlet. The inlet system provides a particle enhancement while rejecting vapor. Sample air is vigorously heated before flowing into the gas phase analyzer. We present statistics that demonstrate the performance and calibration of the instrument. Measured profiles show that environmental air exhibits significant layering showing controls from boundary layer processes, large scale horizontal advection and regional subsidence. Condensate in clouds is consistent with generally low precipitation efficiency, although there is significant variability in the isotope ratios suggesting heterogeneity within plumes and the stochastic nature of detrainment processes

Forest Canopy Water Cycling Responses to an Intermediate Disturbance Revealed Through Stable Water Vapor Isotopes

NASA Astrophysics Data System (ADS)

Fiorella, R.; Poulsen, C. J.; Matheny, A. M.; Rey Sanchez, C.; Fotis, A. T.; Morin, T. H.; Vogel, C. S.; Gough, C. M.; Aron, P.; Bohrer, G.

2016-12-01

Forest structure, age, and species composition modulate fluxes of carbon and water between the land surface and the atmosphere. The response of forests to intermediate disturbances such as ecological succession, species-specific insect invasion, or selective logging that disrupt the canopy but do not promote complete stand replacement, shape how these fluxes evolve through time. We investigate the impact of an intermediate disturbance to water cycling processes by comparing vertical profiles of stable water isotopes in two closely located forest canopies in the northern lower peninsula of Michigan using cavity ring-down spectroscopy. In one of the canopies, an intermediate disturbance was prescribed in 2008 by inducing mortality in all canopy-dominant early successional species. Isotopic compositions of atmospheric water vapor are measured at six heights during two time periods (summer and early fall) at two flux towers and compared with local meteorology and calculated atmospheric back-trajectories. Disturbance has little impact on low-frequency changes in isotopic composition (e.g., >1 day); at these timescales, isotopic composition is strongly related to large-scale moisture transport. In contrast, disturbance has substantial impacts on the vertical distribution of water isotopes throughout the canopy when transpiration rates are high during the summer, but impact is muted during early fall. Sub-diurnal differences in canopy water vapor cycling are likely related to differences in species composition and response to disturbance and changes in canopy structure. Predictions of transpiration fluxes by land-surface models that do not account species-specific relationships and canopy structure are unlikely to capture these relationships, but addition of stable isotopes to land surface models may provide a useful parameter to improve these predictions.

Water vapor δ(2) H, δ(18) O and δ(17) O measurements using an off-axis integrated cavity output spectrometer - sensitivity to water vapor concentration, delta value and averaging-time.

PubMed

Tian, Chao; Wang, Lixin; Novick, Kimberly A

2016-10-15

High-precision analysis of atmospheric water vapor isotope compositions, especially δ(17) O values, can be used to improve our understanding of multiple hydrological and meteorological processes (e.g., differentiate equilibrium or kinetic fractionation). This study focused on assessing, for the first time, how the accuracy and precision of vapor δ(17) O laser spectroscopy measurements depend on vapor concentration, delta range, and averaging-time. A Triple Water Vapor Isotope Analyzer (T-WVIA) was used to evaluate the accuracy and precision of δ(2) H, δ(18) O and δ(17) O measurements. The sensitivity of accuracy and precision to water vapor concentration was evaluated using two international standards (GISP and SLAP2). The sensitivity of precision to delta value was evaluated using four working standards spanning a large delta range. The sensitivity of precision to averaging-time was assessed by measuring one standard continuously for 24 hours. Overall, the accuracy and precision of the δ(2) H, δ(18) O and δ(17) O measurements were high. Across all vapor concentrations, the accuracy of δ(2) H, δ(18) O and δ(17) O observations ranged from 0.10‰ to 1.84‰, 0.08‰ to 0.86‰ and 0.06‰ to 0.62‰, respectively, and the precision ranged from 0.099‰ to 0.430‰, 0.009‰ to 0.080‰ and 0.022‰ to 0.054‰, respectively. The accuracy and precision of all isotope measurements were sensitive to concentration, with the higher accuracy and precision generally observed under moderate vapor concentrations (i.e., 10000-15000 ppm) for all isotopes. The precision was also sensitive to the range of delta values, although the effect was not as large compared with the sensitivity to concentration. The precision was much less sensitive to averaging-time than the concentration and delta range effects. The accuracy and precision performance of the T-WVIA depend on concentration but depend less on the delta value and averaging-time. The instrument can

Origin of isotopically light Zn in lunar samples through vaporization and the Zn isotope composition of the Moon

NASA Astrophysics Data System (ADS)

Kato, C.; Valdes, M. C.; Dhaliwal, J.; Day, J. M.; Moynier, F.

2013-12-01

the surface of the Moon. This represents secondary effects and mixing with exogenous Zn, explaining the higher abundance of Zn in highland rocks, relative to mare basalts. The pyroclastic green glass (15426) has a higher measured Zn concentration (~50ppm) compared with mare basalts, but is still depleted in Zn relative to most terrestrial basalts (typically >50 to 100 ppm). 15426 is also isotopically light (δ66Zn= -0.98), which is similar to previous measurements of Zn composition made for high-Ti pyroclastic glass beads (74220). We interpret the composition of the lunar pyroclastic glasses to reflect lava fountaining and coating of the surface of the beads by a volatile rich and isotopically light vapor. Thus, we conclude that mare basalts, which are isotopically heavier than the Earth, best represent the lunar silicate composition.

Method and apparatus to measure vapor pressure in a flow system

DOEpatents

Grossman, Mark W.; Biblarz, Oscar

1991-01-01

The present invention is directed to a method for determining, by a condensation method, the vapor pressure of a material with a known vapor pressure versus temperature characteristic, in a flow system particularly in a mercury isotope enrichment process.

Using Stable Isotopes in Water Vapor to Diagnose Relationships Between Lower-Tropospheric Stability, Mixing, and Low-Cloud Cover Near the Island of Hawaii

NASA Astrophysics Data System (ADS)

Galewsky, Joseph

2018-01-01

In situ measurements of water vapor isotopic composition from Mauna Loa, Hawaii, are merged with soundings from Hilo to show an inverse relationship between the estimated inversion strength (EIS) and isotopically derived measures of lower-tropospheric mixing. Remote sensing estimates of cloud fraction, cloud liquid water path, and cloud top pressure were all found to be higher (lower) under low (high) EIS. Inverse modeling of the isotopic data corresponding to terciles of EIS conditions provide quantitative constraints on the last-saturation temperatures and mixing fractions that govern the humidity above the trade inversion. The mixing fraction of water vapor transported from the boundary layer to Mauna Loa decreases with respect to EIS at a rate of about 3% K-1, corresponding to a mixing ratio decrease of 0.6 g kg-1 K-1. A last-saturation temperature of 240 K can match all observations. This approach can be applied in other settings and may be used to test models of low-cloud climate feedbacks.

Method and apparatus to measure vapor pressure in a flow system

DOEpatents

Grossman, M.W.; Biblarz, O.

1991-10-15

The present invention is directed to a method for determining, by a condensation method, the vapor pressure of a material with a known vapor pressure versus temperature characteristic, in a flow system particularly in a mercury isotope enrichment process. 2 figures.

First In-situ Measurements of the HDO/H2O Isotopic Ratio in the Asian Summer Monsoon

NASA Astrophysics Data System (ADS)

Clouser, B.; Sarkozy, L.; Gaeta, D. C.; Singer, C. E.; Moyer, E. J.

2017-12-01

The Asian monsoon is one of the world's largest weather systems, and forms one of the main pathways by which water vapor enters the UT/LS. Satellite measurements of the HDO/H2O ratio of UT/LS water, a strong tracer of convective origin, have suggested significant differences in transport behavior between the Asian and North American monsoons, with strong UT/LS enhancement occurring only over North America. We report here the first in-situ measurements of the HDO/H2O ratio in the Asian monsoon, that help resolve this discrepancy. The Chicago Water Isotope Spectrometer (Chi-WIS) participated in the July/August 2017 StratoClim campaign, measuring water vapor and its isotopic composition between 12 and 20 kilometers. We use these measurements to diagnose the importance of overshooting convection in water transport by the Asian monsoon, and to characterize the extent to which convection-driven water vapor perturbations propagate to higher altitudes and contribute to the overall stratospheric water budget.

Water vapor d2H dynamics over China derived from SCIAMACHY satellite measurements

USDA-ARS?s Scientific Manuscript database

This study investigates water vapor isotopic patterns and controls over China using high-quality water vapor delta2H data retrieved from Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) observations. The results show that water vapor delta2H values on both annual and...

On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals

NASA Astrophysics Data System (ADS)

Bauska, T.; Hodell, D. A.; Walters, G.

2016-12-01

Oxygen (16O,17O,18O) and hydrogen (H,D) isotopes of hydration water in minerals provide a rich source of information about the conditions under which hydrated minerals form on Earth and other planetary bodies (e.g. Mars). We have developed a new method for measuring different types of bonded water (e.g., molecular, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves step heating a mineral sample, precisely measuring the weight loss and enthalpy as the sample undergoes dehydration and dehydroxylation, whilst simultaneously determining the oxygen and hydrogen isotopes of the water vapor evolved from the mineral sample by cavity ring-down laser spectroscopy (CRDS). Nitrogen carrier gas is used to transfer the sample from the TG to the CRDS via a heated line and interface box. The interface includes the capability of (i) cryogenic trapping discrete types of water for samples containing small amounts of water; (ii) injecting small quantities of water of known isotopic value for calibration; and (iii) converting volatile organic compounds to nascent amounts of water using a catalyst. The CRDS continually measures water vapor concentration in the optical cavity and hydrogen and oxygen isotope ratios. Isotopic values are calculated by integrating the product of the water amount and its isotopic value for the separated peaks after correcting for background. Precision of the method was estimated by comparing isotope results of total water for gypsum measured by DTIA with our conventional method of extraction and analysis (Gázquez et al., 2015. Rapid Communications in Mass Spectrometry, 29, 1997-2006). Errors for the isotopic values of total hydration water vary between ±0.08 and ±0.34 ‰ for δ18O and between ±0.16 and ±0.86 ‰ for δD. We demonstrate the application of the DTIA method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous

Fractionation of Cu and Mo isotopes caused by vapor-liquid partitioning, evidence from the Dahutang W-Cu-Mo ore field

NASA Astrophysics Data System (ADS)

Yao, Junming; Mathur, Ryan; Sun, Weidong; Song, Weile; Chen, Huayong; Mutti, Laurence; Xiang, Xinkui; Luo, Xiaohong

2016-05-01

The study presents δ65Cu and δ97Mo isotope values from cogenetic chalcopyrite and molybdenite found in veins and breccias of the Dahutang W-Cu-Mo ore field in China. The samples span a 3-4 km range. Both isotopes show a significant degree of fractionation. Cu isotope values in the chalcopyrite range from -0.31‰ to +1.48‰, and Mo isotope values in the molybdenite range from -0.03‰ to +1.06‰. For the cogenetic sulfide veined samples, a negative slope relationship exists between δ65Cu and δ97Mo values, which suggest a similar fluid history. Rayleigh distillation models the vein samples' change in isotope values. The breccia samples do not fall on the trend, thus indicating a different source mineralization event. Measured fluid inclusion and δD and δ18O data from cogenetic quartz indicate changes in temperature, and mixing of fluids do not appear to cause the isotopic shifts measure. Related equilibrium processes associated with the partitioning of metal between the vapor-fluid in the hydrothermal system could be the probable cause for the relationship seen between the two isotope systems.

Effects of Water Vapor on the Data Quality of the Stable Oxygen Isotopic Ratio of Atmospheric Carbon Dioxide

NASA Astrophysics Data System (ADS)

Evans, C. U.; White, J. W.; Vaughn, B.; Tans, P. P.; Pardo, L.

2007-12-01

The stable oxygen isotopic ratio of carbon dioxide can potentially track fundamental indicators of environmental change such as the balance between photosynthesis and respiration on regional to global scales. The Stable Isotope Laboratory (SIL) at the Institute of Arctic and Alpine Research (INSTAAR), University of Colorado at Boulder, has measured the stable isotopes of atmospheric carbon dioxide from more than 60 NOAA/Earth System Research Laboratory (ESRL) air flask-sampling sites since the early 1990s. If air is sampled without drying, oxygen can exchange between carbon dioxide and water in the flasks, entirely masking the desired signal. An attempt to investigate how water vapor is affecting the δ18O signal is accomplished by comparing the SIL measurements with specific humidity, calculated from the National Climatic Data Center (NCDC) global integrated surface hourly temperature and dew point database, at the time of sampling. Analysis of sites where samples have been collected initially without drying, and subsequently with a drying kit, in conjunction with the humidity data, has led to several conclusions. Samples that initially appear isotopically unaltered, in that their δ18O values are within the expected range, are being subtly influenced by the water vapor in the air. At Bermuda and other tropical to semi-tropical sites, the 'wet' sampling values have a seasonal cycle that is strongly anti-correlated to the specific humidity, while the 'dry' values have a seasonal cycle that is shifted earlier than the specific humidity cycle by 1-2 months. The latter phasing is expected given the seasonal phasing between climate over the ocean and land, while the former is consistent with a small, but measurable isotope exchange in the flasks. In addition, we note that there is a strong (r > 0.96) correlation between the average specific humidity and the percent of rejected samples for 'wet' sampling. This presents an opportunity for determining a threshold of

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds

PubMed Central

Lamb, Kara D.; Clouser, Benjamin W.; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J.

2017-01-01

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (−40 °C), conditions necessary to form cirrus clouds in the Earth’s atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122–127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H2O equilibrium fractionation between vapor and ice (αeq) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of αeq, and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice–vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems. PMID:28495968

Laboratory measurements of HDO/H2O isotopic fractionation during ice deposition in simulated cirrus clouds.

PubMed

Lamb, Kara D; Clouser, Benjamin W; Bolot, Maximilien; Sarkozy, Laszlo; Ebert, Volker; Saathoff, Harald; Möhler, Ottmar; Moyer, Elisabeth J

2017-05-30

The stable isotopologues of water have been used in atmospheric and climate studies for over 50 years, because their strong temperature-dependent preferential condensation makes them useful diagnostics of the hydrological cycle. However, the degree of preferential condensation between vapor and ice has never been directly measured at temperatures below 233 K (-40 °C), conditions necessary to form cirrus clouds in the Earth's atmosphere, routinely observed in polar regions, and typical for the near-surface atmospheric layers of Mars. Models generally assume an extrapolation from the warmer experiments of Merlivat and Nief [Merlivat L, Nief G (1967) Tellus 19:122-127]. Nonequilibrium kinetic effects that should alter preferential partitioning have also not been well characterized experimentally. We present here direct measurements of HDO/H 2 O equilibrium fractionation between vapor and ice ([Formula: see text]) at cirrus-relevant temperatures, using in situ spectroscopic measurements of the evolving isotopic composition of water vapor during cirrus formation experiments in a cloud chamber. We rule out the recent proposed upward modification of [Formula: see text], and find values slightly lower than Merlivat and Nief. These experiments also allow us to make a quantitative validation of the kinetic modification expected to occur in supersaturated conditions in the ice-vapor system. In a subset of diffusion-limited experiments, we show that kinetic isotope effects are indeed consistent with published models, including allowing for small surface effects. These results are fundamental for inferring processes on Earth and other planets from water isotopic measurements. They also demonstrate the utility of dynamic in situ experiments for studying fractionation in geochemical systems.

Evaluation of soil water stable isotope analysis by H2O(liquid)-H2O(vapor) equilibration method

NASA Astrophysics Data System (ADS)

Gralher, Benjamin; Stumpp, Christine

2014-05-01

Environmental tracers like stable isotopes of water (δ18O, δ2H) have proven to be valuable tools to study water flow and transport processes in soils. Recently, a new technique for soil water isotope analysis has been developed that employs a vapor phase being in isothermal equilibrium with the liquid phase of interest. This has increased the potential application of water stable isotopes in unsaturated zone studies as it supersedes laborious extraction of soil water. However, uncertainties of analysis and influencing factors need to be considered. Therefore, the objective of this study was to evaluate different methodologies of analysing stable isotopes in soil water in order to reduce measurement uncertainty. The methodologies included different preparation procedures of soil cores for equilibration of vapor and soil water as well as raw data correction. Two different inflatable sample containers (freezer bags, bags containing a metal layer) and equilibration atmospheres (N2, dry air) were tested. The results showed that uncertainties for δ18O were higher compared to δ2H that cannot be attributed to any specific detail of the processing routine. Particularly, soil samples with high contents of organic matter showed an apparent isotope enrichment which is indicative for fractionation due to evaporation. However, comparison of water samples obtained from suction cups with the local meteoric water line indicated negligible fractionation processes in the investigated soils. Therefore, a method was developed to correct the raw data reducing the uncertainties of the analysis.. We conclude that the evaluated method is advantageous over traditional methods regarding simplicity, resource requirements and sample throughput but careful consideration needs to be made regarding sample handling and data processing. Thus, stable isotopes of water are still a good tool to determine water flow and transport processes in the unsaturated zone.

Water isotope ratio (δ2H and δ18O) measurements in atmospheric moisture using an optical feedback cavity enhanced absorption laser spectrometer

NASA Astrophysics Data System (ADS)

Iannone, Rosario Q.; Romanini, Daniele; Cattani, Olivier; Meijer, Harro A. J.; Kerstel, Erik R. Th.

2010-05-01

Water vapor isotopes represent an innovative and excellent tool for understanding complex mechanisms in the atmospheric water cycle over different time scales, and they can be used for a variety of applications in the fields of paleoclimatology, hydrology, oceanography, and ecology. We use an ultrasensitive near-infrared spectrometer, originally designed for use on airborne platforms in the upper troposphere and lower stratosphere, to measure the water deuterium and oxygen-18 isotope ratios in situ, in ground-level tropospheric moisture, with a high temporal resolution (from 300 s down to less than 1 s). We present some examples of continuous monitoring of near-surface atmospheric moisture, demonstrating that our infrared laser spectrometer could be used successfully to record high-concentration atmospheric water vapor mixing ratios in continuous time series, with a data coverage of ˜90%, interrupted only for daily calibration to two isotope ratio mass spectrometry-calibrated local water standards. The atmospheric data show that the water vapor isotopic composition exhibits a high variability that can be related to weather conditions, especially to changes in relative humidity. Besides, the results suggest that observed spatial and temporal variations of the stable isotope content of atmospheric water vapor are strongly related to water vapor transport in the atmosphere.

The effect of heated vapor-phase acidification on organic carbon concentrations and isotopic values in geologic rock samples

NASA Astrophysics Data System (ADS)

Wang, R. Z.; West, A. J.; Yager, J. A.; Rollins, N.; Li, G.; Berelson, W.

2016-12-01

Carbon signatures recorded in the modern and geologic rock record can give insight on the Earth's carbon cycle through time. This is especially true for organic carbon (OC), which can help us understand how the biosphere has evolved over Earth's history. However, carbon recorded in rocks is a combination of OC and inorganic carbon (IC) mostly in the form of carbonate minerals. To measure OC, IC must therefore first be removed through a process called "decarbonation." This is often done through a leaching process with hydrochloric acid (HCl). However, three well known problems exist for the decarbonation process: 1) Incomplete removal of IC, 2) Unintentional removal of OC, and 3) Addition of false carbon blank. Currently, vapor (gas) phase removal of OC is preferred to liquid phase treatment because it has been shown that OC is lost to solubilization during liquid phase acidification. Vapor phase treatment is largely thought to avoid the problem of OC loss, but this has not yet been rigorously investigated. This study investigates that assumption and shows that vapor phase treatment can cause unintentional OC loss. We show that vapor phase treatment must be sensitive to rock type and treatment length to produce robust OC isotopic measurements and concentrations.

Simulated shifts in the mid-latitude storm tracks over the western US detected through isotopes in precipitation and vapor

NASA Astrophysics Data System (ADS)

Buenning, N. H.; Stott, L. D.; Kanner, L.; Yoshimura, K.

2013-12-01

One of the most robust features of climate model projections for the 21st century includes a poleward shift of middle latitude storm tracks in response to enhanced radiative forcing. This study evaluates how shifts in the middle latitude storm tracks over the North Pacific has been expressed in the stable isotopic composition of atmospheric vapor and precipitation in the past 60 years. Previous work has demonstrated how the isotopic composition of precipitation (δ18Op) in the Pacific Northwest and in atmospheric vapor (δ18Ov) across the western US reflects the large-scale atmospheric circulation. Thus, it is possible to use the isotopic composition of water in these regions to detect shifts in mid-latitude storm tracks. Results from the Isotope-incorporated Global Spectral Model (IsoGSM) are presented to better understand the recent low frequency variations in δ18O values over the western US. The IsoGSM simulations presented here were spectrally nudged every six hours to the NCEP/NCAR Reanalysis wind and temperature fields. The spectral nudging technique allows for realistic isotopic simulations that are consistent with observed large-scale mid-latitude storm systems. Model results suggest that δ18Op has risen over the Pacific Northwest and δ18Ov has increased across the western US since the 1950s (see Figure), an indication of more moisture advection from the tropics and less moisture transported from the middle latitudes. Water tagging simulations reveal that as δ18Ov increased in the western US, the fraction of vapor from the subtropics had also increased, while the fraction from the middle latitudes had decreased. Similarly, the tagging simulations resulted in increased subtropical precipitation falling in the Pacific Northwest and decreased precipitation from the middle latitudes. These model simulations suggest that a northward shift in storm tracks has already taken place over the last 60 years in the western US. Furthermore, the results underscore the

Relationships between lower tropospheric stability, low cloud cover, and water vapor isotopic composition in the subtropical Pacific

NASA Astrophysics Data System (ADS)

Galewsky, J.

2017-12-01

Understanding the processes that govern the relationships between lower tropospheric stability and low-cloud cover is crucial for improved constraints on low-cloud feedbacks and for improving the parameterizations of low-cloud cover used in climate models. The stable isotopic composition of atmospheric water vapor is a sensitive recorder of the balance of moistening and drying processes that set the humidity of the lower troposphere and may thus provide a useful framework for improving our understanding low-cloud processes. In-situ measurements of water vapor isotopic composition collected at the NOAA Mauna Loa Observatory in Hawaii, along with twice-daily soundings from Hilo and remote sensing of cloud cover, show a clear inverse relationship between the estimated inversion strength (EIS) and the mixing ratios and water vapor δ -values, and a positive relationship between EIS, deuterium excess, and Δ δ D, defined as the difference between an observation and a reference Rayleigh distillation curve. These relationships are consistent with reduced moistening and an enhanced upper-tropospheric contribution above the trade inversion under high EIS conditions and stronger moistening under weaker EIS conditions. The cloud fraction, cloud liquid water path, and cloud-top pressure were all found to be higher under low EIS conditions. Inverse modeling of the isotopic data for the highest and lowest terciles of EIS conditions provide quantitative constraints on the cold-point temperatures and mixing fractions that govern the humidity above the trade inversion. The modeling shows the moistening fraction between moist boundary layer air and dry middle tropospheric air 24±1.5% under low EIS conditions is and 6±1.5% under high EIS conditions. A cold-point (last-saturation) temperature of -30C can match the observations for both low and high EIS conditions. The isotopic composition of the moistening source as derived from the inversion (-114±10‰ ) requires moderate

Coupling Stable Water Isotopes in Vapor and Precipitation to Raindrop Size Distributions at a Mid-latitude Tall-tower Site to Evaluate the Role of Rain Evaporation in Boundary Layer Moisture Recycling

NASA Astrophysics Data System (ADS)

Kaushik, A.; Noone, D.

2016-12-01

The continental boundary layer moisture balance plays an important role in regulating water and energy exchange between the surface and the atmosphere, yet the mechanisms associated with moistening and drying are both poorly observed and modeled. Stable water isotope ratio measurements can provide insights into air mass origins, convection dynamics and mechanisms dominating atmosphere-land surface water fluxes. Profiles can be exploited to improve estimates of boundary layer moistening associated with evaporation of falling precipitation and contributions from surface evapotranspiration. We present two years of in situ tower-based measurements of isotope ratios of water vapor and precipitation (δD and δ18O) and raindrop size distributions from the Boulder Atmospheric Observatory (BAO) tall-tower site in Erie, Colorado. Isotope vapor measurements were made at 1 Hz with a full cycle from the surface to 300 meters recorded every 80 minutes. At the surface and 300m, water samples were collected during precipitation events and raindrop sizes were measured continuously using Parsivel instruments. We use this unique suite of measurements and, in particular, exploit the differences between the surface and 300m observations to constrain the surface layer hydrological mass balance during and after rain events, and evaluate parameterization choices for rain evaporation and moisture recycling in current isotope-enabled climate models. Aggregate raindrop size measurements showed shifts from populations of smaller raindrops at 300m to larger raindrops at the surface, contrary to what is expected for rain evaporation. Convective storms resulted in more uniform signatures between the surface and 300m, as well as longer isotope equilibration and adjustment time scales, whereas low Dexcess signatures (<9 to negative) during stratiform drizzle events were indicative of a greater degree of rain evaporation. Our observational results suggest that water vapor-rain equilibration is

Assessing the ability of isotope-enabled General Circulation Models to simulate the variability of Iceland water vapor isotopic composition

NASA Astrophysics Data System (ADS)

Erla Sveinbjornsdottir, Arny; Steen-Larsen, Hans Christian; Jonsson, Thorsteinn; Ritter, Francois; Riser, Camilla; Messon-Delmotte, Valerie; Bonne, Jean Louis; Dahl-Jensen, Dorthe

2014-05-01

During the fall of 2010 we installed an autonomous water vapor spectroscopy laser (Los Gatos Research analyzer) in a lighthouse on the Southwest coast of Iceland (63.83°N, 21.47°W). Despite initial significant problems with volcanic ash, high wind, and attack of sea gulls, the system has been continuously operational since the end of 2011 with limited down time. The system automatically performs calibration every 2 hours, which results in high accuracy and precision allowing for analysis of the second order parameter, d-excess, in the water vapor. We find a strong linear relationship between d-excess and local relative humidity (RH) when normalized to SST. The observed slope of approximately -45 o/oo/% is similar to theoretical predictions by Merlivat and Jouzel [1979] for smooth surface, but the calculated intercept is significant lower than predicted. Despite this good linear agreement with theoretical calculations, mismatches arise between the simulated seasonal cycle of water vapour isotopic composition using LMDZiso GCM nudged to large-scale winds from atmospheric analyses, and our data. The GCM is not able to capture seasonal variations in local RH, nor seasonal variations in d-excess. Based on daily data, the performance of LMDZiso to resolve day-to-day variability is measured based on the strength of the correlation coefficient between observations and model outputs. This correlation coefficient reaches ~0.8 for surface absolute humidity, but decreases to ~0.6 for δD and ~0.45 d-excess. Moreover, the magnitude of day-to-day humidity variations is also underestimated by LMDZiso, which can explain the underestimated magnitude of isotopic depletion. Finally, the simulated and observed d-excess vs. RH has similar slopes. We conclude that the under-estimation of d-excess variability may partly arise from the poor performance of the humidity simulations.

Stable isotopes in water vapor and rainwater over Indian sector of Southern Ocean and estimation of fraction of recycled moisture.

PubMed

Rahul, P; Prasanna, K; Ghosh, Prosenjit; Anilkumar, N; Yoshimura, Kei

2018-05-15

Stable Hydrogen and Oxygen isotopic composition of water vapor, rainwater and surface seawater show a distinct trend across the latitude over the Southern Indian Ocean. Our observations on isotopic composition of surface seawater, water vapor and rainwater across a transect covering the tropical Indian Ocean to the regions of the Southern Ocean showed a strong latitudinal dependency; characterized by the zonal process of evaporation and precipitation. The sampling points were spread across diverse zones of SST, wind speed and rainfall regimes. The observed physical parameters such as sea surface temperature, wind speed and relative humidity over the oceanic regions were used in a box model calculation across the latitudes to predict the isotopic composition of water vapor under equilibrium and kinetic conditions, and compared with results from isotope enabled global spectral model. Further, we obtained the average fraction of recycled moisture across the oceanic transect latitudes as 13.4 ± 7.7%. The values of recycled fraction were maximum at the vicinity of the Inter Tropical Convergence Zone (ITCZ), while the minimum values were recorded over the region of subsidence and evaporation, at the Northern and Southern latitudes of the ITCZ. These estimates are consistent with the earlier reported recyling values.

Membrane inlet laser spectroscopy to measure H and O stable isotope compositions of soil and sediment pore water with high sample throughput

DOE PAGES

Oerter, Erik J.; Perelet, Alexei; Pardyjak, Eric; ...

2016-10-20

Here, the fast and accurate measurement of H and O stable isotope compositions (δ 2H and δ 18O values) of soil and sediment pore water remains an impediment to scaling-up the application of these isotopes in soil and vadose hydrology. Here we describe a method and its calibration to measuring soil and sediment pore water δ 2H and δ 18O values using a water vapor-permeable probe coupled to an isotope ratio infrared spectroscopy analyzer.

Using water vapor isotopes to examine evapotranspiration dynamics in corn and miscanthus reveals challenges to the technique as well as seasonal differences between crops.

NASA Astrophysics Data System (ADS)

Miller, J. N.; Bernacchi, C.

2016-12-01

Second-generation biofuel crops are being planted at an increasing extent around the globe. Changing land use from common field crops to perennial biofuel crops such as miscanthus or switchgrass is expected to alter ecohydrology via changes in evapotranspiration (ET). However, the direction in which evapotranspiration will shift, either partitioning more moisture through soil evaporation (E) or through plant transpiration (T) is uncertain. To investigate how land conversion from maize to miscanthus affects ET partitioning we measured the isotopic composition of water vapor via continuous air sampling. We obtained continuous diurnal measurements of δ2H and δ18O for miscanthus and maize on multiple days over the course of the growing season. Water vapor isotopes drawn from two heights were measured at 2 Hz using a cavity ringdown spectrometer and partitioned into components of E and T using a simple mixing equation. Partitioning was also accomplished with a combination of sap flow sensors and soil lysimeters. Preliminary results reveal that while daily transpiration fraction can be strongly influenced by meteorological events, the whole season transpiration fraction dominates variations in ET in miscanthus fields more so than in fields of maize.

Vapor pressure measured with inflatable plastic bag

NASA Technical Reports Server (NTRS)

1965-01-01

Deflated plastic bag in a vacuum chamber measures initial low vapor pressures of materials. The bag captures the test sample vapors and visual observation of the vapor-inflated bag under increasing external pressures yields pertinent data.

The activity-composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: III. Vapor-liquid water equilibration of NaCl solutions to 350°C

NASA Astrophysics Data System (ADS)

Horita, Juske; Cole, David R.; Wesolowski, David J.

1995-03-01

The effect of dissolved NaCl on equilibrium oxygen and hydrogen isotope fractionation factors between liquid water and water vapor was precisely determined in the temperature range from 130-350°C, using two different types of apparatus with static or dynamic sampling techniques of the vapor phase. The magnitude of the oxygen and hydrogen isotope effects of NaCl is proportional to the molality of liquid NaCl solutions at a given temperature. Dissolved NaCl lowers appreciably the hydrogen isotope fractionation factor between liquid water and water vapor over the entire temperature range. NaCl has little effect on the oxygen isotope fractionation factor at temperatures below about 200°C, with the magnitude of the salt effect gradually increasing from 200-350°C. Our results are at notable variance with those of Truesdell (1974) and Kazahaya (1986), who reported large oxygen and hydrogen isotope effects of NaCl with very complex dependencies on temperature and NaCl molality. Our high-temperature results have been regressed along with our previous results between 50 and 100°C (Horita et al., 1993a) and the low-temperature literature data to simple equations which are valid for NaCl solutions from 0 to at least 5 molal NaCl in the temperature range from 10-350°C. Our preliminary results of oxygen isotope fractionation in the system CaCO3-water ± NaCl at 300°C and 1 kbar are consistent with those obtained from the liquid-vapor equilibration experiments, suggesting that the isotope salt effects are common to systems involving brines and any other coexisting phases or species (gases, minerals, dissolved species, etc.). The observed NaCl isotope effects at elevated temperatures should be taken into account in the interpretation of isotopic data of brine-dominated natural systems.

Water vapor δ17O measurements using an off-axis integrated cavity output spectrometer and seasonal variation in 17O-excess of precipitation in the east-central United States

NASA Astrophysics Data System (ADS)

Tian, C.; Wang, L.; Novick, K. A.

2016-12-01

High-precision triple oxygen isotope analysis can be used to improve our understanding of multiple hydrological and meteorological processes. Recent studies focus on understanding 17O-excess variation of tropical storms, high-latitude snow and ice-core as well as spatial distribution of meteoric water (tap water). The temporal scale of 17O-excess variation in middle-latitude precipitation is needed to better understand which processes control on the 17O-excess variations. This study focused on assessing how the accuracy and precision of vapor δ17O laser spectroscopy measurements depend on vapor concentration, delta range, and averaging-time. Meanwhile, we presented 17O-excess data from two-year, event based precipitation sampling in the east-central United States. A Triple Water Vapor Isotope Analyzer (T-WVIA) was used to evaluate the accuracy and precision of δ2H, δ18O and δ17O measurements. GISP and SLAP2 from IAEA and four working standards were used to evaluate the sensitivity in the three factors. Overall, the accuracy and precision of all isotope measurements were sensitive to concentration, with higher accuracy and precision generally observed under moderate vapor concentrations (i.e., 10000-15000 ppm) for all isotopes. Precision was also sensitive to the range of delta values, though the effect was not as large when compared to the sensitivity to concentration. The precision was much less sensitive to averaging time when compared with concentration and delta range effects. The preliminary results showed that 17O-excess variation was lower in summer (23±17 per meg) than in winter (34±16 per meg), whereas spring values (30±21 per meg) was similar to fall (29±13 per meg). That means kinetic fractionation influences the isotopic composition and 17O-excess in different seasons.

Isotopic Abundances as Tracers of the Processes of Lunar Formation

NASA Astrophysics Data System (ADS)

Pahlevan, K.

2011-12-01

different, if the Moon preferentially forms from the liquid or vapor relative to the Earth, mass-dependent isotopic differences at the planetary scale may arise. The large density contrast between liquid and vapor makes phase separation possible. (3) The precision with which planetary isotopic compositions can be determined has increased such that measurements are sensitive to even small degrees of high-temperature phase separation. Using thermodynamic models of silicate liquids to determine the partial vaporization behavior of the major elements, we will present calculations of isotopic fractionation due to liquid-vapor separation for the elements iron, magnesium, silicon, and oxygen. Improvements in analytical precision have largely settled the question of the source of the lunar material - the Earth's mantle - and isotopic measurements are now beginning to yield insight into the high-temperatures processes operating during lunar formation.

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial

Vapor Pressure Measurements in a Closed System

ERIC Educational Resources Information Center

Iannone, Mark

2006-01-01

An alternative method that uses a simple apparatus to measure vapor pressure versus temperature in a closed system, in which the total pressure is the vapor pressure of the liquid sample, is described. The use of this apparatus gives students a more direct picture of vapor pressure than the isoteniscope method and results have generally been quite…

Variability in the combustion-derived fraction of urban humidity in Salt Lake City winter estimated from stable water vapor isotopes and its relationship to atmospheric stability and inversion structure

NASA Astrophysics Data System (ADS)

Fiorella, R.; Bares, R.; Lin, J. C.; Strong, C.; Bowen, G. J.

2017-12-01

Water released from the combustion of fossil fuels, while a negligible part of the global hydrological cycle, may be a significant contributor to urban humidity as fossil fuel emissions are strongly concentrated in space and time. The fraction of urban humidity comprised of combustion-derived vapor (CDV) cannot be observed through humidity measurements alone. However, the distinct stable isotopic composition of CDV, which arises from the reaction of 18O-enriched atmospheric O2 with 2H-depleted organic molecules, represents a promising method to apportion observed humidity between CDV and advected vapor. We apply stable water vapor isotopes to investigate variability in CDV amount and its relationship to atmospheric conditions in Salt Lake City, Utah. The Salt Lake Valley experiences several periods of atmospheric stratification during winter known as cold air pools, during which concentrations of CDV and pollutants can be markedly elevated due to reduced atmospheric mixing. Therefore, the SLV during winter is an ideal place to investigate variability in CDV fraction across a spectrum of boundary layer conditions, ranging from well-mixed to very stable. We present water vapor isotope data from four winters (2013-2017) from the top of a 30 m building on the University of Utah (U of U) Campus. Additionally, we present water vapor isotope data from the summit of Hidden Peak from the 2016-2017 winter, 25 km SE and 2000 m above the U of U site. The Hidden Peak site is consistently above the cold air pool emplaced in the SLV during stable events. We find the expression of the CDV signal in the valley is related to the atmospheric structure of the cold air pools in the SLV, and that the fraction of CDV inferred in the valley is likely related to the mixing height within the cold air pool. Furthermore, we find that patterns between the Hidden Peak and U of U sites during inversion events may record the large-scale atmospheric dynamics promoting emplacement of the cold air

Connection between ENSO and Asian Summer Monsoon Precipitation Oxygen Isotope

NASA Astrophysics Data System (ADS)

Cai, Z.; Tian, L.

2016-12-01

In an effort to understand the connection between El Niño Southern Oscillation (ENSO) and Asian Summer Monsoon (ASM) precipitation oxygen isotope, this study investigates the spatial and interannual patterns in summer (JJAS) monsoon precipitation δ18O and satellite water vapor isotope retrievals, especially those patterns associated with convection and vapor transport. Both precipitation and vapor isotope values exhibit a "V" shaped longitudinal pattern in their spatial variations, reflecting the gradual rainout and increase in convective intensity along vapor transport routes. In order to understand interannual variations, an ASM precipitation δ18O index (ASMOI) is introduced to measure the temporal variations in regional precipitation δ18O; and these variations are consistent with central Indo-Pacific convection and cloud-top height. The counter variations in the ASMOI in El Niño and La Niña years confirm the existence of a positive isotope- ENSO response (e.g., high values corresponding to warm phases) over the eastern Indian Ocean and southeastern Asia (80°E-120°E/10°S-30°N) as a response to changes in convection. However, JJAS vapor δD over the western Pacific (roughly east of 120oE) varies in opposition, due to the influence of water vapor transport. This opposite variation does not support the interpretation of precipitation isotope-ENSO relationship as changing proportion of vapor transported from different regions, but rather condensation processes associated with convection. These findings are important for studying past ASM and ENSO activity from various isotopic archives and have implications for the study of the atmospheric water cycle.

Physical and Mathematical Methods for Removing Organic Interference from Optical Isotope Measurements

NASA Astrophysics Data System (ADS)

Hsiao, G.; Chappellet-Volini, L.; Vu, D.

2012-12-01

Portable high precision isotope analyzers using CRDS technology have greatly increased the use of stable isotopes in hydrological, oceanographic, and ecological studies over the past five years. However studies of some water samples yielded incorrect isotopic values indicating some form of spectroscopic interference. Subsequent work has shown that waters derived from some plants containing interfering alcohols but meteoric waters are not affected. The initial approach to handling such samples was to use spectroscopic anomalies to identify and flag affected samples for later analysis by non-optical methods. This presentation will examine the approaches developed within the past year to allow for accurate analysis of such samples by optical methods. The first approach uses an advanced spectroscopic model to identify and quantify alcohols present in the sample. The alcohol signal is incorporated into the overall fit of the measure spectra to calculate the concentration of the individual isotopes. It was found that the δ18O value could be calculated with high accuracy, the result for the δ2H value was sufficient for many applications. The second approach uses physical treatment of the sample to break down the organic molecules into non-interfering species. The liquid sample is injected into a flash vaporizer then the vapor travels through a cartridge for physical treatment prior to analysis by CRDS. Inside the cartridge the organic molecules undergo oxidation at high temperature in the air carrier gas when exposed to the catalyst. This approach is highly effective for ethanol solutions as high as 5% as well as for the complex mixtures of alcohols found in plants. Comparison of the results of both of these methods will be compared with tertiary techniques such as IRMS where possible.

Experimental study of flash boiling spray vaporization through quantitative vapor concentration and liquid temperature measurements

NASA Astrophysics Data System (ADS)

Zhang, Gaoming; Hung, David L. S.; Xu, Min

2014-08-01

Flash boiling sprays of liquid injection under superheated conditions provide the novel solutions of fast vaporization and better air-fuel mixture formation for internal combustion engines. However, the physical mechanisms of flash boiling spray vaporization are more complicated than the droplet surface vaporization due to the unique bubble generation and boiling process inside a superheated bulk liquid, which are not well understood. In this study, the vaporization of flash boiling sprays was investigated experimentally through the quantitative measurements of vapor concentration and liquid temperature. Specifically, the laser-induced exciplex fluorescence technique was applied to distinguish the liquid and vapor distributions. Quantitative vapor concentration was obtained by correlating the intensity of vapor-phase fluorescence with vapor concentration through systematic corrections and calibrations. The intensities of two wavelengths were captured simultaneously from the liquid-phase fluorescence spectra, and their intensity ratios were correlated with liquid temperature. The results show that both liquid and vapor phase of multi-hole sprays collapse toward the centerline of the spray with different mass distributions under the flash boiling conditions. Large amount of vapor aggregates along the centerline of the spray to form a "gas jet" structure, whereas the liquid distributes more uniformly with large vortexes formed in the vicinity of the spray tip. The vaporization process under the flash boiling condition is greatly enhanced due to the intense bubble generation and burst. The liquid temperature measurements show strong temperature variations inside the flash boiling sprays with hot zones present in the "gas jet" structure and vortex region. In addition, high vapor concentration and closed vortex motion seem to have inhibited the heat and mass transfer in these regions. In summary, the vapor concentration and liquid temperature provide detailed information

Synthetic isotope mixtures for the calibration of isotope amount ratio measurements of carbon

NASA Astrophysics Data System (ADS)

Russe, K.; Valkiers, S.; Taylor, P. D. P.

2004-07-01

Synthetic isotope mixtures for the calibration of carbon isotope amount ratio measurements have been prepared by mixing carbon tetrafluoride highly enriched in 13C with carbon tetrafluoride depleted in 13C. Mixing procedures based on volumetry and gravimetry are described. The mixtures served as primary measurement standards for the calibration of isotope amount ratio measurements of the Isotopic Reference Materials PEF1, NBS22 and USGS24. Thus SI-traceable measurements of absolute carbon isotope amount ratios have been performed for the first time without any hypothesis needed for a correction of oxygen isotope abundances, such as is the case for measurements on carbon dioxide. As a result, "absolute" carbon isotope amount ratios determined via carbon tetrafluoride have smaller uncertainties than those published for carbon dioxide. From the measurements of the Reference Materials concerned, the absolute carbon isotope amount ratio of Vienna Pee Dee Belemnite (VPDB)--the hypothetical material upon which the scale for relative carbon isotope ratio measurements is based--was calculated to be R13(VPDB) = (11 101 +/- 16) × 10-6.

Deuterium excess reveals diurnal sources of water vapor in forest air.

PubMed

Lai, Chun-Ta; Ehleringer, James R

2011-01-01

An understanding of atmospheric water vapor content and its isotopic composition is important if we are to be able to model future water vapor dynamics and their potential feedback on future climate change. Here we present diurnal and vertical patterns of water isotope ratios in forest air (δ(2)H(v) and δ(18)O(v)) not observed previously. Water vapor observed at three heights over 3 consecutive days in a coniferous forest in the Pacific Northwest of the United States, shows a stratified nocturnal structure of δ(2)H(v) and δ(18)O(v), with the most positive values consistently observed above the canopy (60 m). Differences between 0.5 m and 60 m range between 2-6‰ for δ(18)O and 20-40‰ for δ(2)H at night. Using a box model, we simulated H(2)O isotope fluxes and showed that the low to high δ(2)H(v) and δ(18)O(v) profiles can be explained by the vapor flux associated with evaporation from the forest floor and canopy transpiration. We used d-excess as a diagnostic tracer to identify processes that contribute to the diurnal variation in atmospheric moisture. Values of d-excess derived from water vapor measurements showed a repeated diel pattern, with the lowest values occurring in the early morning and the highest values occurring at midday. The isotopic composition of rain water, collected during a light rain event in the first morning of our experiment, suggested that considerable below-cloud secondary evaporation occurred during the descent of raindrops. We conclude that atmospheric entrainment appears to drive the isotopic variation of water vapor in the early morning when the convective boundary layer rapidly develops, while evapotranspiration becomes more important in the mid-afternoon as a primary moisture source of water vapor in this forest. Our results demonstrate the interplay between the effects of vegetation and boundary layer mixing under the influence of rain evaporation, which has implications for larger-scale predictions of precipitation

Characterization of upper troposphere water vapor measurements during AFWEX using LASE.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferrare, R. A.; Browell, E. V.; Ismail, I.

2002-07-15

Water vapor profiles from NASA's Lidar Atmospheric Sensing Experiment (LASE) system acquired during the ARM/FIRE Water Vapor Experiment (AFWEX) are used to characterize upper troposphere (UT) water vapor measured by ground-based Raman lidars, radiosondes, and in situ aircraft sensors. Initial comparisons showed the average Vaisala radiosonde measurements to be 5-15% drier than the average LASE, Raman lidar, and DC-8 in situ diode laser hygrometer measurements. They show that corrections to the Raman lidar and Vaisala measurements significantly reduce these differences. Precipitable water vapor (PWV) derived from the LASE water vapor profiles agrees within 3% on average with PWV derived frommore » the ARM ground-based microwave radiometer (MWR). The agreement among the LASE, Raman lidar, and MWR measurements demonstrates how the LASE measurements can be used to characterize both profile and column water vapor measurements and that ARM Raman lidar, when calibrated using the MWR PWV, can provide accurate UT water vapor measurements.« less

Partitioning evapotranspiration fluxes with water stable isotopic measurements: from the lab to the field

NASA Astrophysics Data System (ADS)

Quade, M. E.; Brueggemann, N.; Graf, A.; Rothfuss, Y.

2017-12-01

Water stable isotopes are powerful tools for partitioning net into raw water fluxes such as evapotranspiration (ET) into soil evaporation (E) and plant transpiration (T). The isotopic methodology for ET partitioning is based on the fact that E and T have distinct water stable isotopic compositions, which in turn relies on the fact that each flux is differently affected by isotopic kinetic effects. An important work to be performed in parallel to field measurements is to better characterize these kinetic effects in the laboratory under controlled conditions. A soil evaporation laboratory experiment was conducted to retrieve characteristic values of the kinetic fractionation factor (αK) under varying soil and atmospheric water conditions. For this we used a combined soil and atmosphere column to monitor the soil and atmospheric water isotopic composition profiles at a high temporal and vertical resolution in a nondestructive manner by combining micro-porous membranes and laser spectroscopy. αK was calculated by using a well-known isotopic evaporation model in an inverse mode with the isotopic composition of E as one input variable, which was determined using a micro-Keeling regression plot. Knowledge on αK was further used in the field (Selhausen, North Rhine-Westphalia, Germany) to partition ET of catch crops and sugar beet (Beta vulgaris) during one growing season. Soil and atmospheric water isotopic profiles were measured automatically across depths and heights following a similar modus operandi as in the laboratory experiment. Additionally, a newly developed continuously moving elevator was used to obtain water vapor isotopic composition profiles with a high vertical resolution between soil surface, plant canopy and atmosphere. Finally, soil and plant samples were collected destructively to provide a comparison with the traditional isotopic methods. Our results illustrate the changing proportions of T and E along the growing season and demonstrate the

Role of Deep Convection in Establishing the Isotopic Composition of Water Vapor in the Tropical Transition Layer

NASA Technical Reports Server (NTRS)

Smith, Jamison A.; Ackerman, Andrew S.; Jensen, Eric J.; Toon, Owen B.

2006-01-01

The transport of H2O and HDO within deep convection is investigated with 3-D large eddy simulations (LES) using bin microphysics. The lofting and sublimation of HDO-rich ice invalidate the Rayleigh fractionation model of isotopologue distribution within deep convection. Bootstrapping the correlation of the ratio of HDO to H2O (deltaD) to water vapor mixing ratio (q(sub v)) through a sequence of convective events produced non-Rayleigh correlations resembling observations. These results support two mechanisms for stratospheric entry. Deep convection can inject air with water vapor of stratospheric character directly into the tropical transition layer (TTL). Alternatively, moister air detraining from convection may be dehydrated via cirrus formation n the TTL to produce stratospheric water vapor. Significant production of subsaturated air in the TTL via convective dehydration is not observed in these simulations, nor is it necessary to resolve the stratospheric isotope paradox.

Characterization of Upper Troposphere Water Vapor Measurements during AFWEX using LASE

NASA Technical Reports Server (NTRS)

Ferrare, R. A.; Browell, E. V.; Ismail, S.; Kooi, S.; Brasseur, L. H.; Brackett, V. G.; Clayton, M.; Barrick, J.; Linne, H.; Lammert, A.

2002-01-01

Water vapor profiles from NASA's Lidar Atmospheric Sensing Experiment (LASE) system acquired during the ARM/FIRE Water Vapor Experiment (AFWEX) are used to characterize upper troposphere water vapor (UTWV) measured by ground-based Raman lidars, radiosondes, and in situ aircraft sensors. Initial comparisons showed the average Vaisala radiosonde measurements to be 5-15% drier than the average LASE, Raman lidar, and DC-8 in situ diode laser hygrometer measurements. We show that corrections to the Raman lidar and Vaisala measurements significantly reduce these differences. Precipitable water vapor (PWV) derived from the LASE water vapor profiles agrees within 3% on average with PWV derived from the ARM ground-based microwave radiometer (MWR). The agreement among the LASE, Raman lidar, and MWR measurements demonstrates how the LASE measurements can be used to characterize both profile and column water vapor measurements and that ARM Raman lidar, when calibrated using the MWR PWV, can provide accurate UTWV measurements.

Mass spectrometry for water vapor measurements in the UT/LS

NASA Astrophysics Data System (ADS)

Kaufmann, S.; Voigt, C.; Schäuble, D.; Schäfler, A.; Schlager, H.; Thornberry, T. D.; Fahey, D. W.

2012-12-01

Water vapor in the lower stratosphere plays a crucial role for the atmospheric radiation budget (Solomon et al., 2011). However, large uncertainties remain in measuring atmospheric water vapor mixing ratios below 10 ppmv typical for the lower stratosphere. To this end, we have developed the Atmospheric Ionization Mass Spectrometer (AIMS) for the accurate and fast detection of water vapor in the UT/LS from aircraft. In the AIMS instrument atmospheric air is directly ionized in a discharge ion source and the resulting water vapor clusters H3O+(H2O)n (n = 0..3) are detected with a linear quadrupole mass spectrometer as a direct measure of the atmospheric water vapor mixing ratio. AIMS is calibrated in-flight with a H2O calibration source using the catalytic reaction of H2 and O2 on a heated platinum surface to form gaseous H2O. This calibration setup combined with the water vapor mass spectrometry offers a powerful technical development in atmospheric hygrometry, enriching existing H2O measurement techniques by a new independent method. Here, we present AIMS water vapor measurements performed during the CONCERT2011 campaign (Contrail and Cirrus Experiment) with the DLR research aircraft Falcon. In September 2011 a deep stratospheric intrusion was probed over northern Europe with a dynamical tropopause lowered down to 6 km. We found sharp humidity gradients between tropospheric and stratospheric air at the edge of the tropopause fold, which we crossed 4 times at altitudes between 6 and 11 km. In the center of the tropopause fold, we measured water vapor mixing ratios down to 4 ppmv. The observed water vapor distribution is compared to water vapor analysis fields of the ECMWF's Integrated Forecast System (IFS) to evaluate the representation water vapor in this specific meteorological situation.

Determination of Hg Content in a Shallow Firn Core From Summit, Greenland Using Isotope Dilution Cold Vapor Inductively Coupled Plasma - Mass Spectrometry

NASA Astrophysics Data System (ADS)

Mann, J. L.; Long, S. E.; Shuman, C. A.

2002-05-01

Considerable attention has recently been focused on mercury (Hg) owing to its ability to bioaccumulate as highly toxic species in the biosphere. Hg in the environment is derived from both natural and anthropogenic sources and present day emissions for both are thought to be of similar magnitude. Once introduced into the atmosphere, Hgo can be transported long distances and as a result is considered to have global environmental influence. High levels of Hg have been found in Arctic food supplies and elevated levels have been observed in the native people of the circumpolar countries including Greenland. Mercury content was determined in surface snow and a 7 m shallow snow/firn core, recovered in May 2001 from Summit, Greenland (72.58oN, 38.53oW; elevation 3238 m), using a new method employing isotope dilution cold vapor inductively coupled plasma - mass spectrometry (ID-CV-ICPMS). The method, recently developed at the National Institute of Standards and Technology, uses a 201Hg spike that is equilibrated with the sample. Hg is measured by chemical reduction with tin (II) chloride and generation of a "cold vapor" (elemental Hg vapor) whereby the Hg vapor is separated from the matrix using a gas-liquid separator and is collected on gold guaze. Hg is then released by thermal desorption and the Hg isotope ratio (201Hg/202Hg) measured by quadrapole ICP-MS. There are considerable advantages to this new method in the analysis of very low concentration snow/firn/ice samples which include: 1) very high sensitivity (detection limit < 1 pg/mL, 3 sigma); 2) accuracy and precision of the order of one percent or better; and 3) complete freedom from spectral and matrix interferences. The concentrations determined ranged from 0.1 to 1.1 pg/g, which fall within the range of those previously determined by Boutron et al. (1998). Hg contributed from core processing, storage in LDPE bottles, and the analytical procedure yielded a blank value of 0.10 pg Hg/g equivalent. This was used to

Triple isotope composition of oxygen in atmospheric water vapor

NASA Astrophysics Data System (ADS)

Uemura, Ryu; Barkan, Eugeni; Abe, Osamu; Luz, Boaz

2010-02-01

Recently, an excess of 17O (17O-excess) has been demonstrated in meteoric water and ice cores. Based on theory and experiments, it has been suggested that this excess originates from evaporation of ocean water into under-saturated air. However, there has never been direct demonstration of this excess in marine vapor. Here, we present results of the first measurements of δ17O and δ18O in vapor samples collected over the South Indian and the Southern Oceans. Our data show the existence of 17O-excess in marine vapor and also clear negative correlation between 17O-excess and relative humidity. Thus, 17O-excess is useful for constraining oceanic humidity in hydrological and climatic models. Using the obtained values of 17O-excess, we estimated the fractionation factor between H218O and H216O for diffusion in air above the ocean (18αdiff). The new estimation of 18αdiff (1.008) is larger than the widely accepted value in hydrological studies.

METHOD AND APPARATUS FOR COLLECTING ISOTOPES

DOEpatents

Leyshon, W.E.

1957-08-01

A method and apparatus for collecting isotopes having a high vapor pressure, such as isotopes of mercury, in a calutron are described. Heretofore, the collected material would vaporize and escape from the ion receiver as fast as it was received. By making the receiver of pure silver, the mercury isotopes form a nonvolatile amalgam with the silver at the water cooled temperature of the receiver, and the mercury is thus retained.

Characterization of Upper-Troposphere Water Vapor Measurements during AFWEX Using LASE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferrare, Richard; Browell, E. V.; Ismail, S.

Water vapor profiles from NASA's Lidar Atmospheric Sensing Experiment (LASE) system acquired during the ARM/FIRE Water Vapor Experiment (AFWEX) are used to characterize upper troposphere water vapor (UTWV) measured by ground-based Raman lidars, radiosondes, and in situ aircraft sensors over the Department of Energy Atmospheric Radiation Measurement (ARM) Southern Great Plains (SGP) site in northern Oklahoma. LASE was deployed from the NASA DC-8 aircraft and measured water vapor over the ARM SGP Central Facility (CF) site during seven flights between November 27 and December 10, 2000. Initially, the DOE ARM SGP Cloud and Radiation Testbed (CART) Raman lidar (CARL) UTWVmore » profiles were about 5-7% wetter than LASE in the upper troposphere, and the Vaisala RS80-H radiosonde profiles were about 10% drier than LASE between 8-12 km. Scaling the Vaisala water vapor profiles to match the precipitable water vapor (PWV) measured by the ARM SGP microwave radiometer (MWR) did not change these results significantly. By accounting for an overlap correction of the CARL water vapor profiles and by employing schemes designed to correct the Vaisala RS80-H calibration method and account for the time response of the Vaisala RS80H water vapor sensor, the average differences between the CARL and Vaisala radiosonde upper troposphere water vapor profiles are reduced to about 5%, which is within the ARM goal of mean differences of less than 10%. The LASE and DC-8 in situ Diode Laser Hygrometer (DLH) UTWV measurements generally agreed to within about 3 to 4%. The DC-8 in situ frost point cryogenic hygrometer and Snow White chilled mirror measurements were drier than the LASE, Raman lidars, and corrected Vaisala RS80H measurements by about 10-25% and 10-15%, respectively. Sippican (formerly VIZ manufacturing) carbon hygristor radiosondes exhibited large variabilities and poor agreement with the other measurements. PWV derived from the LASE profiles agreed to within about 3% on average

Experimental Artifacts in Nitrogen Isotope Measurements of Meteorites

NASA Astrophysics Data System (ADS)

Kim, J. S.; Marti, K.

1993-07-01

Several research groups have studied contamination problems and molecular interferences in nitrogen isotope measurements, but some problems still require clarification. Protocols adopted for nitrogen isotope measurements generally consider questions such as CO interference, removal of hydrocarbons, and N2O and NO conversion [1]. In the analysis of nanogram amounts of N, contamination, exchange reactions, and interferences are more visible than in large N samples. During nitrogen measurements we observed several potential problems and developed an improved protocol to achieve high-quality isotopic data: 1. Nitrogen loss and isotopic exchange were observed on the extraction system wall. The wall has active surfaces produced by vapor deposition (previous samples) that absorb many molecules, including nitrogen. This absorbed nitrogen releases or exchanges nitrogen with sample N in the following extraction steps. Therefore the losses need to be calibrated and the extent of isotopic exchange determined at the nanogram level. A continuous adsorption during sample extraction of the gas phase onto zeolite at liquid nitrogen temperature reduces nitrogen loss and amount of exchange. 2. We also found nitrogen isotopic memory effect by CuO. During sample gas cleaning by CuO, nitrogen exchanges with residual nitrogen in the CuO, and losses to CuO by solubility and/or uptake of nitrogen during oxygen uptake. This effect is clearly visible after analysis of large amounts of nitrogen. In such cases the CuO blank showed traces of previously measured isotopic signatures. Therefore, the isotopic signature of the CuO blank must be assessed before proceeding. 3. NO interference was recognized. In measurements of N in bulk H chondrites, the steps above 900 degrees C show anomalous contribution to the mass 30 peak, which decreases rapidly with time in the mass spectrometer. Using the ratio mass 30 to mass 31 and the corresponding physical properties of the interfering compound, we

Raman scattering method and apparatus for measuring isotope ratios and isotopic abundances

DOEpatents

Harney, Robert C.; Bloom, Stewart D.

1978-01-01

Raman scattering is used to measure isotope ratios and/or isotopic abundances. A beam of quasi-monochromatic photons is directed onto the sample to be analyzed, and the resulting Raman-scattered photons are detected and counted for each isotopic species of interest. These photon counts are treated mathematically to yield the desired isotope ratios or isotopic abundances.

Subatmospheric vapor pressures evaluated from internal-energy measurements

NASA Astrophysics Data System (ADS)

Duarte-Garza, H. A.; Magee, J. W.

1997-01-01

Vapor pressures were evaluated from measured internal-energy changes in the vapor+liquid two-phase region, Δ U (2). The method employed a thermodynamic relationship between the derivative quantity (ϖ U (2)/ϖ V) T and the vapor pressure ( p σ) and its temperature derivative (ϖ p/ϖ T)σ. This method was applied at temperatures between the triple point and the normal boiling point of three substances: 1,1,1,2-tetrafluoroethane (R134a), pentafluoroethane (R125), and difluoromethane (R32). Agreement with experimentally measured vapor pressures near the normal boiling point (101.325 kPa) was within the experimental uncertainty of approximately ±0.04 kPa (±0.04%). The method was applied to R134a to test the thermodynamic consistency of a published p-p-T equation of state with an equation for p σ for this substance. It was also applied to evaluate published p σ data which are in disagreement by more than their claimed uncertainty.

Tunable lasers for water vapor measurements and other lidar applications

NASA Technical Reports Server (NTRS)

Gammon, R. W.; Mcilrath, T. J.; Wilkerson, T. D.

1977-01-01

A tunable dye laser suitable for differential absorption (DIAL) measurements of water vapor in the troposphere was constructed. A multi-pass absorption cell for calibration was also constructed for use in atmospheric DIAL measurements of water vapor.

Determination of the isotopic composition of evapotranspiration in a mature oil palm plantation in Jambi province, Indonesia.

NASA Astrophysics Data System (ADS)

Bonazza, Mattia; Meijide, Ana; Knohl, Alexander

2017-04-01

Evapotranspiration (ET) is defined as the sum of the water vapor fluxes from evaporation (E) and transpiration (T). The relative proportion between these two quantities depends on the species, on their age and on the structure of the stand and canopy. Evaporation represents the fraction of water that doesn't contribute to plants growth hence it often considered as "unused" water by the plants root system. For this reason, in a fast changing environment like Indonesia where, since almost 30 years, tropical rainforests are gradually converted into extensive oil palm plantation, it is important to quantify the amount of evaporated water to improve agricultural practices and water quality. As powerful tracers of the hydrological cycle, water stable isotopes represent an important tool to estimate the isotopic composition of the evapotranspiration flux and they can be used as a starting point for the determination of the T/ET ratio, which can be considered as a plant water uptake efficiency indicator. The isotopic composition (δDvand δ18Ov) and the mixing ratio (qv) of water vapor measured in a stand is the result of the isotopic mixing between two members; ecosystem evapotranspiration (δET) and background air (δa). With the implementation of laser-based isotopic analysers we are now able to improve the measurement frequency of δDvand δ18Ov that leads us to an improved estimation of δET. Here we present the results of a measurement campaign, performed with a Picarro L-2120i and conducted in a mature oil palm plantation in the province of Jambi, Indonesia. We measured the atmospheric water vapor mixing ratio and isotopic composition at 5 sampling heights (21 m, 16 m, 9 m, 3.5 and 0.3 m) along a flux tower throughout the oil palm canopy (average height 10 m). The range of the water vapor isotopic composition was between -19 and -11 and -134 and -82 ‰ for δ18Ov and δDvrespectively. A fairly open canopy structure resulted in small mixing ratio gradients along the

Predictions and Verification of an Isotope Marine Boundary Layer Model

NASA Astrophysics Data System (ADS)

Feng, X.; Posmentier, E. S.; Sonder, L. J.; Fan, N.

2017-12-01

A one-dimensional (1D), steady state isotope marine boundary layer (IMBL) model is constructed. The model includes meteorologically important features absent in Craig and Gordon type models, namely height-dependent diffusion/mixing and convergence of subsiding external air. Kinetic isotopic fractionation results from this height-dependent diffusion which starts as pure molecular diffusion at the air-water interface and increases linearly with height due to turbulent mixing. The convergence permits dry, isotopically depleted air subsiding adjacent to the model column to mix into ambient air. In δD-δ18O space, the model results fill a quadrilateral, of which three sides represent 1) vapor in equilibrium with various sea surface temperatures (SSTs) (high d18O boundary of quadrilateral); 2) mixture of vapor in equilibrium with seawater and vapor in the subsiding air (lower boundary depleted in both D and 18O); and 3) vapor that has experienced the maximum possible kinetic fractionation (high δD upper boundary). The results can be plotted in d-excess vs. δ18O space, indicating that these processes all cause variations in d-excess of MBL vapor. In particular, due to relatively high d-excess in the descending air, mixing of this air into the MBL causes an increase in d-excess, even without kinetic isotope fractionation. The model is tested by comparison with seven datasets of marine vapor isotopic ratios, with excellent correspondence; >95% of observational data fall within the quadrilateral area predicted by the model. The distribution of observations also highlights the significant influence of vapor from the nearby converging descending air on isotopic variations in the MBL. At least three factors may explain the <5% of observations that fall slightly outside of the predicted region in both δD-δ18O and d-excess - δ18O space: 1) variations in seawater isotopic ratios, 2) variations in isotopic composition of subsiding air, and 3) influence of sea spray. The model

Method for isotope enrichment by photoinduced chemiionization

DOEpatents

Dubrin, James W.

1985-01-01

Isotope enrichment, particularly .sup.235 U enrichment, is achieved by irradiating an isotopically mixed vapor feed with radiant energy at a wavelength or wavelengths chosen to selectively excite the species containing a desired isotope to a predetermined energy level. The vapor feed if simultaneously reacted with an atomic or molecular reactant species capable of preferentially transforming the excited species into an ionic product by a chemiionization reaction. The ionic product, enriched in the desired isotope, is electrostatically or electromagnetically extracted from the reaction system.

Determination of kinetic isotopic fractionation of water during bare soil evaporation

NASA Astrophysics Data System (ADS)

Quade, Maria; Brüggemann, Nicolas; Graf, Alexander; Rothfuss, Youri

2017-04-01

A process-based understanding of the water cycle in the atmosphere is important for improving meteorological and hydrological forecasting models. Usually only net fluxes of evapotranspiration - ET are measured, while land-surface models compute their raw components evaporation -E and transpiration -T. Isotopologues can be used as tracers to partition ET, but this requires knowledge of the isotopic kinetic fractionation factor (αK) which impacts the stable isotopic composition of water pools (e.g., soil and plant waters) during phase change and vapor transport by soil evaporation and plant transpiration. It is defined as a function of the ratio of the transport resistances in air of the less to the most abundant isotopologue. Previous studies determined αK for free evaporating water (Merlivat, 1978) or bare soil evaporation (Braud et al. 2009) at only low temporal resolution. The goal of this study is to provide estimates at higher temporal resolution. We performed a soil evaporation laboratory experiment to determine the αK by applying the Craig and Gordon (1965) model. A 0.7 m high column (0.48 m i.d.) was filled with silt loam (20.1 % sand, 14.9 % loam, 65 % silt) and saturated with water of known isotopic composition. Soil volumetric water content, temperature and the isotopic composition (δ) of the soil water vapor were measured at six different depths. At each depth microporous polypropylene tubing allowed the sampling of soil water vapor and the measurement of its δ in a non-destructive manner with high precision and accuracy as detailed in Rothfuss et al. (2013). In addition, atmospheric water vapor was sampled at seven different heights up to one meter above the surface for isotopic analysis. Results showed that soil and atmospheric δ profiles could be monitored at high temporal and vertical resolutions during the course of the experiment. αK could be calculated by using an inverse modeling approach and the Keeling (1958) plot method at high temporal

Stable Calibration of Raman Lidar Water-Vapor Measurements

NASA Technical Reports Server (NTRS)

Leblanc, Thierry; McDermid, Iain S.

2008-01-01

A method has been devised to ensure stable, long-term calibration of Raman lidar measurements that are used to determine the altitude-dependent mixing ratio of water vapor in the upper troposphere and lower stratosphere. Because the lidar measurements yield a quantity proportional to the mixing ratio, rather than the mixing ratio itself, calibration is necessary to obtain the factor of proportionality. The present method involves the use of calibration data from two sources: (1) absolute calibration data from in situ radiosonde measurements made during occasional campaigns and (2) partial calibration data obtained by use, on a regular schedule, of a lamp that emits in a known spectrum determined in laboratory calibration measurements. In this method, data from the first radiosonde campaign are used to calculate a campaign-averaged absolute lidar calibration factor (t(sub 1)) and the corresponding campaign-averaged ration (L(sub 1)) between lamp irradiances at the water-vapor and nitrogen wavelengths. Depending on the scenario considered, this ratio can be assumed to be either constant over a long time (L=L(sub 1)) or drifting slowly with time. The absolutely calibrated water-vapor mixing ratio (q) obtained from the ith routine off-campaign lidar measurement is given by q(sub 1)=P(sub 1)/t(sub 1)=LP(sub 1)/P(sup prime)(sub 1) where P(sub 1) is water-vapor/nitrogen measurement signal ration, t(sub 1) is the unknown and unneeded overall efficiency ratio of the lidar receiver during the ith routine off-campaign measurement run, and P(sup prime)(sub 1) is the water-vapor/nitrogen signal ratio obtained during the lamp run associated with the ith routine off-campaign measurement run. If L is assumed constant, then the lidar calibration is routinely obtained without the need for new radiosonde data. In this case, one uses L=L(sub 1) = P(sup prime)(sub 1)/t(sub 1), where P(sub 1)(sup prime) is the water-vapor/nitrogen signal ratio obtained during the lamp run associated

Airborne Observations of Water Vapor Deuterium Excess in the Mid-Latitude Lower Troposphere

NASA Astrophysics Data System (ADS)

Salmon, O. E.; Welp, L.; Shepson, P. B.; Stirm, B. H.

2017-12-01

Water vapor is responsible for over half of the natural atmospheric greenhouse effect. As global temperatures increase due to fossil fuel combustion, atmospheric water vapor concentrations are also expected to increase in positive feedback. Additionally, studies have shown that urban areas can influence humidity levels, and the frequency and intensity of precipitation events. It is thus important to understand anthropogenic modification of the hydrological cycle, particularly around urban areas, where over half of the world's population resides. Airborne measurements of water vapor isotopologues containing 2H and 18O were conducted to better understand processes influencing atmospheric moisture levels around urban areas. Airborne measurements were conducted around the Indianapolis and Washington, D.C.-Baltimore areas during afternoon hours in February and March 2016, using a Los Gatos Research Water Vapor Isotope Analyzer installed in Purdue University's experimental aircraft, the Airborne Laboratory for Atmospheric Research. The measurements of 2H and 18O allow for the calculation of deuterium excess (= δ2H - 8*δ18O), which provides information about non-equilibrium processes, such as kinetic effects, air parcel mixing, and transpiration. There are few studies that have reported observations of deuterium excess above the surface level ( 100 m). During the measurement campaign, vertical profiles were frequently conducted from 300 m above the ground to an altitude of approximately 1.5 km, effectively characterizing water vapor isotope profiles spanning the boundary layer and lower free troposphere. Measurements probed the transition from planetary boundary layer air to free troposphere air to provide high resolution deuterium excess information across this interface. Processes such as Rayleigh distillation, atmospheric mixing, and surface fluxes potentially impacting water vapor deuterium excess through the boundary layer and free troposphere with be discussed.

Apparatus of the Vapor-pressure Measurements for Natural Refrigerants

NASA Astrophysics Data System (ADS)

Higuchi, Satoru; Higashi, Yukihiro

An apparatus for measuring the vapor-pressures was newly designed and constructed in order to make the basic thermodynamic properties for environmentally acceptable refrigerants clear. The temperature of sample fluid was measured with 100Ω platinum resistance thermometer calibrated against ITS-90 using a 25Ω standard platinum resistance thermometer. With respect to the pressure measurement, two kinds of presure transducer were adopted. One is a diaphragm semi-conductor strain pressure transducer with the uncertainty of ±0.09%. This pressure transducer was calibrated against quartz crystal pressure transducer with the uncertainty of ±0.01% after every series of experiments. Another is a quartz crystal pressure transducer with the uncertainty of ±0.01%. A quartz crystal pressure transducer was calibrated against the dead weight pressure gauge and barometer. The vapor-pressures for R-32, R-134a, R-290 (propane), R-600a (iso-butane) and n-pentane were measured in the temperature range between273.15 and 323.15K. As the results of vapor-pressure measurements, the reliability of the experimental apparatus as well as the reproducibility of the experimental data were confirmed. In addition, coefficients of Antoine vapor pressure equation were determined from the experimental data. Normal boiling points for environmentally acceptable refrigerants were also determined with high accuracy.

High-resolution continuous-flow analysis setup for water isotopic measurement from ice cores using laser spectroscopy

NASA Astrophysics Data System (ADS)

Emanuelsson, B. D.; Baisden, W. T.; Bertler, N. A. N.; Keller, E. D.; Gkinis, V.

2015-07-01

Here we present an experimental setup for water stable isotope (δ18O and δD) continuous-flow measurements and provide metrics defining the performance of the setup during a major ice core measurement campaign (Roosevelt Island Climate Evolution; RICE). We also use the metrics to compare alternate systems. Our setup is the first continuous-flow laser spectroscopy system that is using off-axis integrated cavity output spectroscopy (OA-ICOS; analyzer manufactured by Los Gatos Research, LGR) in combination with an evaporation unit to continuously analyze water samples from an ice core. A Water Vapor Isotope Standard Source (WVISS) calibration unit, manufactured by LGR, was modified to (1) enable measurements on several water standards, (2) increase the temporal resolution by reducing the response time and (3) reduce the influence from memory effects. While this setup was designed for the continuous-flow analysis (CFA) of ice cores, it can also continuously analyze other liquid or vapor sources. The custom setups provide a shorter response time (~ 54 and 18 s for 2013 and 2014 setup, respectively) compared to the original WVISS unit (~ 62 s), which is an improvement in measurement resolution. Another improvement compared to the original WVISS is that the custom setups have a reduced memory effect. Stability tests comparing the custom and WVISS setups were performed and Allan deviations (σAllan) were calculated to determine precision at different averaging times. For the custom 2013 setup the precision after integration times of 103 s is 0.060 and 0.070 ‰ for δ18O and δD, respectively. The corresponding σAllan values for the custom 2014 setup are 0.030, 0.060 and 0.043 ‰ for δ18O, δD and δ17O, respectively. For the WVISS setup the precision is 0.035, 0.070 and 0.042 ‰ after 103 s for δ18O, δD and δ17O, respectively. Both the custom setups and WVISS setup are influenced by instrumental drift with δ18O being more drift sensitive than δD. The �

Environmental site description for a Uranium Atomic Vapor Laser Isotope Separation (U-AVLIS) production plant at the Paducah Gaseous Diffusion Plant site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marmer, G.J.; Dunn, C.P.; Moeller, K.L.

Uranium enrichment in the United States has utilized a diffusion process to preferentially enrich the U-235 isotope in the uranium product. The U-AVLIS process is based on electrostatic extraction of photoionized U-235 atoms from an atomic vapor stream created by electron-beam vaporization of uranium metal alloy. The U-235 atoms are ionized when precisely tuned laser light -- of appropriate power, spectral, and temporal characteristics -- illuminates the uranium vapor and selectively photoionizes the U-235 isotope. A programmatic document for use in screening DOE site to locate a U-AVLIS production plant was developed and implemented in two parts. The first partmore » consisted of a series of screening analyses, based on exclusionary and other criteria, that identified a reasonable number of candidate sites. These sites were subjected to a more rigorous and detailed comparative analysis for the purpose of developing a short list of reasonable alternative sites for later environmental examination. This environmental site description (ESD) provides a detailed description of the PGDP site and vicinity suitable for use in an environmental impact statement (EIS). The report is based on existing literature, data collected at the site, and information collected by Argonne National Laboratory (ANL) staff during a site visit. 65 refs., 15 tabs.« less

Stable-isotope studies of rocks and secondary minerals in a vapor-dominated hydrothermal system at The Geysers, Sonoma County, California

NASA Astrophysics Data System (ADS)

Lambert, Steven J.; Epstein, Samuel

1992-11-01

The Geysers, a vapor-dominated hydrothermal system, is developed in host rock of the Franciscan Formation, which contains veins of quartz and calcite whose δ 18O values record the temperatures and isotopic compositions of fluids prevailing during at least two different episodes of rock-fluid interaction. The first episode took place at about 200°C, during which marine silica and carbonate apparently interacted with ocean water entrapped in the sediments to form veins of quartz and calcite whose δ 18O values were around +19 and +16%, respectively. The calculated water/mineral ratios were less than unity. The water may have profoundly influenced the δ 18O values of spilitic basalts during their metamorphism to greenstones. Serpentinization and structural emplacement of ophiolite slabs were isotopically unrelated to this episode, which was essentially a low-grade (post-Cretaceous?) burial metamorphism. D/H ratios of actinolite, chlorite, and micas in host rocks were more profoundly altered during this episode than were 18O/ 16O ratios. A paleogeothermal gradient of about 53°C/km has been inferred for this episode, from δ 18O-depth distributions of vein minerals. The second episode, in part recorded by cogenetic vein quartz and calcite δ 18O values of +4 to +6% and +1 to +3%, respectively, began with large quantities of meteoric water circulating in fractures in the rock at temperatures of 160-180°C in response to the initiation of the Pliocene-Pleistocene Clear Lake magmatism. The temperature rose, and with the restricted circulation of fluids the ancestral hot-water system evolved into the presently active vapor-dominated system, which according to the cogenetic vein quartz and calcite δ 18O values involved temperatures as high as 320°C and fluid/mineral ratios near unity. The change in the oxygen-isotopic composition of the serpentinite within the host rock during this later activity was negligible. The δ 13C values of vein calcite at The Geysers reflect

Chlorine isotopic compositions of apatite in Apollo 14 rocks: Evidence for widespread vapor-phase metasomatism on the lunar nearside ∼4 billion years ago

NASA Astrophysics Data System (ADS)

Potts, Nicola J.; Barnes, Jessica J.; Tartèse, Romain; Franchi, Ian A.; Anand, Mahesh

2018-06-01

Compared to most other planetary materials in the Solar System, some lunar rocks display high δ37Cl signatures. Loss of Cl in a H ≪ Cl environment has been invoked to explain the heavy signatures observed in lunar samples, either during volcanic eruptions onto the lunar surface or during large scale degassing of the lunar magma ocean. To explore the conditions under which Cl isotope fractionation occurred in lunar basaltic melts, five Apollo 14 crystalline samples were selected (14053,19, 14072,13, 14073,9, 14310,171 along with basaltic clast 14321,1482) for in situ analysis of Cl isotopes using secondary ion mass spectrometry. Cl isotopes were measured within the mineral apatite, with δ37Cl values ranging from +14.6 ± 1.6‰ to +40.0 ± 2.9‰. These values expand the range previously reported for apatite in lunar rocks, and include some of the heaviest Cl isotope compositions measured in lunar samples to date. The data here do not display a trend between increasing rare earth elements contents and δ37Cl values, reported in previous studies. Other processes that can explain the wide inter- and intra-sample variability of δ37Cl values are explored. Magmatic degassing is suggested to have potentially played a role in fractionating Cl isotope in these samples. Degassing alone, however, could not create the wide variability in isotopic signatures. Our favored hypothesis, to explain small scale heterogeneity, is late-stage interaction with a volatile-rich gas phase, originating from devolatilization of lunar surface regolith rocks ∼4 billion years ago. This period coincides with vapor-induced metasomastism recorded in other lunar samples collected at the Apollo 16 and 17 landing sites, pointing to the possibility of widespread volatile-induced metasomatism on the lunar nearside at that time, potentially attributed to the Imbrium formation event.

Evaluating climate model performance in the tropics with retrievals of water isotopic composition from Aura TES

NASA Astrophysics Data System (ADS)

Field, Robert; Kim, Daehyun; Kelley, Max; LeGrande, Allegra; Worden, John; Schmidt, Gavin

2014-05-01

Observational and theoretical arguments suggest that satellite retrievals of the stable isotope composition of water vapor could be useful for climate model evaluation. The isotopic composition of water vapor is controlled by the same processes that control water vapor amount, but the observed distribution of isotopic composition is distinct from amount itself . This is due to the fractionation that occurs between the abundant H216O isotopes (isotopologues) and the rare and heavy H218O and HDO isotopes during evaporation and condensation. The fractionation physics are much simpler than the underlying moist physics; discrepancies between observed and modeled isotopic fields are more likely due to problems in the latter. Isotopic measurements therefore have the potential for identifying problems that might not be apparent from more conventional measurements. Isotopic tracers have existed in climate models since the 1980s but it is only since the mid 2000s that there have been enough data for meaningful model evaluation in this sense, in the troposphere at least. We have evaluated the NASA GISS ModelE2 general circulation model over the tropics against water isotope (HDO/H2O) retrievals from the Aura Tropospheric Emission Spectrometer (TES), alongside more conventional measurements. A small ensemble of experiments was performed with physics perturbations to the cumulus and planetary boundary layer schemes, done in the context of the normal model development process. We examined the degree to which model-data agreement could be used to constrain a select group of internal processes in the model, namely condensate evaporation, entrainment strength, and moist convective air mass flux. All are difficult to parameterize, but exert strong influence over model performance. We found that the water isotope composition was significantly more sensitive to physics changes than precipitation, temperature or relative humidity through the depth of the tropical troposphere. Among the

Tropical stratospheric water vapor measured by the microwave limb sounder (MLS)

NASA Technical Reports Server (NTRS)

Carr, E. S.; Harwood, R. S.; Mote, P. W.; Peckham, G. E.; Suttie, R. A.; Lahoz, W. A.; O'Neill, A.; Froidevaux, L.; Jarnot, R. F.; Read, W. G.

1995-01-01

The lower stratospheric variability of equatorial water vapor, measured by the Microwave Limb Sounder (MLS), follows an annual cycle modulated by the quasi-biennial oscillation. At levels higher in the stratosphere, water vapor measurements exhibit a semi-annual oscillatory signal with the largest amplitudes at 2.2 and 1hPa. Zonal-mean cross sections of MLS water vapor are consistent with previous satellite measurements from the limb infrared monitor of the stratosphere (LIMS) and the stratospheric Aerosol and Gas Experiment 2 (SAGE 2) instruments in that they show water vapor increasing upwards and the polewards from a well defined minimum in the tropics. The minimum values vary in height between the retrieved 46 and 22hPa pressure levels.

High-resolution continuous flow analysis setup for water isotopic measurement from ice cores using laser spectroscopy

NASA Astrophysics Data System (ADS)

Emanuelsson, B. D.; Baisden, W. T.; Bertler, N. A. N.; Keller, E. D.; Gkinis, V.

2014-12-01

Here we present an experimental setup for water stable isotopes (δ18O and δD) continuous flow measurements. It is the first continuous flow laser spectroscopy system that is using Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS; analyzer manufactured by Los Gatos Research - LGR) in combination with an evaporation unit to continuously analyze sample from an ice core. A Water Vapor Isotopic Standard Source (WVISS) calibration unit, manufactured by LGR, was modified to: (1) increase the temporal resolution by reducing the response time (2) enable measurements on several water standards, and (3) to reduce the influence from memory effects. While this setup was designed for the Continuous Flow Analysis (CFA) of ice cores, it can also continuously analyze other liquid or vapor sources. The modified setup provides a shorter response time (~54 and 18 s for 2013 and 2014 setup, respectively) compared to the original WVISS unit (~62 s), which is an improvement in measurement resolution. Another improvement compared to the original WVISS is that the modified setup has a reduced memory effect. Stability tests comparing the modified WVISS and WVISS setups were performed and Allan deviations (σAllan) were calculated to determine precision at different averaging times. For the 2013 modified setup the precision after integration times of 103 s are 0.060 and 0.070‰ for δ18O and δD, respectively. For the WVISS setup the corresponding σAllan values are 0.030, 0.060 and 0.043‰ for δ18O, δD and δ17O, respectively. For the WVISS setup the precision is 0.035, 0.070 and 0.042‰ after 103 s for δ18O, δD and δ17O, respectively. Both the modified setups and WVISS setup are influenced by instrumental drift with δ18O being more drift sensitive than δD. The σAllan values for δ18O of 0.30 and 0.18‰ for the modified (2013) and WVISS setup, respectively after averaging times of 104 s (2.78 h). The Isotopic Water Analyzer (IWA)-modified WVISS setup used during the

Evaporation Induced Oxygen Isotope Fractionation in Impact Ejecta

NASA Astrophysics Data System (ADS)

Macris, C. A.; Young, E. D.; Kohl, I. E.; zur Loye, T. E.

2017-12-01

Tektites are natural glasses formed as quenched impact melt ejecta. Because they experienced extreme heating while entrained in a hot impact vapor plume, tektites allow insight into the nature of these ephemeral events, which play a critical role in planetary accretion and evolution. During tektite formation, the chemical and isotopic composition of parent materials may be modified by (1) vapor/liquid fractionation at high T in the plume, (2) incorporation of meteoric water at the target site, (3) isotope exchange with atmospheric oxygen (if present), or some combination of the three. Trends from O isotope studies reveal a dichotomy: some tektite δ18O values are 4.0-4.5‰ lower than their protoliths (Luft et al. 1987; Taylor & Epstein 1962), opposite in direction to a vaporization induced fractionation; increases in δ18O with decreasing SiO2 in tektites (Taylor & Epstein 1969) is consistent with vapor fractionation. Using an aerodynamic levitation laser furnace (e.g. Macris et al. 2016), we can experimentally determine the contributions of processes (1), (2) and (3) above to tektite compositions. We conducted a series of evaporation experiments to test process (1) using powdered tektite fused into 2 mm spheres and heated to 2423-2473 K for 50-90 s while levitated in Ar in the furnace. Mass losses were from 23 to 26%, reflecting evaporation of Si and O from the melt. The starting tektite had a δ18O value of 10.06‰ (±0.01 2se) and the residues ranged from 13.136‰ (±0.006) for the least evaporated residue to 14.30‰ (±0.02) for the most evaporated (measured by laser fluorination). The increase in δ18O with increasing mass loss is consistent with Rayleigh fractionation during evaporation, supporting the idea that O isotopes are fractionated due to vaporization at high T in an impact plume. Because atmospheric O2 and water each have distinctive Δ17O values, we should be able to use departures from our measured three-isotope fractionation law to evaluate

Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).

PubMed

Chew, Gina; Walczyk, Thomas

2013-04-02

Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

Vapor pressures of a homologous series of polyethylene glycols as a reference data set for validating vapor pressure measurement techniques.

NASA Astrophysics Data System (ADS)

Krieger, Ulrich; Marcolli, Claudia; Siegrist, Franziska

2015-04-01

The production of secondary organic aerosol (SOA) by gas-to-particle partitioning is generally represented by an equilibrium partitioning model. A key physical parameter which governs gas-particle partitioning is the pure component vapor pressure, which is difficult to measure for low- and semivolatile compounds. For typical atmospheric compounds like e.g. citric acid or tartaric acid, vapor pressures have been reported in the literature which differ by up to six orders of magnitude [Huisman et al., 2013]. Here, we report vapor pressures of a homologous series of polyethylene glycols (triethylene glycol to octaethylene glycol) determined by measuring the evaporation rate of single, levitated aerosol particles in an electrodynamic balance. We propose to use those as a reference data set for validating different vapor pressure measurement techniques. With each addition of a (O-CH2-CH2)-group the vapor pressure is lowered by about one order of magnitude which makes it easy to detect the lower limit of vapor pressures accessible with a particular technique down to a pressure of 10-8 Pa at room temperature. Reference: Huisman, A. J., Krieger, U. K., Zuend, A., Marcolli, C., and Peter, T., Atmos. Chem. Phys., 13, 6647-6662, 2013.

Winds, Water Budgets and Stable Isotopes in Tropical Cyclones using TRMM and QUICKSCAT

NASA Technical Reports Server (NTRS)

Lawrence, James R.

2004-01-01

Water vapor is the most abundant greenhouse gas in the atmosphere. Changes in its concentration and distribution are controlled by the hydrologic cycle. Because of its capacity to absorb and emit long wave radiation, release latent heat during condensation in storms and reflect short wave radiation when clouds form it has a major impact on Global climate change. The stable isotope ratios of water are H20 H2l6O and H0 H2l6O. These ratios change whenever water undergoes a phase change. They also change in both rain and water vapor whenever an air parcel is exposed to rain. In addition the relative changes in the two ratios differ as a &nction of the relative humidity. In short, the stable isotope ratios in water vapor in the atmosphere contain an integrated history of the processes affecting the concentration and distribution of water vapor in the atmosphere. Therefore the measurement and interpretation of changes in these stable isotope ratios are a powerful tool matched by no other method in tracing the transport history of water in the atmosphere. Our initial studies under this grant focused on the changes of the stable isotope ratios of precipitation and water vapor in tropical cyclones. The changes in time and space were found to be very large and to trace the transport of water in the storms reflecting changes in basic structural features. Because the stable isotope ratios of rains from tropical cyclones are so low flooding associated with land falling tropical cyclones introduces a negative isotopic spike into the coastal surface waters. In addition the stable isotope ratios of water vapor in the vicinity of tropical cyclones is anomalously low. This suggests that carbonate shelled organisms such as ostracoda living in coastal waters have the potential to record the isotopic spike and thereby provide a long term record of tropical storm activity in sediment cores containing fossil shells. Likewise, tree rings in coastal environments offer a similar potential

Long Term and High Frequency Non-Destructive Monitoring of Soil Water Stable Isotope Compositions in the Laboratory

NASA Astrophysics Data System (ADS)

Rothfuss, Y.; Merz, S.; Pohlmeier, A. J.; Vereecken, H.; Brueggemann, N.

2014-12-01

The fate and dynamics of water stable isotopologues (1H2H16O and 1H218O) are currently well implemented into physically based Soil-Vegetation-Atmosphere Transfer (SVAT) models (e.g. Hydrus 1D, SiSPAT-I, Soil-Litter iso, TOUGHREACT). However, contrary to other state variables (e.g., water content and tension) that can be monitored over long periods (e.g., by time-domain reflectometry, capacitive sensing, tensiometry or micro-psychrometry), water stable isotope compositions (δ2H and δ18O) are analyzed following destructive sampling, and thus are available only at a given time. Thus, there are important discrepancies in time resolution between soil water and stable isotope information which greatly limit the insight potential of the latter. Recently however, a technique based on direct infrared laser absorption spectroscopy was developed that allows simultaneous and direct measurements of δ2H and δ18O in water vapor. Here, we present a non-destructive method for monitoring soil liquid δ2H and δ18O by sampling and measuring water vapor equilibrated with soil water using gas-permeable polypropylene tubing and a Cavity Ring-Down laser Spectrometer (CRDS). An acrylic glass column (d=11 cm, h=60 cm) was (i) equipped with temperature and soil water probes in addition to gas-permeable tubing sections at eight different depths, (ii) filled with pure quartz sand, (iii) saturated from the bottom, and (iv) installed on weighing balances and let dry for 250 days. Each day, soil vapor δ2H and δ18O were measured for each depth by purging the soil water vapor sampled in the tubing sections with dry air and analyzing it with a CRDS. Soil liquid water δ2H and δ18O were then inferred from the values measured in the vapor. The experimental setup allowed following the evolution of the soil water δ2H and δ18O profile, which developed as a result of isotope convective capillary rise and back-diffusion of the stable isotope excess at the soil surface due to fractionating soil

Measurement and Modeling of Water-Vapor Diffusion in Elastomers with Impact in Humidity and Vacuum Measurements

NASA Astrophysics Data System (ADS)

Šetina, Janez; Sefa, Makfir; Erjavec, Bojan; Hudoklin, Domen

2013-03-01

The dynamics of water-vapor dissolution in Viton O-rings is measured with a gravimetric method using a precise mass comparator. A sample gasket was degassed in high vacuum for a sufficiently long period to remove more than 99 % of the dissolved water vapor. After that, it was exposed to the ambient atmosphere with a controlled temperature, and relative humidity and water-vapor uptake curves were measured gravimetrically with a precise balance. The dynamics of a water-vapor release into vacuum from another sample that was previously saturated with water vapor at room temperature was determined. The sample was placed in a vacuum outgassing rate measurement apparatus. The time dependence of the evolved water vapor was calculated by integrating the measured outgassing rate. The physical process of water absorption can be described by the diffusion equation. The geometry of the samples required solving the diffusion equation in cylindrical coordinates. This was done numerically using a finite-difference method. As a result of the modeling, room temperature values of the diffusion constant D, the solubility s, and the permeability K = D× s of water vapor in the sample material (Viton A-401C) were obtained. For sample 1, we obtained D = 8.0 × 10 ^{-8} cm2 {\\cdot } s^{-1} and s = 6.5 × 10^{-7} g {\\cdot } cm^-3 Pa^{-1}, while for sample 2, D = 3.0 × 10^{-7} cm2 s^{-1} and s = 3.5 × 10^{-7} g {\\cdot } cm^{-3} {\\cdot } Pa^{-1}.

Isotopically pure magnesium isotope-24 is prepared from magnesium-24 oxide

NASA Technical Reports Server (NTRS)

Chellew, N. R.; Schilb, J. D.; Steunenberg, R. K.

1968-01-01

Apparatus is used to prepare isotopically pure magnesium isotope-24, suitable for use in neutron scattering and polarization experiments. The apparatus permits thermal reduction of magnesium-24 oxide with aluminum and calcium oxide, and subsequent vaporization of the product metal in vacuum. It uses a resistance-heated furnace tube and cap assembly.

Precise and accurate isotope ratio measurements by ICP-MS.

PubMed

Becker, J S; Dietze, H J

2000-09-01

The precise and accurate determination of isotope ratios by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) is important for quite different application fields (e.g. for isotope ratio measurements of stable isotopes in nature, especially for the investigation of isotope variation in nature or age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, quality assurance of fuel material, for reprocessing plants, nuclear material accounting and radioactive waste control, for tracer experiments using stable isotopes or long-lived radionuclides in biological or medical studies). Thermal ionization mass spectrometry (TIMS), which used to be the dominant analytical technique for precise isotope ratio measurements, is being increasingly replaced for isotope ratio measurements by ICP-MS due to its excellent sensitivity, precision and good accuracy. Instrumental progress in ICP-MS was achieved by the introduction of the collision cell interface in order to dissociate many disturbing argon-based molecular ions, thermalize the ions and neutralize the disturbing argon ions of plasma gas (Ar+). The application of the collision cell in ICP-QMS results in a higher ion transmission, improved sensitivity and better precision of isotope ratio measurements compared to quadrupole ICP-MS without the collision cell [e.g., for 235U/238U approximately 1 (10 microg x L(-1) uranium) 0.07% relative standard deviation (RSD) vs. 0.2% RSD in short-term measurements (n = 5)]. A significant instrumental improvement for ICP-MS is the multicollector device (MC-ICP-MS) in order to obtain a better precision of isotope ratio measurements (with a precision of up to 0.002%, RSD). CE- and HPLC-ICP-MS are used for the separation of isobaric interferences of long-lived radionuclides and stable isotopes by determination of spallation nuclide abundances in an irradiated tantalum target.

Towards absolute laser spectroscopic CO2 isotope ratio measurements

NASA Astrophysics Data System (ADS)

Anyangwe Nwaboh, Javis; Werhahn, Olav; Ebert, Volker

2017-04-01

Knowledge of isotope composition of carbon dioxide (CO2) in the atmosphere is necessary to identify sources and sinks of this key greenhouse gas. In the last years, laser spectroscopic techniques such as cavity ring-down spectroscopy (CRDS) and tunable diode laser absorption spectroscopy (TDLAS) have been shown to perform accurate isotope ratio measurements for CO2 and other gases like water vapour (H2O) [1,2]. Typically, isotope ratios are reported in literature referring to reference materials provided by e.g. the International Atomic Energy Agency (IAEA). However, there could be some benefit if field deployable absolute isotope ratio measurement methods were developed to address issues such as exhausted reference material like the Pee Dee Belemnite (PDB) standard. Absolute isotope ratio measurements would be particularly important for situations where reference materials do not even exist. Here, we present CRDS and TDLAS-based absolute isotope ratios (13C/12C ) in atmospheric CO2. We demonstrate the capabilities of the used methods by measuring CO2 isotope ratios in gas standards. We compare our results to values reported for the isotope certified gas standards. Guide to the expression of uncertainty in measurement (GUM) compliant uncertainty budgets on the CRDS and TDLAS absolute isotope ratio measurements are presented, and traceability is addressed. We outline the current impediments in realizing high accuracy absolute isotope ratio measurements using laser spectroscopic methods, propose solutions and the way forward. Acknowledgement Parts of this work have been carried out within the European Metrology Research Programme (EMRP) ENV52 project-HIGHGAS. The EMRP is jointly funded by the EMRP participating countries within EURAMET and the European Union. References [1] B. Kühnreich, S. Wagner, J. C. Habig,·O. Möhler, H. Saathoff, V. Ebert, Appl. Phys. B 119:177-187 (2015). [2] E. Kerstel, L. Gianfrani, Appl. Phys. B 92, 439-449 (2008).

Stable isotope tracers of water vapor sources in the Atacama Desert, Northern Chile: a pilot study on the Chajnantor Plateau

NASA Astrophysics Data System (ADS)

Samuels, K. E.; Galewsky, J.; Sharp, Z. D.; Rella, C.; Ward, D.

2010-12-01

Subtropical deserts form in response to the interaction of large-scale processes, including atmospheric circulation and oceanic currents, with local features like topography. The degree to which each of these factors controls desert formation and the anticipated impacts of variations in each as climate changes, however, are poorly understood. Stable isotope compositions of water vapor in desert air can help to distinguish between moisture sources and processes that control aridity. The Atacama Desert, located in northern Chile between latitudes 23S and 27S, provides a natural laboratory in which to test the degree to which water vapor isotopologues enable the distinction between processes that control humidity, including the Hadley Circulation, the cold Humboldt Current off the coast of Chile, and the orographic effect of the Andes, in this subtropical desert. Water vapor isotopologues and concentrations were measured in real time using a cavity-ringdown spectrometer deployed on the Chajnantor Plateau over a three-week period from mid-July early August 2010. The elevation of the Plateau, 5000 m amsl (~550 hPa), places it above the boundary layer, allowing the evaluation of the Rayleigh fractionation model from the coast inland. Values reported by the instrument were verified with air samples taken at the coast and the Plateau, which were analyzed on an MAT-252 mass spectrometer. Water vapor concentrations and δD values varied spatially and temporally. Water vapor concentrations on the Plateau ranged from 200 to 3664 ppmv with a mean value of 536 ppmv. In contrast, water vapor concentrations at the coast were approximately 10000 ppmv, and at Yungay, 60 km inland, water vapor concentrations ranged from 1300 to 2000 ppmv from morning to evening. δD values on the Plateau ranged from -526‰ to -100‰ with a mean value of 290‰ with enriched values correlated to periods with higher water vapor concentrations. There are no strong diurnal variations in water vapor

Strong variations in water vapor in the Asian Monsoon UTLS region observed during the 2017 StratoClim campaign

NASA Astrophysics Data System (ADS)

Moyer, E. J.; Clouser, B.; Sarkozy, L.; Gaeta, D. C.; Singer, C. E.

2017-12-01

The StratoClim campaign in July/August 2017 provided the first in-situ sampling in the UTLS region over the Asian monsoon. Preliminary results from high-precision water vapor measurements from a new instrument, the Chicago Water Isotope Spectrometer, imply substantial variation in water vapor above the local cold-point tropopause and above the 380 K potential temperature surface. Profiles across the cold-point tropopause and attendant variability appear to differ from those both in the Tropical Tropopause Layer in the deep tropics and in the North American Monsoon region. We discuss how these water vapor fluctuations relate to implied convective influence and variations in long-range transport. In at least some cases, enhanced water at high altitudes appears correlated with relative isotopic enhancement, suggesting convective influence. Although results at the time of writing are necessarily very preliminary, measurements suggest that the monsoon anticyclone region is characterized by dynamic transport and convective influence up to and beyond the local cold-point tropopause.

Hydrogen isotope ratios of terrestrial leaf wax n-alkanes from the Tibetan Plateau: Controls on apparent enrichment factors, effect of vapor sources and implication for altimetry

NASA Astrophysics Data System (ADS)

Zhang, Xiaolong; Xu, Baiqing; Günther, Franziska; Mügler, Ines; Lange, Markus; Zhao, Huabiao; Li, Jiule; Gleixner, Gerd

2017-08-01

Empirical evidence suggested that the altitudinal dependence of hydrogen isotope ratios of leaf wax n-alkanes (δDwax) can be used to estimate paleoaltitudinal changes. However, the application of δDwax-based paleoaltimetry remains difficult, as the impacts of evaporative, transpirative and biosynthetic processes on hydrogen isotope fractionations in changing environments and the influence of likely changing water vapor sources are not well explored. For this study, we sampled stream waters, soils and plant leaves along two transects spanning large gradients of altitude, precipitation amount, vapor source, temperature and vegetation type on the Tibetan Plateau (TP). δD values of stream water (as an approximation for δDp), soil water (δDsw) and plant leaf water (δDlw) as well as leaf wax n-alkanes were measured in order to quantify isotopic fractionations in the formation of leaf waxes. Most interestingly, we found a strong negative correlation between the evapotranspirative enrichment of leaf water against precipitation (εlw-p), which combines the effects of soil evaporation and leaf transpiration, and the biosynthetic hydrogen isotope fractionation (εwax-lw), which describes isotopic enrichment between leaf wax and leaf water. The relationship yields a steady apparent isotopic enrichment factor (εwax-p) between leaf wax and precipitation, which is independent from climatic parameters and has an average value of -107 ± 26‰ for grasses (monocotyledons) and -77 ± 22‰ for trees (dicotyledons). Since the terrestrial n-alkanes, especially n-C27 and n-C29, in sediments are derived from trees and grasses, the likely change of the vegetation type in the uplift of mountains can change the isotopic estimates by about ±30‰, which corresponds to an altitudinal change of ∼1600 m. We, therefore, suggest that hydrogen isotope ratio of sedimentary n-C31 alkane, which is mainly derived from grasses might be better proxies to reconstruct paleoaltitudes. Our large

Water vapor measurements in- and outside cirrus with the novel water vapor mass spectrometer AIMS-H2O

NASA Astrophysics Data System (ADS)

Kaufmann, Stefan; Schlage, Romy; Voigt, Christiane; Jurkat, Tina; Krämer, Martina; Rolf, Christian; Zöger, Martin; Schäfler, Andreas; Dörnbrack, Andreas

2015-04-01

Water vapor plays a crucial role for the earth's climate both directly via its radiative properties and indirectly due to its ability to form clouds. However, accurate measurements of especially low water vapor concentrations prevalent in the upper troposphere and lower stratosphere are difficult and exhibit large discrepancies between different instruments and methods. In order to address this issue and to provide a comprehensive water vapor data set necessary to gather a complete picture of cloud formation processes, four state-of-the-art hygrometers including the novel water vapor mass spectrometer AIMS-H2O were deployed on the DLR research aircraft HALO during the ML-Cirrus campaign in March/April 2014 over Europe. Here, we present first water vapor measurements of AIMS-H2O on HALO. The instrument performance is validated by intercomparison with the fluorescence hygrometer FISH and the laser hygrometer SHARC, both also mounted in the aircraft. This intercomparison shows good agreement between the instruments from low stratospheric mixing ratios up to higher H2O concentrations at upper tropospheric conditions. Gathering data from over 24 flight hours, no significant offsets between the instruments were found (mean of relative deviation

[Study of high temperature water vapor concentration measurement method based on absorption spectroscopy].

PubMed

Chen, Jiu-ying; Liu, Jian-guo; He, Jun-feng; He, Ya-bai; Zhang, Guang-le; Xu, Zhen-yu; Gang, Qiang; Wang, Liao; Yao, Lu; Yuan, Song; Ruan, Jun; Dai, Yun-hai; Kan, Rui-feng

2014-12-01

Tunable diode laser absorption spectroscopy (TDLAS) has been developed to realize the real-time and dynamic measurement of the combustion temperature, gas component concentration, velocity and other flow parameters, owing to its high sensitivity, fast time response, non-invasive character and robust nature. In order to obtain accurate water vapor concentration at high temperature, several absorption spectra of water vapor near 1.39 μm from 773 to 1273 K under ordinary pressure were recorded in a high temperature experiment setup using a narrow band diode laser. The absorbance of high temperature absorption spectra was calculated by combined multi-line nonlinear least squares fitting method. Two water vapor absorption lines near 7154.35 and 7157.73 cm(-1) were selected for measurement of water vapor at high temperature. A model method for high temperature water vapor concentration was first proposed. Water vapor concentration from the model method at high temperature is in accordance with theoretical reasoning, concentration measurement standard error is less than 0.2%, and the relative error is less than 6%. The feasibility of this measuring method is verified by experiment.

Advances in Raman Lidar Measurements of Water Vapor

NASA Technical Reports Server (NTRS)

Whiteman, D. N.; Evans, K.; Demoz, B.; DiGirolamo, P.; Mielke, B.; Stein, B.; Goldsmith, J. E. M.; Tooman, T.; Turner, D.; Starr, David OC. (Technical Monitor)

2002-01-01

Recent technology upgrades to the NASA/GSFC Scanning Raman Lidar have permitted significant improvements in the daytime and nighttime measurement of water vapor using Raman lidar. Numerical simulation has been used to study the temperature sensitivity of the narrow spectral band measurements presented here.

Probe for measurement of velocity and density of vapor in vapor plume

DOEpatents

Berzins, Leon V.; Bratton, Bradford A.; Fuhrman, Paul W.

1997-01-01

A probe which directs a light beam through a vapor plume in a first direction at a first angle ranging from greater than 0.degree. to less than 90.degree., reflecting the light beam back through the vapor plume at a 90.degree. angle, and then reflecting the light beam through the vapor plume a third time at a second angle equal to the first angle, using a series of mirrors to deflect the light beam while protecting the mirrors from the vapor plume with shields. The velocity, density, temperature and flow direction of the vapor plume may be determined by a comparison of the energy from a reference portion of the beam with the energy of the beam after it has passed through the vapor plume.

Effect of Advection on Evaporative Fluxes and Vapor Isotopic Ratios: The Lake Size Effect

NASA Astrophysics Data System (ADS)

Feng, X.; Lauder, A. M.; Kopec, B. G.; Posmentier, E. S.

2015-12-01

It has been reported that advection of air from land can be identified hundreds of kilometers off shore. With advection, moisture builds up downwind, and the evaporative flux decreases and isotopic flux ratios increase with distance. If a lake is small relative to the equilibration distance, the fluxes of all water isotopologues averaged over the lake are different from those calculated using models without advection. The magnitude of the discrepancy depends on the lake size; we refer to this as the "lake size effect". In Kangerlussuaq, Greenland, we observed significant horizontal gradients in concentration, δD, and δ18O of vapor up to 5 km along the wind direction. Over a 0.5 km long lake, the observed average gradients were 1380 ppm/km for vapor content, 21‰/km for δD, 2.4‰/km for δ18O, and 5‰/km for d-excess. These gradients decreased with distance from the upwind shore. Over a stretch of another, much larger lake 4-5 km from the upwind shore, we observed gradients of 354 ppm/km, 1.5‰/km, 0.22‰/km and 0.3‰/km, for vapor concentration, δD, δ18O, and d-excess, respectively. These observations were modeled successfully using a two-dimensional (2-D, horizontal and vertical) steady state advection diffusion model. This model also computes evaporative fluxes. Using the model results, we assess the magnitude of the lake size effect and its impact on water balance calculations. Under the condition of our field observations and for lakes less than 500 m along the wind direction, the mean flux δ18O and δD were at least 2‰ lower than the corresponding values from a 1-D model (vertical only). If using biased isotopic flux values for water balance calculations, the lake size effect would lead to an underestimation of the lake I/E (input to evaporation) ratio. For example, if the lake effect is 1‰, the corresponding underestimation of the I/E ratio is about 10% if using δ18O, and less than 2% if using δD for the computation. This argues for

Probe for measurement of velocity and density of vapor in vapor plume

DOEpatents

Berzins, L.V.; Bratton, B.A.; Fuhrman, P.W.

1997-03-11

A probe is disclosed which directs a light beam through a vapor plume in a first direction at a first angle ranging from greater than 0{degree} to less than 90{degree}, reflecting the light beam back through the vapor plume at a 90{degree} angle, and then reflecting the light beam through the vapor plume a third time at a second angle equal to the first angle, using a series of mirrors to deflect the light beam while protecting the mirrors from the vapor plume with shields. The velocity, density, temperature and flow direction of the vapor plume may be determined by a comparison of the energy from a reference portion of the beam with the energy of the beam after it has passed through the vapor plume. 10 figs.

Reconciling Isotopic Partitioning Estimates of Moisture Fluxes in Semi-arid Landscapes Through a New Modeling Approach for Evaporation

NASA Astrophysics Data System (ADS)

Kaushik, A.; Berkelhammer, M. B.; O'Neill, M.; Noone, D.

2017-12-01

The partitioning of land surface latent heat flux into evaporation and transpiration remains a challenging problem despite a basic understanding of the underlying mechanisms. Water isotopes are useful tracers for separating evaporation and transpiration contributions because E and T have distinct isotopic ratios. Here we use the isotope-based partitioning method at a semi-arid grassland tall-tower site in Colorado. Our results suggest that under certain conditions evaporation cannot be isotopically distinguished from transpiration without modification of existing partitioning techniques. Over a 4-year period, we measured profiles of stable oxygen and hydrogen isotope ratios of water vapor from the surface to 300 m and soil water down to 1 m along with standard meteorological fluxes. Using these data, we evaluated the contributions of rainfall, equilibration, surface water vapor exchange and sub-surface vapor diffusion to the isotopic composition of evapotranspiration (ET). Applying the standard isotopic approach to find the transpiration portion of ET (i.e., T/ET), we see a significant discrepancy compared with a method to constrain T/ET based on gross primary productivity (GPP). By evaluating the kinetic fractionation associated with soil evaporation and vapor diffusion we find that a significant proportion (58-84%) of evaporation following precipitation is non-fractionating. This is possible when water from isolated soil layers is being nearly completely evaporated. Non-fractionating evaporation looks isotopically like transpiration and therefore leads to an overestimation of T/ET. Including non-fractionating evaporation reconciles the isotope-based partitioning estimates of T/ET with the GPP method, and may explain the overestimation of T/ET from isotopes compared to other methods. Finally, we examine the application of non-fractionating evaporation to other boundary layer moisture flux processes such as rain evaporation, where complete evaporation of smaller

Water vapor variance measurements using a Raman lidar

NASA Technical Reports Server (NTRS)

Evans, K.; Melfi, S. H.; Ferrare, R.; Whiteman, D.

1992-01-01

Because of the importance of atmospheric water vapor variance, we have analyzed data from the NASA/Goddard Raman lidar to obtain temporal scales of water vapor mixing ratio as a function of altitude over observation periods extending to 12 hours. The ground-based lidar measures water vapor mixing ration from near the earth's surface to an altitude of 9-10 km. Moisture profiles are acquired once every minute with 75 m vertical resolution. Data at each 75 meter altitude level can be displayed as a function of time from the beginning to the end of an observation period. These time sequences have been spectrally analyzed using a fast Fourier transform technique. An example of such a temporal spectrum obtained between 00:22 and 10:29 UT on December 6, 1991 is shown in the figure. The curve shown on the figure represents the spectral average of data from 11 height levels centered on an altitude of 1 km (1 plus or minus .375 km). The spectra shows a decrease in energy density with frequency which generally follows a -5/3 power law over the spectral interval 3x10 (exp -5) to 4x10 (exp -3) Hz. The flattening of the spectrum for frequencies greater than 6x10 (exp -3) Hz is most likely a measure of instrumental noise. Spectra like that shown in the figure are calculated for other altitudes and show changes in spectral features with height. Spectral analysis versus height have been performed for several observation periods which demonstrate changes in water vapor mixing ratio spectral character from one observation period to the next. The combination of these temporal spectra with independent measurements of winds aloft provide an opportunity to infer spatial scales of moisture variance.

Evaluating Volatility-controlled Isotope Fractionation During Planet Formation: Kinetics versus Equilibrium

NASA Astrophysics Data System (ADS)

Young, E. D.

2017-12-01

Recent advances in our ability to measure stable isotope ratios of light, rock-forming elements, including those for Zn, K, Fe, Si, and Mg, among others, has resulted in an emerging hypothesis that collisions among rocky planetesimals, planetary embryos, and/or proto-planets caused losses of moderately volatile elements (e.g., K) and "common" or moderately refractory elements (e.g., Mg and Si). The primary evidence is in the form of heavy isotope enrichments in rock-forming elements relative to the chondrite groups that are thought to be representative of planetary precursors. Equilibrium volatility-controlled isotope fractionation for planetesimal magma oceans might have occurred for bodies larger than 0.1% of an Earth mass (½ the mass of Pluto) as these bodies had sufficient gravity to overpower the escape velocities of hot gas at 2000K. Both Jean's escape and viscous drag hydrodynamic escape can obviate the escape velocity limit but will fractionate by mass, not by volatility. Equilibrium vapor/melt fractionation is qualitatively consistent with the greater disparity in 29Si/28Si between Earth and chondrites than in 25Mg/24Mg. However, losses of large masses of vapor are required to record the fractionation in the melts. We consider that if Earth was derived from E chondrite-like materials, the bulk composition of the Earth, assuming refractory Ca was retained, requires > 60% loss of Mg. This is a lot of vapor loss for a process relying on at least intermittent equilibrium, although it comports with the isotopic lever-rule requirements. Paradoxically, the alternative of evaporative loss of rock-forming elements requires less total mass loss. For example, the calculated Mg and Si isotopic compositions of residues resulting from evaporation of chondritic melts can fit the Mg and Si isotopic compositions of Earth, Mars, and angrites with varying background pressures and with total mass losses of near 5% or less. These mass losses are closer to, and even lower than

Vapor cell geometry effect on Rydberg atom-based microwave electric field measurement

NASA Astrophysics Data System (ADS)

Zhang, Linjie; Liu, Jiasheng; Jia, Yue; Zhang, Hao; Song, Zhenfei; Jia, Suotang

2018-03-01

The geometry effect of a vapor cell on the metrology of a microwave electric field is investigated. Based on the splitting of the electromagnetically induced transparency spectra of cesium Rydberg atoms in a vapor cell, high-resolution spatial distribution of the microwave electric field strength is achieved for both a cubic cell and a cylinder cell. The spatial distribution of the microwave field strength in two dimensions is measured with sub-wavelength resolution. The experimental results show that the shape of a vapor cell has a significant influence on the abnormal spatial distribution because of the Fabry–Pérot effect inside a vapor cell. A theoretical simulation is obtained for different vapor cell wall thicknesses and shows that a restricted wall thickness results in a measurement fluctuation smaller than 3% at the center of the vapor cell. Project supported by the National Key Research and Development Program of China (Grant Nos. 2017YFA03044200 and 2016YFF0200104), the National Natural Science Foundation of China (Grant Nos. 91536110, 61505099, and 61378013), and the Fund for Shanxi “331 Project” Key Subjects Construction, China.

LASE measurements of aerosols and water vapor during TARFOX

NASA Technical Reports Server (NTRS)

Ferrare, Richard A.; Ismail, Syed; Browell, Edward V.; Brackett, Vincent G.; Kooi, Susan A.; Clayton, Marian B.; Melfi, Harvey; Whiteman, David N.; Schwenner, Geary; Evans, Keith D.;

Soil tension mediates isotope fractionation during soil water evaporation

NASA Astrophysics Data System (ADS)

Gaj, Marcel; McDonnell, Jeffrey

2017-04-01

Isotope tracing of the water cycle is increasing in its use and usefulness. Many new studies are extracting soil waters and relating these to streamflow, groundwater recharge and plant transpiration. Nevertheless, unlike isotope fractionation factors from open water bodies, soil water fractionation factors are poorly understood and until now, only empirically derived. In contrast to open water evaporation where temperature, humidity and vapor pressure gradient define fractionation (as codified in the well-known Craig and Gordon model), soil water evaporation includes additionally, fractionation by matrix effects. There is yet no physical explanation of kinetic and equilibrium fraction from soil water within the soil profile. Here we present a simple laboratory experiment with four admixtures of soil grain size (from sand to silt to clay). Oven-dried samples were spiked with water of known isotopic composition at different soil water contents. Soils were then stored in sealed bags and the headspace filled with dry air and allowed to equilibrate for 24hours. Isotopic analysis of the headspace vapor was done with a Los Gatos Inc. water vapor isotope analyzer. Soil water potential of subsamples were measured with a water potential meter. We show for the first time that soil tension controls isotope fractionation in the resident soil water. Below a Pf 3.5 the δ-values of 18O and 2H of the headspace vapor is more positive and increases with increasing soil water potential. Surprisingly, we find that the relationship between soil tension and equilibrium fractionation is independent of soil type. However, δ-values of each soil type plot along a distinct evaporation line. These results indicate that equilibrium fractionation is affected by soil tension in addition to temperature. Therefore, at high soil water tension (under dry conditions) equilibrium fractionation is not consistent with current empirical formulations that ignore these effects. These findings may have

A reference data set for validating vapor pressure measurement techniques: homologous series of polyethylene glycols

NASA Astrophysics Data System (ADS)

Krieger, Ulrich K.; Siegrist, Franziska; Marcolli, Claudia; Emanuelsson, Eva U.; Gøbel, Freya M.; Bilde, Merete; Marsh, Aleksandra; Reid, Jonathan P.; Huisman, Andrew J.; Riipinen, Ilona; Hyttinen, Noora; Myllys, Nanna; Kurtén, Theo; Bannan, Thomas; Percival, Carl J.; Topping, David

2018-01-01

To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well-established saturation vapor pressures. However, vapor pressures of semivolatile and low-volatility organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of 2. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem, we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H - (O - CH2 - CH2)n - OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10-7 to 5×10-2 Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows outlying data to be rejected more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressure values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass

Imaging spectrometer measurement of water vapor in the 400 to 2500 nm spectral region

NASA Technical Reports Server (NTRS)

Green, Robert O.; Roberts, Dar A.; Conel, James E.; Dozier, Jeff

1995-01-01

The Airborne Visible-Infrared Imaging Spectrometer (AVIRIS) measures the total upwelling spectral radiance from 400 to 2500 nm sampled at 10 nm intervals. The instrument acquires spectral data at an altitude of 20 km above sea level, as images of 11 by up to 100 km at 17x17 meter spatial sampling. We have developed a nonlinear spectral fitting algorithm coupled with a radiative transfer code to derive the total path water vapor from the spectrum, measured for each spatial element in an AVIRIS image. The algorithm compensates for variation in the surface spectral reflectance and atmospheric aerosols. It uses water vapor absorption bands centered at 940 nm, 1040 nm, and 1380 nm. We analyze data sets with water vapor abundances ranging from 1 to 40 perceptible millimeters. In one data set, the total path water vapor varies from 7 to 21 mm over a distance of less than 10 km. We have analyzed a time series of five images acquired at 12 minute intervals; these show spatially heterogeneous changes of advocated water vapor of 25 percent over 1 hour. The algorithm determines water vapor for images with a range of ground covers, including bare rock and soil, sparse to dense vegetation, snow and ice, open water, and clouds. The precision of the water vapor determination approaches one percent. However, the precision is sensitive to the absolute abundance and the absorption strength of the atmospheric water vapor band analyzed. We have evaluated the accuracy of the algorithm by comparing several surface-based determinations of water vapor at the time of the AVIRIS data acquisition. The agreement between the AVIRIS measured water vapor and the in situ surface radiometer and surface interferometer measured water vapor is 5 to 10 percent.

Effect of perfluorocarbon (perfluorooctyl bromide) vapor on tidal volume measurement during partial liquid ventilation.

PubMed

Davies, Mark W; Dunster, Kimble R

2002-05-01

To compare measured tidal volumes with and without perfluorocarbon (perfluorooctyl bromide) vapor, by using tidal volumes in the range suitable for neonates ventilated with partial liquid ventilation. We also aimed to determine the correction factor needed to calculate tidal volumes measured in the presence of perfluorooctyl bromide vapor. Prospective, experimental study. Neonatal research laboratory. Reproducible tidal volumes from 5 to 30 mL were produced with a rodent ventilator and drawn from humidifier chambers immersed in a water bath at 37 degrees C. Control tidal volumes were drawn from a chamber containing oxygen and water vapor, and the perfluorocarbon tidal volumes were drawn from a chamber containing oxygen, water vapor, and perfluorooctyl bromide vapor. Tidal volumes were measured by a VenTrak respiratory mechanics monitor with a neonatal flow sensor and a Dräger pneumotachometer attached to a Dräger neonatal ventilator. All tidal volumes measured with perfluorooctyl bromide vapor were increased compared with control. The VenTrak-measured tidal volumes increased by 1.8% to 3.5% (an overall increase of 2.2%). The increase was greater with the Dräger hot-wire anemometer: from 2.4% to 6.1% (an overall increase of 5.9%). Regression equations for mean control tidal volumes (response, Y) vs. mean perfluorooctyl bromide tidal volumes (predictor, X) are as follows: for the VenTrak, Y = -0.026 + (0.978 x X), r =.9999, p <.0001; and for the Dräger, Y = 0.251 + (0.944 x X), r =.9996, p <.0001. The presence of perfluorooctyl bromide vapor in the gas flowing through pneumotachometers gives falsely high tidal volume measurements. An estimate of the true tidal volume allowing for the presence of perfluorooctyl bromide vapor can be made from regression equations. Any calculation of lung mechanics must take into account the effect of perfluorooctyl bromide vapor on the measurement of tidal volume.

A New Technique for the Retrieval of Near Surface Water Vapor Using DIAL Measurements

NASA Technical Reports Server (NTRS)

Ismail, Syed; Kooi, Susan; Ferrare, Richard; Winker, David; Hair, Johnathan; Nehrir, Amin; Notari, Anthony; Hostetler, Chris

2015-01-01

Water vapor is one of the most important atmospheric trace gas species and influences radiation, climate, cloud formation, surface evaporation, precipitation, storm development, transport, dynamics, and chemistry. For improvements in NWP (numerical weather prediction) and climate studies, global water vapor measurements with higher accuracy and vertical resolution are needed than are currently available. Current satellite sensors are challenged to characterize the content and distribution of water vapor in the Boundary Layer (BL) and particularly near the first few hundred meters above the surface within the BL. These measurements are critically needed to infer surface evaporation rates in cloud formation and climate studies. The NASA Langley Research Center Lidar Atmospheric Sensing Experiment (LASE) system, which uses the Differential Absorption Lidar (DIAL) technique, has demonstrated the capability to provide high quality water vapor measurements in the BL and across the troposphere. A new retrieval technique is investigated to extend these DIAL water vapor measurements to the surface. This method uses signals from both atmospheric backscattering and the strong surface returns (even over low reflectivity oceanic surfaces) using multiple gain channels to cover the large signal dynamic range. Measurements can be made between broken clouds and in presence of optically thin cirrus. Examples of LASE measurements from a variety of conditions encountered during NASA hurricane field experiments over the Atlantic Ocean are presented. Comparisons of retrieved water vapor profiles from LASE near the surface with dropsonde measurements show very good agreement. This presentation also includes a discussion of the feasibility of developing space-based DIAL capability for high resolution water vapor measurements in the BL and above and an assessment of the technology needed for developing this capability.

Determination of compound-specific Hg isotope ratios from transient signals using gas chromatography coupled to multicollector inductively coupled plasma mass spectrometry (MC-ICP/MS).

PubMed

Dzurko, Mark; Foucher, Delphine; Hintelmann, Holger

2009-01-01

MeHg and inorganic Hg compounds were measured in aqueous media for isotope ratio analysis using aqueous phase derivatization, followed by purge-and-trap preconcentration. Compound-specific isotope ratio measurements were performed by gas chromatography interfaced to MC-ICP/MS. Several methods of calculating isotope ratios were evaluated for their precision and accuracy and compared with conventional continuous flow cold vapor measurements. An apparent fractionation of Hg isotopes was observed during the GC elution process for all isotope pairs, which necessitated integration of signals prior to the isotope ratio calculation. A newly developed average peak ratio method yielded the most accurate isotope ratio in relation to values obtained by a continuous flow technique and the best reproducibility. Compound-specific isotope ratios obtained after GC separation were statistically not different from ratios measured by continuous flow cold vapor measurements. Typical external uncertainties were 0.16 per thousand RSD (n = 8) for the (202)Hg(/198)Hg ratio of MeHg and 0.18 per thousand RSD for the same ratio in inorganic Hg using the optimized operating conditions. Using a newly developed reference standard addition method, the isotopic composition of inorganic Hg and MeHg synthesized from this inorganic Hg was measured in the same run, obtaining a value of delta (202)Hg = -1.49 +/- 0.47 (2SD; n = 10). For optimum performance a minimum mass of 2 ng per Hg species should be introduced onto the column.

Water vapor retrieval from near-IR measurements of polarized scanning atmospheric corrector

NASA Astrophysics Data System (ADS)

Qie, Lili; Ning, Yuanming; Zhang, Yang; Chen, Xingfeng; Ma, Yan; Li, Zhengqiang; Cui, Wenyu

2018-02-01

Water vapor and aerosol are two key atmospheric factors effecting the remote sensing image quality. As water vapor is responsible for most of the solar radiation absorption occurring in the cloudless atmosphere, accurate measurement of water content is important to not only atmospheric correction of remote sensing images, but also many other applications such as the study of energy balance and global climate change, land surface temperature retrieval in thermal remote sensing. A multi-spectral, single-angular, polarized radiometer called Polarized Scanning Atmospheric Corrector (PSAC) were developed in China, which are designed to mount on the same satellite platform with the principle payload and provide essential parameters for principle payload image atmospheric correction. PSAC detect water vapor content via measuring atmosphere reflectance at water vapor absorbing channels (i.e. 0.91 μm) and nearby atmospheric window channel (i.e. 0.865μm). A near-IR channel ratio method was implemented to retrieve column water vapor (CWV) amount from PSAC measurements. Field experiments were performed at Yantai, in Shandong province of China, PSAC aircraft observations were acquired. The comparison between PSAC retrievals and ground-based Sun-sky radiometer measurements of CWV during the experimental flights illustrates that this method retrieves CWV with relative deviations ranging from 4% 13%. This method retrieve CWV more accurate over land than over ocean, as the water reflectance is low.

Determination of nitrogen-15 isotope fractionation in tropine: evaluation of extraction protocols for isotope ratio measurement by isotope ratio mass spectrometry.

PubMed

Molinié, Roland; Kwiecień, Renata A; Silvestre, Virginie; Robins, Richard J

2009-12-01

N-Demethylation of tropine is an important step in the degradation of this compound and related metabolites. With the purpose of understanding the reaction mechanism(s) involved, it is desirable to measure the 15N kinetic isotope effects (KIEs), which can be accessed through the 15N isotope shift (Deltadelta15N) during the reaction. To measure the isotope fractionation in 15N during tropine degradation necessitates the extraction of the residual substrate from dilute aqueous solution without introducing artefactual isotope fractionation. Three protocols have been compared for the extraction and measurement of the 15N/14N ratio of tropine from aqueous medium, involving liquid-liquid phase partitioning or silica-C18 solid-phase extraction. Quantification was by gas chromatography (GC) on the recovered organic phase and delta15N values were obtained by isotope ratio measurement mass spectrometry (irm-MS). Although all the protocols used can provide satisfactory data and both irm-EA-MS and irm-GC-MS can be used to obtain the delta15N values, the most convenient method is liquid-liquid extraction from a reduced aqueous volume combined with irm-GC-MS. The protocols are applied to the measurement of 15N isotope shifts during growth of a Pseudomonas strain that uses tropane alkaloids as sole source of carbon and nitrogen. The accuracy of the determination of the 15N/14N ratio is sufficient to be used for the determination of 15N-KIEs. Copyright 2009 John Wiley & Sons, Ltd.

Improved methodologies for continuous-flow analysis of stable water isotopes in ice cores

NASA Astrophysics Data System (ADS)

Jones, Tyler R.; White, James W. C.; Steig, Eric J.; Vaughn, Bruce H.; Morris, Valerie; Gkinis, Vasileios; Markle, Bradley R.; Schoenemann, Spruce W.

2017-02-01

Water isotopes in ice cores are used as a climate proxy for local temperature and regional atmospheric circulation as well as evaporative conditions in moisture source regions. Traditional measurements of water isotopes have been achieved using magnetic sector isotope ratio mass spectrometry (IRMS). However, a number of recent studies have shown that laser absorption spectrometry (LAS) performs as well or better than IRMS. The new LAS technology has been combined with continuous-flow analysis (CFA) to improve data density and sample throughput in numerous prior ice coring projects. Here, we present a comparable semi-automated LAS-CFA system for measuring high-resolution water isotopes of ice cores. We outline new methods for partitioning both system precision and mixing length into liquid and vapor components - useful measures for defining and improving the overall performance of the system. Critically, these methods take into account the uncertainty of depth registration that is not present in IRMS nor fully accounted for in other CFA studies. These analyses are achieved using samples from a South Pole firn core, a Greenland ice core, and the West Antarctic Ice Sheet (WAIS) Divide ice core. The measurement system utilizes a 16-position carousel contained in a freezer to consecutively deliver ˜ 1 m × 1.3 cm2 ice sticks to a temperature-controlled melt head, where the ice is converted to a continuous liquid stream and eventually vaporized using a concentric nebulizer for isotopic analysis. An integrated delivery system for water isotope standards is used for calibration to the Vienna Standard Mean Ocean Water (VSMOW) scale, and depth registration is achieved using a precise overhead laser distance device with an uncertainty of ±0.2 mm. As an added check on the system, we perform inter-lab LAS comparisons using WAIS Divide ice samples, a corroboratory step not taken in prior CFA studies. The overall results are important for substantiating data obtained from LAS

Doubly labeled water method: in vivo oxygen and hydrogen isotope fractionation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schoeller, D.A.; Leitch, C.A.; Brown, C.

The accuracy and precision of the doubly labeled water method for measuring energy expenditure are influenced by isotope fractionation during evaporative water loss and CO/sub 2/ excretion. To characterize in vivo isotope fractionation, we collected and isotopically analyzed physiological fluids and gases. Breath and transcutaneous water vapor were isotopically fractionated. The degree of fractionation indicated that the former was fractionated under equilibrium control at 37/sup 0/C, and the latter was kinetically fractionated. Sweat and urine were unfractionated. By use of isotopic balance models, the fraction of water lost via fractionating routes was estimated from the isotopic abundances of body water,more » local drinking water, and dietary solids. Fractionated water loss averaged 23% (SD = 10%) of water turnover, which agreed with our previous estimates based on metabolic rate, but there was a systematic difference between the results based on O/sub 2/ and hydrogen. Corrections for isotopic fractionation of water lost in breath and (nonsweat) transcutaneous loss should be made when using labeled water to measure water turnover or CO/sub 2/ production.« less

Grasland Stable Isotope Flux Measurements: Three Isotopomers of Carbon Dioxide Measured by QCL Spectroscopy

NASA Astrophysics Data System (ADS)

Zeeman, M. J.; Tuzson, B.; Eugster, W.; Werner, R. A.; Buchmann, N.; Emmenegger, L.

2007-12-01

To improve our understanding of greenhouse gas dynamics of managed ecosystems such as grasslands, we not only need to investigate the effects of management (e.g., grass cuts) and weather events (e.g., rainy days) on carbon dioxide fluxes, but also need to increase the time resolution of our measurements. Thus, for the first time, we assessed respiration and assimilation fluxes with high time resolution (5Hz) stable isotope measurements at an intensively managed farmland in Switzerland (Chamau, 400m ASL). Two different methods were used to quantify fluxes of carbon dioxide and associated fluxes of stable carbon isotopes: (1) the flux gradient method, and (2) the eddy covariance method. During a week long intensive measurement campaign, we (1) measured mixing ratios of carbon dioxide isotopomers (12C16O2, 12C16O18O, 13C16O2) with a Quantum Cascade Laser (QCL, Aerodyne Inc.) spectroscope and (2) collected air samples for isotope analyses (13C/12C) and (18O/16O) of carbon dioxide by Isotope Ratio Mass Spectrometry (IRMS, Finnigan) every two hours, concurrently along a height profile (z = 0.05; 0.10; 0.31; 2.15m). In the following week, the QCL setup was used for closed-path eddy covariance flux measurement of the carbon dioxide isotopomers, with the air inlet located next to an open-path Infra Red Gas Analyzers (IRGA, LiCor 7500) used simultaneously for carbon dioxide measurements. During this second week, an area of grass inside the footprint was cut and harvested after several days. The first results of in-field continuous QCL measurements of carbon dioxide mixing ratios and their stable isotopic ratios show good agreement with IRGA measurements and isotope analysis of flask samples by IRMS. Thus, QCL spectroscopy is a very promising tool for stable isotope flux investigations.

Observations of Hydrogen and Oxygen Isotopes in Leaf Water Confirm the Craig-Gordon Model under Wide-Ranging Environmental Conditions1

PubMed Central

Roden, John S.; Ehleringer, James R.

1999-01-01

The Craig-Gordon evaporative enrichment model of the hydrogen (δD) and oxygen (δ18O) isotopes of water was tested in a controlled-environment gas exchange cuvette over a wide range (400‰ δD and 40‰ δ18O) of leaf waters. (Throughout this paper we use the term “leaf water” to describe the site of evaporation, which should not be confused with “bulk leaf water” a term used exclusively for uncorrected measurements obtained from whole leaf water extractions.) Regardless of how the isotopic composition of leaf water was achieved (i.e. by changes in source water, atmospheric vapor δD or δ18O, vapor pressure gradients, or combinations of all three), a modified version of the Craig-Gordon model was shown to be sound in its ability to predict the δD and δ18O values of water at the site of evaporation. The isotopic composition of atmospheric vapor was shown to have profound effects on the δD and δ18O of leaf water and its influence was dependent on vapor pressure gradients. These results have implications for conditions in which the isotopic composition of atmospheric vapor is not in equilibrium with source water, such as experimental systems that grow plants under isotopically enriched water regimes. The assumptions of steady state were also tested and found not to be a major limitation for the utilization of the leaf water model under relatively stable environmental conditions. After a major perturbation in the δD and δ18O of atmospheric vapor, the leaf reached steady state in approximately 2 h, depending on vapor pressure gradients. Following a step change in source water, the leaf achieved steady state in 24 h, with the vast majority of changes occurring in the first 3 h. Therefore, the Craig-Gordon model is a useful tool for understanding the environmental factors that influence the hydrogen and oxygen isotopic composition of leaf water as well as the organic matter derived from leaf water. PMID:10444100

Mid-infrared laser-absorption diagnostic for vapor-phase measurements in an evaporating n-decane aerosol

NASA Astrophysics Data System (ADS)

Porter, J. M.; Jeffries, J. B.; Hanson, R. K.

2009-09-01

A novel three-wavelength mid-infrared laser-based absorption/extinction diagnostic has been developed for simultaneous measurement of temperature and vapor-phase mole fraction in an evaporating hydrocarbon fuel aerosol (vapor and liquid droplets). The measurement technique was demonstrated for an n-decane aerosol with D 50˜3 μ m in steady and shock-heated flows with a measurement bandwidth of 125 kHz. Laser wavelengths were selected from FTIR measurements of the C-H stretching band of vapor and liquid n-decane near 3.4 μm (3000 cm -1), and from modeled light scattering from droplets. Measurements were made for vapor mole fractions below 2.3 percent with errors less than 10 percent, and simultaneous temperature measurements over the range 300 K< T<900 K were made with errors less than 3 percent. The measurement technique is designed to provide accurate values of temperature and vapor mole fraction in evaporating polydispersed aerosols with small mean diameters ( D 50<10 μ m), where near-infrared laser-based scattering corrections are prone to error.

Enthalpy of Vaporization and Vapor Pressures: An Inexpensive Apparatus

ERIC Educational Resources Information Center

Battino, Rubin; Dolson, David A.; Hall, Michael A.; Letcher, Trevor M.

2007-01-01

A simple and inexpensive method to determine the enthalpy of vaporization of liquids by measuring vapor pressure as a function of temperature is described. The vapor pressures measured with the stopcock cell were higher than the literature values and those measured with the sidearm rubber septum cell were both higher and lower than literature…

Continual in situ monitoring of pore water stable isotopes in the subsurface

NASA Astrophysics Data System (ADS)

Volkmann, T. H. M.; Weiler, M.

2014-05-01

Stable isotope signatures provide an integral fingerprint of origin, flow paths, transport processes, and residence times of water in the environment. However, the full potential of stable isotopes to quantitatively characterize subsurface water dynamics is yet unfolded due to the difficulty in obtaining extensive, detailed, and repeated measurements of pore water in the unsaturated and saturated zone. This paper presents a functional and cost-efficient system for non-destructive continual in situ monitoring of pore water stable isotope signatures with high resolution. Automatic controllable valve arrays are used to continuously extract diluted water vapor in soil air via a branching network of small microporous probes into a commercial laser-based isotope analyzer. Normalized liquid-phase isotope signatures are then obtained based on a specific on-site calibration approach along with basic corrections for instrument bias and temperature dependent isotopic fractionation. The system was applied to sample depth profiles on three experimental plots with varied vegetation cover in southwest Germany. Two methods (i.e., based on advective versus diffusive vapor extraction) and two modes of sampling (i.e., using multiple permanently installed probes versus a single repeatedly inserted probe) were tested and compared. The results show that the isotope distribution along natural profiles could be resolved with sufficiently high accuracy and precision at sampling intervals of less than four minutes. The presented in situ approaches may thereby be used interchangeably with each other and with concurrent laboratory-based direct equilibration measurements of destructively collected samples. It is thus found that the introduced sampling techniques provide powerful tools towards a detailed quantitative understanding of dynamic and heterogeneous shallow subsurface and vadose zone processes.

Laser separation of lithium isotopes by double resonance enhanced multiphoton ionization of Li/sub 2/

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balz, J.G.; Bernheim, R.A.; Gold, L.P.

1987-01-01

Multiphoton ionization spectra of /sup 7/Li/sub 2/, /sup 6/Li/sub 2/, and /sup 7/Li/sup 6/Li vapors have been measured in the 570--650 nm region using a single, low resolution, multimode cw dye laser. A number of wavelengths provide selective multiphoton ionization of one isotopic species demonstrating the possibility of efficient laser-driven isotopic separation in lithium in this wavelength region.

Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation

NASA Astrophysics Data System (ADS)

Lu, G.; Depaolo, D. J.; Kang, Q.; Zhang, D.

2007-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically-symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over- saturation, determines crystal morphology, there are no quantitative models that relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be direct relationships between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D lattice Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. Crystal growth patterns can be varied between random growth and deterministic growth (along the maximum concentration gradient for example). The input parameters needed are the isotope- dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the condensation coefficient for ice is uncertain. The ratio D/k is a length (order 1 micron) that determines the minimum scale of dendritic growth features

Isotopic composition of zinc, copper, and iron in lunar samples

NASA Astrophysics Data System (ADS)

Moynier, F.; Albarède, F.; Herzog, G. F.

2006-12-01

We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ 66Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ 65Cu ˜ +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ 56Fe = -0.24‰, δ 65Cu = -0.42‰, and δ 66Zn ˜ -3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰ ⩽ δ 56Fe ⩽ 0.51‰, 2.6‰ ⩽ δ 65Cu ⩽ 4.5‰, and 2.2‰ ⩽ δ 66Zn ⩽ 6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on

Mass-Dependent and -Independent Fractionation of Mercury Isotope during Gas-Phase Oxidation of Elemental Mercury Vapor by Atomic Cl and Br.

PubMed

Sun, Guangyi; Sommar, Jonas; Feng, Xinbin; Lin, Che-Jen; Ge, Maofa; Wang, Weigang; Yin, Runsheng; Fu, Xuewu; Shang, Lihai

2016-09-06

This study presents the first measurement of Hg stable isotope fractionation during gas-phase oxidation of Hg(0) vapor by halogen atoms (Cl(•), Br(•)) in the laboratory at 750 ± 1 Torr and 298 ± 3 K. Using a relative rate technique, the rate coefficients for Hg(0)+Cl(•) and Hg(0)+Br(•) reactions are determined to be (1.8 ± 0.5) × 10(-11) and (1.6 ± 0.8) × 10(-12) cm(3) molecule(-1) s(-1), respectively. Results show that heavier isotopes are preferentially enriched in the remaining Hg(0) during Cl(•) initiated oxidation, whereas being enriched in the product during oxidation by Br(•). The fractionation factors for (202)Hg/(198)Hg during the Cl(•) and Br(•) initiated oxidations are α(202/198) = 0.99941 ± 0.00006 (2σ) and 1.00074 ± 0.00014 (2σ), respectively. A Δ(199)Hg/Δ(201)Hg ratio of 1.64 ± 0.30 (2σ) during oxidation of Hg(0) by Br atoms suggests that Hg-MIF is introduced by the nuclear volume effect (NVE). In contrast, the Hg(0) + Cl(•) reaction produces a Δ(199)Hg/Δ(201)Hg-slope of 1.89 ± 0.18 (2σ), which in addition to a high degree of odd-mass-number isotope MIF suggests impacts from MIF effects other than NVE. This reaction also exhibits significant MIF of (200)Hg (Δ(200)Hg, up to -0.17‰ in the reactant) and is the first physicochemical process identified to trigger (200)Hg anomalies that are frequently detected in atmospheric samples.

Nitrogen isotope fractionation during archaeal ammonia oxidation: Coupled estimates from isotopic measurements of ammonium and nitrite

NASA Astrophysics Data System (ADS)

Mooshammer, Maria; Stieglmeier, Michaela; Bayer, Barbara; Jochum, Lara; Melcher, Michael; Wanek, Wolfgang

2014-05-01

Ammonia-oxidizing archaea (AOA) are ubiquitous in marine and terrestrial environments and knowledge about the nitrogen (N) isotope effect associated with their ammonia oxidation activity will allow a better understanding of natural abundance isotope ratios, and therefore N transformation processes, in the environment. Here we examine the kinetic isotope effect for ammonia oxidation in a pure soil AOA culture (Ca. Nitrososphaera viennensis) and a marine AOA enrichment culture. We estimated the isotope effect from both isotopic signatures of ammonium and nitrite over the course of ammonia oxidation. Estimates of the isotope effect based on the change in the isotopic signature of ammonium give valuable insight, because these estimates are not subject to the same concerns (e.g., accumulation of an intermediate) as estimates based on isotopic measurements of nitrite. Our results show that both the pure soil AOA culture and a marine AOA enrichment culture have similar but substantial isotope effect during ammonia consumption (31-34 per mill; based on ammonium) and nitrite production (43-45 per mill; based on nitrite). The 15N fractionation factors of both cultures tested fell in the upper range of the reported isotope effects for archaeal and bacterial ammonia oxidation (10-41 per mill) or were even higher than those. The isotope fractionation for nitrite production was significantly larger than for ammonium consumption, indicating that (1) some intermediate (e.g., hydroxylamine) of ammonia oxidation accumulates, allowing for a second 15N fractionation step to be expressed, (2) a fraction of ammonia oxidized is lost via gaseous N forms (e.g., NO or N2O), which is 15N-enriched or (3) a fraction of ammonium is assimilated into AOA biomass, biomass becoming 15N-enriched. The significance of these mechanisms will be explored in more detail for the soil AOA culture, based on isotope modeling and isotopic measurements of biomass and N2O.

An exposure system for measuring nasal and lung uptake of vapors in rats

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dahl, A.R.; Brookins, L.K.; Gerde, P.

1995-12-01

Inhaled gases and vapors often produce biological damage in the nasal cavity and lower respiratory tract. The specific site within the respirator tract at which a gas or vapor is absorbed strongly influences the tissues at risk to potential toxic effects; to predict or to explain tissue or cell specific toxicity of inhaled gases or vapors, the sites at which they are absorbed must be known. The purpose of the work reported here was to develop a system for determining nose and lung absorption of vapors in rats, an animal commonly used in inhalation toxicity studies. In summary, the exposuremore » system described allows us to measure in the rate: (1) nasal absorption and desorption of vapors; (2) net lung uptake of vapors; and (3) the effects of changed breathing parameters on vapor uptake.« less

A New Raman Water Vapor Lidar Calibration Technique and Measurements in the Vicinity of Hurricane Bonnie

NASA Technical Reports Server (NTRS)

Evans, Keith D.; Demoz, Belay B.; Cadirola, Martin P.; Melfi, S. H.; Whiteman, David N.; Schwemmer, Geary K.; Starr, David OC.; Schmidlin, F. J.; Feltz, Wayne

2000-01-01

The NAcA/Goddard Space Flight Center Scanning Raman Lidar has made measurements of water vapor and aerosols for almost ten years. Calibration of the water vapor data has typically been performed by comparison with another water vapor sensor such as radiosondes. We present a new method for water vapor calibration that only requires low clouds, and surface pressure and temperature measurements. A sensitivity study was performed and the cloud base algorithm agrees with the radiosonde calibration to within 10- 15%. Knowledge of the true atmospheric lapse rate is required to obtain more accurate cloud base temperatures. Analysis of water vapor and aerosol measurements made in the vicinity of Hurricane Bonnie are discussed.

Performance Measurements and Mapping of a R-407C Vapor Injection Scroll Compressor

NASA Astrophysics Data System (ADS)

Lumpkin, Domenique; Spielbauer, Niklas; Groll, Eckhard

2017-08-01

Environmental conditions significantly define the performance of HVAC&R systems. Vapor compression systems in hot climates tend to operate at higher pressure ratios, leading to increased discharge temperatures. Higher discharge temperatures can lead to higher irreversibilities in the compression process, lower specific enthalpies differences across the evaporator, and possibly a reduction in the compressor life due to the breakdown of the oil used for lubrication. To counter these effects, the use of economized, vapor injection compressors is proposed for vapor compression systems in high temperature climates. Such compressors are commercially available for refrigeration applications, in particular, supermarket refrigeration systems. However, compressor maps for vapor injection compressors are limited and none exist for R-407C. Through calorimeter testing, a compressor map for a single-port vapor injection compressor using R-407C was developed. A standard correlation for mapping single-port vapor injection compressors is proposed and validated using the compressor test results. The system and compressor performance with and without vapor injection was considered. As expected, with vapor injection there was a reduction in compressor discharge temperatures and an increase in the system coefficient of performance. The proposed dimensionless correlation is more accurate than the AHRI polynomial for mapping the injection ratio, discharge temperature, and compressor heat loss. The predicted volumetric efficiency values from the dimensionless correlation is within 1% of the measured valued. Similarly, the predicted isentropic efficiency values are within 2% of the measured values.

Measurements of Forest-Atmosphere Isotopic CO2 Exchange by Eddy Covariance

NASA Astrophysics Data System (ADS)

Wehr, R. A.; Munger, J. W.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Saleska, S. R.

2010-12-01

Isotopic CO2 flux measurements are a promising means for partitioning the net ecosystem exchange of CO2 into photosynthetic and respiratory components. This approach to partitioning is possible in principle because of the distinct isotopic signatures of respired and photosynthesized CO2, but has been infeasible in practice—especially in forests—because of the difficulty of measuring isotopic ratios with sufficient precision and time response for use in eddy covariance (EC) flux calculations. Recent advances in laser spectroscopic instrumentation have changed that. We report measurements of isotopic (13C and 18O) CO2 exchange made by eddy covariance at Harvard Forest between April and December, 2010. The measurements were made using a continuous-wave quantum cascade laser spectrometer (Aerodyne Research Inc.) sampling at 4 Hz and are, to our knowledge, the first EC isotopic flux measurements at a forest site. The spectrometer can measure δ13C and δ18O with internal precisions (standard deviation of 1-minute averages) of 0.03 ‰, and [CO2] with an internal precision of 15 ppb; the instrumental accuracy, calibration, and long-term stability are discussed in detail. The isotopic data are considered in relation to environmental variables (PAR, temperature, humidity, soil temperature and moisture), and a first attempt at flux partitioning using the isotopic fluxes is presented.

Low temperature measurement of the vapor pressures of planetary molecules

NASA Technical Reports Server (NTRS)

Kraus, George F.

1989-01-01

Interpretation of planetary observations and proper modeling of planetary atmospheres are critically upon accurate laboratory data for the chemical and physical properties of the constitutes of the atmospheres. It is important that these data are taken over the appropriate range of parameters such as temperature, pressure, and composition. Availability of accurate, laboratory data for vapor pressures and equilibrium constants of condensed species at low temperatures is essential for photochemical and cloud models of the atmospheres of the outer planets. In the absence of such data, modelers have no choice but to assume values based on an educated guess. In those cases where higher temperature data are available, a standard procedure is to extrapolate these points to the lower temperatures using the Clausius-Clapeyron equation. Last summer the vapor pressures of acetylene (C2H2) hydrogen cyanide (HCN), and cyanoacetylene (HC3N) was measured using two different methods. At the higher temperatures 1 torr and 10 torr capacitance manometers were used. To measure very low pressures, a technique was used which is based on the infrared absorption of thin film (TFIR). This summer the vapor pressure of acetylene was measured the TFIR method. The vapor pressure of hydrogen sulfide (H2S) was measured using capacitance manometers. Results for H2O agree with literature data over the common range of temperature. At the lower temperatures the data lie slightly below the values predicted by extrapolation of the Clausius-Clapeyron equation. Thin film infrared (TFIR) data for acetylene lie significantly below the values predicted by extrapolation. It is hoped to bridge the gap between the low end of the CM data and the upper end of the TFIR data in the future using a new spinning rotor gauge.

Error analysis of integrated water vapor measured by CIMEL photometer

NASA Astrophysics Data System (ADS)

Berezin, I. A.; Timofeyev, Yu. M.; Virolainen, Ya. A.; Frantsuzova, I. S.; Volkova, K. A.; Poberovsky, A. V.; Holben, B. N.; Smirnov, A.; Slutsker, I.

2017-01-01

Water vapor plays a key role in weather and climate forming, which leads to the need for continuous monitoring of its content in different parts of the Earth. Intercomparison and validation of different methods for integrated water vapor (IWV) measurements are essential for determining the real accuracies of these methods. CIMEL photometers measure IWV at hundreds of ground-based stations of the AERONET network. We analyze simultaneous IWV measurements performed by a CIMEL photometer, an RPG-HATPRO MW radiometer, and a FTIR Bruker 125-HR spectrometer at the Peterhof station of St. Petersburg State University. We show that the CIMEL photometer calibrated by the manufacturer significantly underestimates the IWV obtained by other devices. We may conclude from this intercomparison that it is necessary to perform an additional calibration of the CIMEL photometer, as well as a possible correction of the interpretation technique for CIMEL measurements at the Peterhof site.

Investigations on atomic-vapor-filter high-spectral-resolution lidar for temperature measurements

NASA Technical Reports Server (NTRS)

Voss, E.; Weitkamp, C.

1992-01-01

The temperature measurement by the analysis of Rayleigh scattered laser radiation with atomic vapor filters is investigated in both theory and laboratory experiments. Synthetic air is irradiated with a cw dye laser at 283 nano-meters, and the backscattered spectrum is analyzed with two lead vapor cells in one oven. Temperature measurements are carried out, and the effect of different parameters on the accuracy is investigated. Important aspects for the realization of a lidar are given.

Isotopic Measurements of Organic Sulfonates From The Murchison Meteorite

NASA Technical Reports Server (NTRS)

Cooper, G. W.; Chang, S.; DeVincenzi, Donald L. (Technical Monitor)

1995-01-01

Organic sulfonates and phosphonates have been extracted from the Murchison meteorite for stable isotope measurements. Preliminary stable isotope measurements of individual alkyl sulfonates, R-SO3H (R=C(sub n)H(sub 2n+l)), are shown. These compounds were found in aqueous extracts of Murchison. Both groups show trends similar to other homologous series of organic compounds indigenous to Murchison. Molecular abundances decrease with increasing carbon number, and all possible isomers at each carbon number (through C-4) are present. Carbon isotope measurements of the sulfonates show a decrease in the C-13/C-12 ratio with increasing carbon number. The overall objectives of this project are to obtain dime element carbon, hydrogen, and sulfur - intramolecular isotopic analyses of individual sulfonates, and isotopic measurement of carbon and hydrogen of the phosphonates as a group. The Murchison meteorite is the best characterized carbonaceous chondrite with respect to organic chemistry. The finding of organic sulfonates and phosphonates in Murchison is of interest because they are the first well-characterized series of sulfur and phosphorus containing organic compounds found in meteorites. Also, meteorites, comets, and interplanetary dust particles may have been involved in chemical evolution on the early Earth. Because of the critical role of organic phosphorus and sulfur in all living systems, it is particularly interesting to see examples of abiotic syntheses of these classes of compounds. The study of the isotopic composition of the sulfonates and phosphonates can yield insight into their possible interstellar origin as well as their mechanisms of synthesis in the early solar system. Previous isotopic analyses of other classes of organic compounds indigenous to meteorites, e.g., amino acids, carboxylic acids, and hydrocarbons indicate the possibility that interstellar molecules were incorporated into meteorite parent bodies. In these compounds the ratios of heavy to

Investigating potential wet bias in the Purple Crow Lidar water vapor measurements

NASA Astrophysics Data System (ADS)

VanKerkhove, Jeffrey; Sica, R. J.; Wing, R.; Argall, P. S.

2018-04-01

The Purple Crow Lidar is a large aperture lidar, capable of retrieving water vapor into the strato-sphere. A comparison with the ALVICE lidar in 2012 showed water vapor measurements were consistently larger than those of ALVICE in the lower stratosphere, prompting an investigation of the system. Processing approaches and additional instrumental corrections are considered.

Advances in Raman Lidar Measurements of Water Vapor, Cirrus Clouds and Carbon Dioxide

NASA Technical Reports Server (NTRS)

Whiteman, David N.; Potter, John R.; Tola, Rebecca; Rush, Kurt; Veselovskii, Igor; Cadirola, Martin; Comer, Joseph

2006-01-01

Narrow-band interference filters with improved transmission in the ultraviolet have been developed under NASA-funded research and used in the Raman Airborne Spectroscopic Lidar (RASL) in ground- based, upward-looking tests. RASL is an airborne Raman Lidar system designed to measure water vapor mixing ratio, and aerosol backscatter/extinction/depolarization. It also possesses the capability to make experimental measurements of cloud liquid water and carbon dioxide. It is being prepared for first flight tests during the summer of 2006. With the newly developed filters installed in RASL, measurements were made of atmospheric water vapor, cirrus cloud optical properties and carbon dioxide that improve upon any previously demonstrated using Raman lidar. Daytime boundary layer profiling of water vapor mixing ratio is performed with less than 5% random error using temporal and spatial resolution of 2-minutes and 60 - 210, respectively. Daytime cirrus cloud optical depth and extinction- to-backscatter ratio measurements are made using 1-minute average. Sufficient signal strength is demonstrated to permit the simultaneous profiling of carbon dioxide and water vapor mixing ratio into the free troposphere during the nighttime. Downward-looking from an airborne RASL should possess the same measurement statistics with approximately a factor of 5 - 10 decrease in averaging time. A description of the technology improvements are provided followed by examples of the improved Raman lidar measurements.

Portable device for generation of ultra-pure water vapor feeds

NASA Astrophysics Data System (ADS)

Velin, P.; Stenman, U.; Skoglundh, M.; Carlsson, P.-A.

2017-11-01

A portable device for the generation of co-feeds of water vapor has been designed, constructed, and evaluated for flexible use as an add-on component to laboratory chemical reactors. The vapor is formed by catalytic oxidation of hydrogen, which benefits the formation of well-controlled minute concentrations of ultra-pure water. Analysis of the effluent stream by on-line mass spectrometry and Fourier transform infrared spectroscopy confirms that water vapor can be, with high precision, generated both rapidly and steadily over extended periods in the range of 100 ppm to 3 vol. % (limited by safety considerations) using a total flow of 100 to 1500 ml/min at normal temperature and pressure. Further, the device has been used complementary to a commercial water evaporator and mixing system to span water concentrations up to 12 vol. %. Finally, an operando diffuse reflective infrared Fourier transform spectroscopic measurement of palladium catalysed methane oxidation in the absence and presence of up to 1.0 vol. % water has been carried out to demonstrate the applicability of the device for co-feeding well-controlled low concentrations of water vapor to a common type of spectroscopic experiment. The possibilities of creating isotopically labeled water vapor as well as using tracer gases for dynamic experiments are discussed.

Portable device for generation of ultra-pure water vapor feeds.

PubMed

Velin, P; Stenman, U; Skoglundh, M; Carlsson, P-A

2017-11-01

A portable device for the generation of co-feeds of water vapor has been designed, constructed, and evaluated for flexible use as an add-on component to laboratory chemical reactors. The vapor is formed by catalytic oxidation of hydrogen, which benefits the formation of well-controlled minute concentrations of ultra-pure water. Analysis of the effluent stream by on-line mass spectrometry and Fourier transform infrared spectroscopy confirms that water vapor can be, with high precision, generated both rapidly and steadily over extended periods in the range of 100 ppm to 3 vol. % (limited by safety considerations) using a total flow of 100 to 1500 ml/min at normal temperature and pressure. Further, the device has been used complementary to a commercial water evaporator and mixing system to span water concentrations up to 12 vol. %. Finally, an operando diffuse reflective infrared Fourier transform spectroscopic measurement of palladium catalysed methane oxidation in the absence and presence of up to 1.0 vol. % water has been carried out to demonstrate the applicability of the device for co-feeding well-controlled low concentrations of water vapor to a common type of spectroscopic experiment. The possibilities of creating isotopically labeled water vapor as well as using tracer gases for dynamic experiments are discussed.

NASA/GSFC Scanning Raman Lidar Measurements of Water Vapor and Cirrus Clouds during WVIOP2000 and AFWEX

NASA Technical Reports Server (NTRS)

Whiteman, D. N.; Evans, K. D.; DiGirolamo, P.; Demoz, B. B.; Turner, D.; Comstock, J.; Ismail, S.; Ferrare, R. A.; Browell, E. V.; Goldsmith, J. E. M.;

Determination of mercury in SRM crude oils and refined products by isotope dilution cold vapor ICP-MS using closed-system combustion.

PubMed

Kelly, W Robert; Long, Stephen E; Mann, Jacqueline L

2003-07-01

Mercury was determined by isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICP-MS) in four different liquid petroleum SRMs. Samples of approximately 0.3 g were spiked with stable (201)Hg and wet ashed in a closed system (Carius tube) using 6 g of high-purity nitric acid. Three different types of commercial oils were measured: two Texas crude oils, SRM 2721 (41.7+/-5.7 pg g(-1)) and SRM 2722 (129+/-13 pg g(-1)), a low-sulfur diesel fuel, SRM 2724b (34+/-26 pg g(-1)), and a low-sulfur residual fuel oil, SRM 1619b (3.5+/-0.74 ng g(-1)) (mean value and 95% CI). The Hg values for the crude oils and the diesel fuel are the lowest values ever reported for these matrices. The method detection limit, which is ultimately limited by method blank uncertainty, is approximately 10 pg g(-1) for a 0.3 g sample. Accurate Hg measurements in petroleum products are needed to assess the contribution to the global Hg cycle and may be needed in the near future to comply with reporting regulations for toxic elements.

SRS-sensor 13C/12C isotops measurements for detecting Helicobacter Pylori

NASA Astrophysics Data System (ADS)

Grishkanich, Aleksandr; Chubchenko, Yan; Elizarov, Valentin; Zhevlakov, Aleksandr; Konopelko, Leonid

2018-02-01

We developed SRS-sensor 13C/12C isotops measurements detecting Helicobacter Pylori for medical diagnostics of human health. Measuring of absolute 13C/12C isotope amount ratios allows to explore the topical problems of the modern world, alcoholic beverages and tobacco, medical diagnostics of human health. SRS method is used to measure the ratio of carbon isotopes in the exhaled carbon dioxide, which is used to diagnose the human infection of Helicobacter pylori and the influence of the Helicobacter pylori bacterium on the occurrence of gastritis, gastric and duodenal ulcers. A method for the analysis of human infection with Helicobacter pylori was developed on the basis of measurements of the ratio of 13C / 12C carbon isotopes in human exhaled air with a high level of measurement accuracy. The article reviews the work in the field of provision comparability of absolute 13C/12C isotope amount ratios in the environment and food. The analysis of the technical and metrological characteristics of traditional and perspective instruments for measuring isotope ratios is presented. The provision of comparability of absolute 13C/12C isotope amount ratios is carried by gravimetrically prepared reference standards. The key features and emerging issues are discussed.

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

Measurement of isotope ratios on transient signals by MC-ICP-MS.

PubMed

Günther-Leopold, Ines; Wernli, Beat; Kopajtic, Zlatko; Günther, Detlef

2004-01-01

Precise and accurate isotope ratio measurements are an important task in many applications such as isotope-dilution mass spectrometry, bioavailability studies, or the determination of isotope variations in geological or nuclear samples. The technique of MC-ICP-MS has attracted much attention because it permits the precise measurement of isotope compositions for a wide range of elements combined with excellent detection limits due to high ionisation efficiencies. However, the results are based mainly on measurements using continuous sample introduction. In the present study the determination of isotope ratios on various transient signals with a time duration of 30 to 60 s has been achieved by coupling high-performance liquid chromatography to a multicollector inductively coupled plasma mass spectrometer. In order to investigate the origin of ratio drifts across the transient signals for this hyphenated technique, measurements with the same standard solutions were also carried out using a flow-injection device for sample introduction. As a result of this application it could be concluded that the main source of the bias in the measured isotope ratios is within the ICP-MS instead of fractionation effects on the chromatographic column material. Preliminary studies on short transient signals of gaseous samples (dry plasma) showed a reverse fractionation effect compared with wet plasma conditions (flow injection and HPLC).

MG Isotopic Measurement of FIB-Isolated Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

Messenger, Scott R.; Nguyen, A.; Ito, M.; Rahman, Z.

2010-01-01

The majority of presolar oxide and silicate grains are ascribed to origins in low-mass red giant and asymptotic giant branch (AGB) stars based on their O isotopic ratios. However, a minor population of these grains (< 10%) has O isotopic ratios incompatible with these sources. Two principle alternative sources are higher-than-solar metallicity (Z) stars or, more likely, supernovae (SN) [1-3]. These rare (Group 4) grains [3] are characterized by enrichments in O-18, and typically also enrichments in O-17. An even rarer subset of grains with extremely large enrichments in O-17 and smaller depletions in O-18 were suggested to come from binary star systems [2]. To establish the origins of these isotopically unusual grains, it is necessary to examine isotopic systems in addition to O. Presolar silicates offer several elements diagnostic of their stellar sources and nuclear processes, including O, Si, Mg, Fe and Ca. However, the database for minor element isotopic compositions in silicates is seriously lacking. To date only two silicate grains have been analyzed for Mg [4] or Fe [5]. One major complicating factor is their small size (average 230 nm), which greatly limits the number of measurements that can be performed on any one grain and makes it more difficult to obtain statistically relevant data. This problem is compounded because the grains are identified among isotopically solar silicates, which contribute a diluting signal in isotopic measurements [1]. Thus, relatively small isotopic anomalies are missed due to this dilution effect. By applying focused ion beam (FIB) milling, we obtain undiluted Mg isotopic ratios of isolated rare presolar silicate grains to investigate their sources.

Measurement of isotope ratio of Ca{sup +} ions in a linear Paul Trap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hashimoto, Y.; Minamino, K.; Nagamoto, D.

2009-03-17

Measurement of isotope ratios of Calcium is very useful in many fields. So we demonstrated the measurement of isotope ratios of {sup 40}Ca{sup +}(abundance 96.4%) to {sup 44}Ca{sup +}(2.09%) ions in a linear Paul trap with several laser lights tuning to the isotope shifts. And we found that the experimental parameters had large influences on the measurement of the isotope ratios.

Method to make accurate concentration and isotopic measurements for small gas samples

NASA Astrophysics Data System (ADS)

Palmer, M. R.; Wahl, E.; Cunningham, K. L.

2013-12-01

Carbon isotopic ratio measurements of CO2 and CH4 provide valuable insight into carbon cycle processes. However, many of these studies, like soil gas, soil flux, and water head space experiments, provide very small gas sample volumes, too small for direct measurement by current constant-flow Cavity Ring-Down (CRDS) isotopic analyzers. Previously, we addressed this issue by developing a sample introduction module which enabled the isotopic ratio measurement of 40ml samples or smaller. However, the system, called the Small Sample Isotope Module (SSIM), does dilute the sample during the delivery with inert carrier gas which causes a ~5% reduction in concentration. The isotopic ratio measurements are not affected by this small dilution, but researchers are naturally interested accurate concentration measurements. We present the accuracy and precision of a new method of using this delivery module which we call 'double injection.' Two portions of the 40ml of the sample (20ml each) are introduced to the analyzer, the first injection of which flushes out the diluting gas and the second injection is measured. The accuracy of this new method is demonstrated by comparing the concentration and isotopic ratio measurements for a gas sampled directly and that same gas measured through the SSIM. The data show that the CO2 concentration measurements were the same within instrument precision. The isotopic ratio precision (1σ) of repeated measurements was 0.16 permil for CO2 and 1.15 permil for CH4 at ambient concentrations. This new method provides a significant enhancement in the information provided by small samples.

Vacuum distillation: vapor filtered-catalytic oxidation water reclamation system utilizing radioisotopes

NASA Technical Reports Server (NTRS)

Honegger, R. J.; Remus, G. A.; Kurg, E. K.

1971-01-01

The development of a functional model water reclamation system is discussed. The system produces potable water by distillation from the urine and respiration-perspiration condensate at the normal rate generated by four men. Basic processes employed are vacuum distillation, vapor filtration, vapor phase catalytic oxidation, and condensation. The system is designed to use four 75-watt isotope heaters for distillation thermal input, and one 45-watt isotope for the catalytic oxidation unit. The system is capable of collecting and storing urine, and provides for stabilizing the urine by chemical pretreatment. The functional model system is designed for operation in a weightless condition with liquid-vapor phase separators for the evaporator still, and centrifugal separators for urine collection and vapor condensation. The system provides for storing and dispensing reclaimed potable water. The system operates in a batch mode for 40 days, with urine residues accumulating in the evaporator. The evaporator still and residue are removed to storage and replaced with a fresh still for the next 40-day period.

LASE Measurements of Water Vapor, Aerosol, and Cloud Distributions in Saharan Air Layers and Tropical Disturbances

NASA Technical Reports Server (NTRS)

Ismail, Syed; Ferrare, Richard A.; Browell, Edward V.; Kooi, Susan A.; Dunion, Jason P.; Heymsfield, Gerry; Notari, Anthony; Butler, Carolyn F.; Burton, Sharon; Fenn, Marta;

Measurement of Low Amounts of Precipitable Water Vapor Using Ground-Based Millimeterwave Radiometry

NASA Technical Reports Server (NTRS)

Racette, Paul E.; Westwater, Ed R.; Han, Yong; Gasiewski, Albin J.; Klein, Marian; Cimini, Domenico; Jones, David C.; Manning, WIll; Kim, Edward J.; Wang, James R.

2003-01-01

Extremely dry conditions characterized by amounts of precipitable water vapor (PWV) as as 1-2 mm commonly occur in high-latitude regions during the winter months. While such atmospheres carry only a few percent of the latent heat energy compared to tropical atmospheres, the effects of low vapor amounts on the polar radiation budget - both directly through modulation of longwave radiation and indirectly through the formation of clouds - are considerable. Accurate measurements of precipitable water vapor (PWV) during such dry conditions are needed to improve polar radiation models for use in understanding and predicting change in the climatically sensitive polar regions. To this end, the strong water vapor absorption at 183.310 GHz provides a unique means of measuring low amounts of PWV. Weighting function analysis, forward model calculations based upon a 7-year radiosonde dataset, and retrieval simulations consistently predict that radiometric measurements made using several millimeter-wavelength (MMW) channels near the 183 GHz line, together with established microwave (MW) measurements at the 22.235 GHz water vapor line and -3 1 GHz atmospheric absorption window can be used to determine within 5% uncertainty the full range of PWV expected in the Arctic. This unique collective capability stands in spite of accuracy limitations stemming from uncertainties due to the sensitivity of the vertical distribution of temperature and water vapor at MMW channels. In this study the potential of MMW radiometry using the 183 GHz line for measuring low amounts of PWV is demonstrated both theoretically and experimentally. The study uses data obtained during March 1999 as part of an experiment conducted at the Department of Energy s Cloud and Radiation Testbed (CART) near Barrow, Alaska. Several radiometers from both NOAA and NASA were deployed during the experiment to provide the first combined MMW and MW ground-based data set during dry arctic conditions. Single-channel retrievals

Differential absorption and Raman lidar for water vapor profile measurements - A review

NASA Technical Reports Server (NTRS)

Grant, William B.

1991-01-01

Differential absorption lidar and Raman lidar have been applied to the range-resolved measurements of water vapor density for more than 20 years. Results have been obtained using both lidar techniques that have led to improved understanding of water vapor distributions in the atmosphere. This paper reviews the theory of the measurements, including the sources of systematic and random error; the progress in lidar technology and techniques during that period, including a brief look at some of the lidar systems in development or proposed; and the steps being taken to improve such lidar systems.

New reference materials for nitrogen-isotope-ratio measurements

USGS Publications Warehouse

Böhlke, John Karl; Gwinn, C. J.; Coplen, T. B.

1993-01-01

Three new reference materials were manufactured for calibration of relative stable nitrogen-isotope-ratio measurements: USGS25 (ammonium sulfate) d15N' = -30 per mil; USGS26 (ammonium sulfate) d15N' = +54 per mil; USGS32 (potassium nitrate) d15N' = +180 per mil, where d15N', relative to atmospheric nitrogen, is an approximate value subject to change following interlaboratory comparisons. These materials are isotopically homogeneous in aliquots at least as small as 10 µmol N2 (or about 1-2 mg of salt). The new reference materials greatly extend the range of d15N values of internationally distributed standards, and they allow normalization of d15N measurements over almost the full range of known natural isotope variation on Earth. The methods used to produce these materials may be adapted to produce homogeneous local laboratory standards for routine use.

Emerging Technologies and Synergies for Airborne and Space-Based Measurements of Water Vapor Profiles

NASA Astrophysics Data System (ADS)

Nehrir, Amin R.; Kiemle, Christoph; Lebsock, Mathew D.; Kirchengast, Gottfried; Buehler, Stefan A.; Löhnert, Ulrich; Liu, Cong-Liang; Hargrave, Peter C.; Barrera-Verdejo, Maria; Winker, David M.

2017-11-01

A deeper understanding of how clouds will respond to a warming climate is one of the outstanding challenges in climate science. Uncertainties in the response of clouds, and particularly shallow clouds, have been identified as the dominant source of the discrepancy in model estimates of equilibrium climate sensitivity. As the community gains a deeper understanding of the many processes involved, there is a growing appreciation of the critical role played by fluctuations in water vapor and the coupling of water vapor and atmospheric circulations. Reduction of uncertainties in cloud-climate feedbacks and convection initiation as well as improved understanding of processes governing these effects will result from profiling of water vapor in the lower troposphere with improved accuracy and vertical resolution compared to existing airborne and space-based measurements. This paper highlights new technologies and improved measurement approaches for measuring lower tropospheric water vapor and their expected added value to current observations. Those include differential absorption lidar and radar, microwave occultation between low-Earth orbiters, and hyperspectral microwave remote sensing. Each methodology is briefly explained, and measurement capabilities as well as the current technological readiness for aircraft and satellite implementation are specified. Potential synergies between the technologies are discussed, actual examples hereof are given, and future perspectives are explored. Based on technical maturity and the foreseen near-mid-term development path of the various discussed measurement approaches, we find that improved measurements of water vapor throughout the troposphere would greatly benefit from the combination of differential absorption lidar focusing on the lower troposphere with passive remote sensors constraining the upper-tropospheric humidity.

The earliest Lunar Magma Ocean differentiation recorded in Fe isotopes

NASA Astrophysics Data System (ADS)

Wang, Kun; Jacobsen, Stein B.; Sedaghatpour, Fatemeh; Chen, Heng; Korotev, Randy L.

2015-11-01

Recent high-precision isotopic measurements show that the isotopic similarity of Earth and Moon is unique among all known planetary bodies in our Solar System. These observations provide fundamental constraints on the origin of Earth-Moon system, likely a catastrophic Giant Impact event. However, in contrast to the isotopic composition of many elements (e.g., O, Mg, Si, K, Ti, Cr, and W), the Fe isotopic compositions of all lunar samples are significantly different from those of the bulk silicate Earth. Such a global Fe isotopic difference between the Moon and Earth provides an important constraint on the lunar formation - such as the amount of Fe evaporation as a result of a Giant Impact origin of the Moon. Here, we show through high-precision Fe isotopic measurements of one of the oldest lunar rocks (4.51 ± 0.10 Gyr dunite 72 415), compared with Fe isotope results of other lunar samples from the Apollo program, and lunar meteorites, that the lunar dunite is enriched in light Fe isotopes, complementing the heavy Fe isotope enrichment in other lunar samples. Thus, the earliest olivine accumulation in the Lunar Magma Ocean may have been enriched in light Fe isotopes. This new observation allows the Fe isotopic composition of the bulk silicate Moon to be identical to that of the bulk silicate Earth, by balancing light Fe in the deep Moon with heavy Fe in the shallow Moon rather than the Moon having a heavier Fe isotope composition than Earth as a result of Giant Impact vaporization.

High precision isotope ratio measurements of mercury isotopes in cinnabar ores using multi-collector inductively coupled plasma mass spectrometry.

PubMed

Hintelmann, Holger; Lu, ShengYong

2003-06-01

Variations in Hg isotope ratios in cinnabar ores obtained from different countries were detected by high precision isotope ratio measurements using multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Values of delta198/202Hg varied from 0.0-1.3 percent per thousand relative to a NIST SRM 1641d Hg solution. The typical external uncertainty of the delta values was 0.06 to 0.26 percent per thousand. Hg was introduced into the plasma as elemental Hg after reduction by sodium borohydride. A significant fractionation of lead isotopes was observed during the simultaneous generation of lead hydride, preventing normalization of the Hg isotope ratios using the measured 208/206Pb ratio. Hg ratios were instead corrected employing the simultaneously measured 205/203T1 ratio. Using a 10 ng ml(-1) Hg solution and 10 min of sampling, introducing 60 ng of Hg, the internal precision of the isotope ratio measurements was as low as 14 ppm. Absolute Hg ratios deviated from the representative IUPAC values by approximately 0.2% per u. This observation is explained by the inadequacy of the exponential law to correct for mass bias in MC-ICP-MS measurements. In the absence of a precisely characterized Hg isotope ratio standard, we were not able to determine unambiguously the absolute Hg ratios of the ore samples, highlighting the urgent need for certified standard materials.

SPADE H2O measurements and the seasonal cycle of statospheric water vapor

NASA Technical Reports Server (NTRS)

Hintsa, Eric J.; Weinstock, Elliot M.; Dessler, Andrew E.; Anderson, James G.; Loewenstein, Max; Podolske, James R.

1994-01-01

We present measurements of lower statospheric water vapor obtained during the Stratospheric Phototchemistry, Aerosols and Dynamics Expedition (SPADE) mission with a new high precision, fast response, Lyman-alpha hygrometer. The H2O data show a distinct seasonal cycle. For air that recently entered the statosphere, data collected during the fall show much more water vapor than data from the spring. Fast quasi-horizontal mixing causes compact relationships between water and N2O to be established on relatively short time scales. The measurements are consistent with horizontal mixing times of a few months or less. Vertical mixing appears to cause the seasonal variations in water vapor to propagate up to levels corresponding to air that has been in the stratosphere approximately one year.

Gas and hydrogen isotopic analyses of volcanic eruption clouds in Guatemala sampled by aircraft

USGS Publications Warehouse

Rose, W.I.; Cadle, R.D.; Heidt, L.E.; Friedman, I.; Lazrus, A.L.; Huebert, B.J.

1980-01-01

Gas samples were collected by aircraft entering volcanic eruption clouds of three Guatemalan volcanoes. Gas chromatographic analyses show higher H2 and S gas contents in ash eruption clouds and lower H2 and S gases in vaporous gas plumes. H isotopic data demonstrate lighter isotopic distribution of water vapor in ash eruption clouds than in vaporous gas plumes. Most of the H2O in the vaporous plumes is probably meteoric. The data are the first direct gas analyses of explosive eruptive clouds, and demonstrate that, in spite of atmospheric admixture, useful compositional information on eruptive gases can be obtained using aircraft. ?? 1980.

Water vapor content in the polar atmosphere measured by Lyman-alpha/OH fluorescence method

NASA Technical Reports Server (NTRS)

Iwasaka, Y.; Saitoh, S.; Ono, A.

1985-01-01

The water vapor of the polar stratosphere possibly plays an important role in various aeronomical processes; for example, OH radical formation through photodissociation of H2O, formation of water cluster ions, radiative energy transfer in the lower stratosphere, condensation onto particulate matter, and so on. In addition to these, it has been speculated, from the viewpoint of global transport and/or budget of water vapor, that the polar stratosphere functions as an active sink. STANFORD (1973) emphasized the existence of the stratospheric Cist cloud in the polar stratosphere which brought a large loss rate of stratospheric water vapor through a so-called freeze-out of cloud particles from the stratosphere into the troposphere. However, these geophysically interesting problems unfortunately remain to be solved, owing to the lack of measurements on water vapor distribution and its temporal variation in the polar stratosphere. The water vapor content measured at Syowa Station (69.00 deg S, 39.35 deg E), Antarctica using a balloon-borne hygrometer (Lyman - alpha/OH fluorescence type) is discussed.

DANCEing with the Stars: Measuring Neutron Capture on Unstable Isotopes with DANCE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Couture, A.; Bond, E.; Bredeweg, T. A.

2009-03-10

Isotopes heavier than iron are known to be produced in stars through neutron capture processes. Two major processes, the slow (s) and rapid (r) processes are each responsible for 50% of the abundances of the heavy isotopes. The neutron capture cross sections of the isotopes on the s process path reveal information about the expected abundances of the elements as well as stellar conditions and dynamics. Until recently, measurements on unstable isotopes, which are most important for determining stellar temperatures and reaction flow, have not been experimentally feasible. The Detector for Advance Neutron Capture Experiments (DANCE) located at the Losmore » Alamos Neutron Science Center (LANSCE) was designed to perform time-of-flight neutron capture measurements on unstable isotopes for nuclear astrophysics, stockpile stewardship, and reactor development. DANCE is a 4-{pi}BaF{sub 2} scintillator array which can perform measurements on sub-milligram samples of isotopes with half-lives as short as a few hundred days. These cross sections are critical for advancing our understanding of the production of the heavy isotopes.« less

Fiber-Optic Gratings for Lidar Measurements of Water Vapor

NASA Technical Reports Server (NTRS)

Vann, Leila B.; DeYoung, Russell J.

2006-01-01

Narrow-band filters in the form of phase-shifted Fabry-Perot Bragg gratings incorporated into optical fibers are being developed for differential-absorption lidar (DIAL) instruments used to measure concentrations of atmospheric water vapor. The basic idea is to measure the relative amounts of pulsed laser light scattered from the atmosphere at two nearly equal wavelengths, one of which coincides with an absorption spectral peak of water molecules and the other corresponding to no water vapor absorption. As part of the DIAL measurement process, the scattered light is made to pass through a filter on the way to a photodetector. Omitting other details of DIAL for the sake of brevity, what is required of the filter is to provide a stop band that: Surrounds the water-vapor spectral absorption peaks at a wavelength of 946 nm, Has a spectral width of at least a couple of nanometers, Contains a pass band preferably no wider than necessary to accommodate the 946.0003-nm-wavelength water vapor absorption peak [which has 8.47 pm full width at half maximum (FWHM)], and Contains another pass band at the slightly shorter wavelength of 945.9 nm, where there is scattering of light from aerosol particles but no absorption by water molecules. Whereas filters used heretofore in DIAL have had bandwidths of =300 pm, recent progress in the art of fiber-optic Bragg-grating filters has made it feasible to reduce bandwidths to less than or equal to 20 pm and thereby to reduce background noise. Another benefit of substituting fiber-optic Bragg-grating filters for those now in use would be significant reductions in the weights of DIAL instruments. Yet another advantage of fiber-optic Bragg-grating filters is that their transmission spectra can be shifted to longer wavelengths by heating or stretching: hence, it is envisioned that future DIAL instruments would contain devices for fine adjustment of transmission wavelengths through stretching or heating of fiber-optic Bragg-grating filters

Effect of the Thermocouple on Measuring the Temperature Discontinuity at a Liquid-Vapor Interface.

PubMed

Kazemi, Mohammad Amin; Nobes, David S; Elliott, Janet A W

2017-07-18

The coupled heat and mass transfer that occurs in evaporation is of interest in a large number of fields such as evaporative cooling, distillation, drying, coating, printing, crystallization, welding, atmospheric processes, and pool fires. The temperature jump that occurs at an evaporating interface is of central importance to understanding this complex process. Over the past three decades, thermocouples have been widely used to measure the interfacial temperature jumps at a liquid-vapor interface during evaporation. However, the reliability of these measurements has not been investigated so far. In this study, a numerical simulation of a thermocouple when it measures the interfacial temperatures at a liquid-vapor interface is conducted to understand the possible effects of the thermocouple on the measured temperature and features in the temperature profile. The differential equations of heat transfer in the solid and fluids as well as the momentum transfer in the fluids are coupled together and solved numerically subject to appropriate boundary conditions between the solid and fluids. The results of the numerical simulation showed that while thermocouples can measure the interfacial temperatures in the liquid correctly, they fail to read the actual interfacial temperatures in the vapor. As the results of our numerical study suggest, the temperature jumps at a liquid-vapor interface measured experimentally by using a thermocouple are larger than what really exists at the interface. For a typical experimental study of evaporation of water at low pressure, it was found that the temperature jumps measured by a thermocouple are overestimated by almost 50%. However, the revised temperature jumps are still in agreement with the statistical rate theory of interfacial transport. As well as addressing the specific application of the liquid-vapor temperature jump, this paper provides significant insight into the role that heat transfer plays in the operation of thermocouples

Defining Uncertainty and Error in Planktic Foraminiferal Oxygen Isotope Measurements

NASA Astrophysics Data System (ADS)

Fraass, A. J.; Lowery, C.

2016-12-01

Foraminifera are the backbone of paleoceanography, and planktic foraminifera are one of the leading tools for reconstructing water column structure. Currently, there are unconstrained variables when dealing with the reproducibility of oxygen isotope measurements. This study presents the first results from a simple model of foraminiferal calcification (Foraminiferal Isotope Reproducibility Model; FIRM), designed to estimate the precision and accuracy of oxygen isotope measurements. FIRM produces synthetic isotope data using parameters including location, depth habitat, season, number of individuals included in measurement, diagenesis, misidentification, size variation, and vital effects. Reproducibility is then tested using Monte Carlo simulations. The results from a series of experiments show that reproducibility is largely controlled by the number of individuals in each measurement, but also strongly a function of local oceanography if the number of individuals is held constant. Parameters like diagenesis or misidentification have an impact on both the precision and the accuracy of the data. Currently FIRM is a tool to estimate isotopic error values best employed in the Holocene. It is also a tool to explore the impact of myriad factors on the fidelity of paleoceanographic records. FIRM was constructed in the open-source computing environment R and is freely available via GitHub. We invite modification and expansion, and have planned inclusions for benthic foram reproducibility and stratigraphic uncertainty.

Measuring Vapor Pressure with an Isoteniscope: A Hands-on Introduction to Thermodynamic Concepts

ERIC Educational Resources Information Center

Chen, Wenqian; Haslam, Andrew J.; Macey, Andrew; Shah, Umang V.; Brechtelsbauer, Clemens

2016-01-01

Characterization of the vapor pressure of a volatile liquid or azeotropic mixture, and its fluid phase diagram, can be achieved with an isoteniscope and an industrial grade digital pressure sensor using the experimental method reported in this study. We describe vapor-pressure measurements of acetone and n-hexane and their azeotrope, and how the…

Preliminary results of oxygen isotope ratio measurement with a particle-gamma coincidence method

NASA Astrophysics Data System (ADS)

Borysiuk, Maciek; Kristiansson, Per; Ros, Linus; Abdel, Nassem S.; Elfman, Mikael; Nilsson, Charlotta; Pallon, Jan

2015-04-01

The possibility to study variations in the oxygen isotopic ratio with photon tagged nuclear reaction analysis (pNRA) is evaluated in the current work. The experiment described in the article was performed at Lund Ion Beam Analysis Facility (LIBAF) with a 2 MeV deuteron beam. Isotopic fractionation of light elements such as carbon, oxygen and nitrogen is the basis of many analytical tools in hydrology, geology, paleobiology and paleogeology. IBA methods provide one possible tool for measurement of isotopic content. During this experimental run we focused on measurement of the oxygen isotopic ratio. The measurement of stable isotopes of oxygen has a number of applications; the particular one driving the current investigation belongs to the field of astrogeology and specifically evaluation of fossil extraterrestrial material. There are three stable isotopes of oxygen: 16O, 17O and 18O. We procured samples highly enriched with all three isotopes. Isotopes 16O and 18O were easily detected in the enriched samples, but no significant signal from 17O was detected in the same samples. The measured yield was too low to detect 18O in a sample with natural abundances of oxygen isotopes, at least in the current experimental setup, but the spectral line from the reaction with 16O was clearly visible.

A survey and new measurements of ice vapor pressure at temperatures between 170 and 250K

NASA Technical Reports Server (NTRS)

Marti, James; Mauersberger, Konrad

1993-01-01

New measurements of ice vapor pressures at temperatures between 170 and 250 K are presented and published vapor pressure data are summarized. An empirical vapor pressure equation was derived and allows prediction of vapor pressures between 170 k and the triple point of water with an accuracy of approximately 2 percent. Predictions obtained agree, within experimental uncertainty, with the most reliable equation derived from thermodynamic principles.

Combined and isolated effects of pCO2 and soil water content on carbon isotope discrimination during C3 photosynthesis

NASA Astrophysics Data System (ADS)

Salmon, O. E.; Welp, L.; Shepson, P. B.; Stirm, B. H.

2016-12-01

Water vapor is responsible for over half of the natural atmospheric greenhouse effect. As global temperatures increase due to fossil fuel combustion, atmospheric water vapor concentrations are also expected to increase in positive feedback. Additionally, studies have shown that urban areas can influence humidity levels, and the frequency and intensity of precipitation events. It is thus important to understand anthropogenic modification of the hydrological cycle, particularly around urban areas, where over half of the world's population resides. Airborne measurements of water vapor isotopologues containing 2H and 18O were conducted to better understand processes influencing atmospheric moisture levels around urban areas. Airborne measurements were conducted around the Indianapolis and Washington, D.C.-Baltimore areas during afternoon hours in February and March 2016, using a Los Gatos Research Water Vapor Isotope Analyzer installed in Purdue University's experimental aircraft, the Airborne Laboratory for Atmospheric Research. The measurements of 2H and 18O allow for the calculation of deuterium excess (= δ2H - 8*δ18O), which provides information about non-equilibrium processes, such as kinetic effects, air parcel mixing, and transpiration. There are few studies that have reported observations of deuterium excess above the surface level ( 100 m). During the measurement campaign, vertical profiles were frequently conducted from 300 m above the ground to an altitude of approximately 1.5 km, effectively characterizing water vapor isotope profiles spanning the boundary layer and lower free troposphere. Measurements probed the transition from planetary boundary layer air to free troposphere air to provide high resolution deuterium excess information across this interface. Processes such as Rayleigh distillation, atmospheric mixing, and surface fluxes potentially impacting water vapor deuterium excess through the boundary layer and free troposphere with be discussed.

Absolute Isotopic Abundance Ratios and the Accuracy of Δ47 Measurements

NASA Astrophysics Data System (ADS)

Daeron, M.; Blamart, D.; Peral, M.; Affek, H. P.

2016-12-01

Conversion from raw IRMS data to clumped isotope anomalies in CO2 (Δ47) relies on four external parameters: the (13C/12C) ratio of VPDB, the (17O/16O) and (18O/16O) ratios of VSMOW (or VPDB-CO2), and the slope of the triple oxygen isotope line (λ). Here we investigate the influence that these isotopic parameters exert on measured Δ47 values, using real-world data corresponding to 7 months of measurements; simulations based on randomly generated data; precise comparisons between water-equilibrated CO2 samples and between carbonate standards believed to share quasi-identical Δ47 values; reprocessing of two carbonate calibration data sets with different slopes of Δ47 versus T. Using different sets of isotopic parameters generally produces systematic offsets as large as 0.04 ‰ in final Δ47 values. What's more, even using a single set of isotopic parameters can produce intra- and inter-laboratory discrepancies in final Δ47 values, if some of these parameters are inaccurate. Depending on the isotopic compositions of the standards used for conversion to "absolute" values, these errors should correlate strongly with either δ13C or δ18O, or more weakly with both. Based on measurements of samples expected to display identical Δ47 values, such as 25°C water-equilibrated CO2 with different carbon and oxygen isotope compositions, or high-temperature standards ETH-1 and ETH-2, we conclude that the isotopic parameters used so far in most clumped isotope studies produces large, systematic errors controlled by the relative bulk isotopic compositions of samples and standards, which should be one of the key factors responsible for current inter-laboratory discrepancies. By contrast, the isotopic parameters of Brand et al. [2010] appear to yield accurate Δ47 values regardless of bulk isotopic composition. References:Brand, Assonov and Coplen [2010] http://dx.doi.org/10.1351/PAC-REP-09-01-05

Stable Isotope Systematics in Grasshopper Assemblages Along an Elevation Gradient, Colorado

NASA Astrophysics Data System (ADS)

Kohn, M. J.; Evans, S.; Dean, J.; Nufio, C.

2012-12-01

Insects comprise over three quarters of all animal species, yet studies of body water isotopic composition are limited to only the cockroach, the hoverfly, and chironomid flies. These studies suggest that oxygen and hydrogen isotopic compositions in body water are primarily controlled by dietary water sources, with modification from respiratory and metabolic processes. In particular, outward diffusion of isotopically depleted water vapor through insect spiracles at low humidity enriches residual body water in 18O and 2H (D). Stable isotope compositions (δ18O and δD) also respond to gradients in elevation and humidity, but these influences remain poorly understood. In this study, we measured grasshopper body water and local vegetation isotopic compositions along an elevation gradient in Colorado to evaluate three hypotheses: 1) Insect body water isotopic composition is directly related to food source water composition 2) Water vapor transport alters body water isotopic compositions relative to original diet sources, and 3) Elevation gradients influence isotopic compositions in insect body water. Thirty-five species of grasshopper were collected from 14 locations in Colorado grasslands, ranging in elevation from 450 to 800 meters (n=131). Body water was distilled from previously frozen grasshopper specimens using a vacuum extraction line, furnaces (90 °C), and liquid nitrogen traps. Water samples were then analyzed for δ18O and δD on an LGR Liquid Water Isotope Analyzer, housed in the Department of Geosciences, Boise State University. Grasshopper body water isotopic compositions show wide variation, with values ranging between -76.64‰ to +42.82‰ in δD and -3.06‰ to +26.78‰ in δ18O. Precipitation δ18O values over the entire Earth excluding the poles vary by approximately 30‰, comparable to the total range measured in our single study area. Most grasshopper values deviate from the global meteoric water line relating δ18O and δD in precipitation

Development of a Trajectory Model for the Analysis of Stratospheric Water Vapor

NASA Astrophysics Data System (ADS)

Koby, Timothy Robert

To study stratospheric water vapor, a new trajectory model was created. The model is built from first principles specific to stratospheric motion and can run on any gridded dataset, making it more versatile than current solutions. The design of a new model was motivated by measurements of elevated stratospheric water vapor, which in situ isotopic measurements have determined to be tropospheric in origin. A moist stratosphere has substantial feedbacks in the climate system including radiative, chemical, and biological effects. Additionally, elevated stratospheric water vapor is theorized as an important coupling in the historical transition to the Eocene, 56 million years ago, as well as emergence from the Eocene 40 million years ago. This transition mirrors modern climate change, both in surface temperature and carbon dioxide increase. However, the historical transition became much more extreme and settled to a state of warm temperatures from the equator to the poles with little variation in between. The lack of latitudinal gradient in temperature is associated with a moist stratosphere, which provides additional motivation for thoroughly understanding the effects of adding water vapor to the stratosphere in a climatological context. The time evolution of water vapor enhancements from convective injection is analyzed by initializing trajectories over satellite-measured water vapor enhancements. The model runs show water vapor concentrations that remain elevated over the background concentrations for several days and often over a week, which is of the timescale that warrants concern over increased halogen catalyzed ozone loss and the subsequent risk to public health. By analyzing stratospheric winds during the summer months over North America using normalized angular momentum, a pattern of frequent stratospheric anticyclonic activity over North America emerges as a unique feature of the region. This provides a mechanism for the modeled persistent elevated water

High-Accuracy Measurements of Total Column Water Vapor From the Orbiting Carbon Observatory-2

NASA Technical Reports Server (NTRS)

Nelson, Robert R.; Crisp, David; Ott, Lesley E.; O'Dell, Christopher W.

2016-01-01

Accurate knowledge of the distribution of water vapor in Earth's atmosphere is of critical importance to both weather and climate studies. Here we report on measurements of total column water vapor (TCWV) from hyperspectral observations of near-infrared reflected sunlight over land and ocean surfaces from the Orbiting Carbon Observatory-2 (OCO-2). These measurements are an ancillary product of the retrieval algorithm used to measure atmospheric carbon dioxide concentrations, with information coming from three highly resolved spectral bands. Comparisons to high-accuracy validation data, including ground-based GPS and microwave radiometer data, demonstrate that OCO-2 TCWV measurements have maximum root-mean-square deviations of 0.9-1.3mm. Our results indicate that OCO-2 is the first space-based sensor to accurately and precisely measure the two most important greenhouse gases, water vapor and carbon dioxide, at high spatial resolution [1.3 x 2.3 km(exp. 2)] and that OCO-2 TCWV measurements may be useful in improving numerical weather predictions and reanalysis products.

Notes on Vapor Pressure Equilibria Measurements

NASA Astrophysics Data System (ADS)

Krieger, Albert G.; Henderson, John W.

1996-11-01

After reading the article in this Journal (1), we would like to share our experience with a similar experiment based on an earlier article in this Journal (2). Freshman students at our institution use manometers and 24/40 ground-glass distillation apparatus (abandoned by our organic chemistry classes) to measure boiling points at reduced pressures. Distilled water and 2-methyl-1-propanol are typical liquids of interest. Students enter their collected data into an Excel template which generates graphs of P vs. T and log P vs 1/T to demonstrate the nonlinear and linear relationships that exist between vapor pressures and temperatures. The templates use the Clausius-Clapeyron equation to determine the normal boiling point and the enthalpy of vaporization of the liquid studies. The boiling point determined for water is 100 oC and for 2-methyl-1-propanol is 106 oC, within 2 o of the CRC Handbook data. We have found that the availability of state-of-the-art equipment need not limit the ability to teach and demonstrate fundamental principles. The Excel template (Macintosh) is available upon request domestically and for the cost of international postage for others. Literature Cited 1. Kidahl, N.; Berka, L. H. J. Chem. Educ. 1995, 72, 258. 2. Schaber, P. M. J. Chem. Educ. 1985, 62, 345.

Laboratory Measurements of Sulfuric Acid Vapor Opacity at Millimeter Wavelengths Under Venus Conditions

NASA Astrophysics Data System (ADS)

Akins, Alexander Brooks; Steffes, Paul G.

2017-10-01

Radio astronomical observations of the lower-cloud and sub-cloud regions of the Venusian atmosphere at millimeter wavelengths can provide insight into the nature of the sub-cloud sulfur chemistry. Previous observations (de Pater et al., Icarus 90, 1991 and Sagawa, J. Natl. Inst. of Inf. And Comm. Tech. 55, 2008) indicate substantial variations in Venus disc brightness at millimeter wavelengths, likely due to variations in SO2 and H2SO4 vapor abundances. Although previous measurements of H2SO4 vapor opacity provide accurate information at centimeter wavelengths (Kolodner and Steffes, Icarus 132, 1998), extrapolation to millimeter wavelength observations is speculative. A Fabry-Perot open resonator with a quality factor in excess of 15,000 has been designed to measure the opacity of H2SO4 vapor in a CO2 atmosphere under Venus temperature and pressure conditions below the clouds. The resonator system has been designed using corrosion-resistant materials to ensure data integrity. Opacity measurements made with this system target the 2-4 millimeter wavelength range, applicable to recent Atacama Large Millimeter Array observations of Venus. Initial laboratory results for H2SO4 vapor opacity will be presented, and the implications of these results for pressure broadened opacity formalisms will be discussed. In addition to radio astronomical observations, these results of these measurements can aid in the interpretation of radiometer and radio occultation measurements from future Venus missions, such as the Venera D orbiter. This work is supported by the NASA Solar System Workings Program under grant NNX17AB19G.

Measurement of natural carbon isotopic composition of acetone in human urine.

PubMed

Yamada, Keita; Ohishi, Kazuki; Gilbert, Alexis; Akasaka, Mai; Yoshida, Naohiro; Yoshimura, Ryoko

2016-02-01

The natural carbon isotopic composition of acetone in urine was measured in healthy subjects using gas chromatography-combustion-isotope ratio mass spectrometry combined with headspace solid-phase microextraction (HS-SPME-GC-C-IRMS). Before applying the technique to a urine sample, we optimized the measurement conditions of HS-SPME-GC-C-IRMS using aqueous solutions of commercial acetone reagents. The optimization enabled us to determine the carbon isotopic compositions within ±0.2 ‰ of precision and ±0.3‰ of error using 0.05 or 0.2 mL of aqueous solutions with acetone concentrations of 0.3-121 mg/L. For several days, we monitored the carbon isotopic compositions and concentrations of acetone in urine from three subjects who lived a daily life with no restrictions. We also monitored one subject for 3 days including a fasting period of 24 h. These results suggest that changes in the availability of glucose in the liver are reflected in changes in the carbon isotopic compositions of urine acetone. Results demonstrate that carbon isotopic measurement of metabolites in human biological samples at natural abundance levels has great potential as a tool for detecting metabolic changes caused by changes in physiological states and disease.

Measurement of Trace Water Vapor in a Carbon Dioxide Removal Assembly Product Stream

NASA Technical Reports Server (NTRS)

Wormhoudt, Joda; Shorter, Joanne H.; McManus, J. Barry; Nelson, David D.; Zahniser, Mark S.; Freedman, Andrew; Campbell, Melissa; Chang, Clarence T.; Smith, Frederick D.

2004-01-01

The International Space Station Carbon Dioxide Removal Assembly (CDRA) uses regenerable adsorption technology to remove carbon dioxide (COP) from cabin air. Product water vapor measurements from a CDRA test bed at the NASA Marshall Space Flight Center were made using a tunable infrared diode laser differential absorption spectrometer (TILDAS) provided by NASA Glenn Research Center. The TILDAS instrument exceeded all the test specifications, including sensitivity, dynamic range, time response, and unattended operation. During the COP desorption phase, water vapor concentrations as low as 5 ppmv were observed near the peak of CO2 evolution, rising to levels of approx. 40 ppmv at the end of a cycle. Periods of high water concentration (>100 ppmv) were detected and shown to be caused by an experimental artifact. Measured values of total water vapor evolved during a single desorption cycle were as low as 1 mg.

Comparison of water vapor from observations and models in the Asian Monsoon UTLS region

NASA Astrophysics Data System (ADS)

Singer, C. E.; Clouser, B.; Gaeta, D. C.; Moyer, E. J.

2017-12-01

As part of the StratoClim campaign in July/August 2017, the Chicago Water Isotope Spectrometer (ChiWIS) made water vapor measurements from the mid-troposphere through the lower stratosphere (to 21 km altitude). We compare in-situ measurements with remote sensing observations and model projections both to validate measurements and to evalute the added value of high-precision in-situ sampling. Preliminary results and comparison with other StratoClim tracer measurements suggest that the UTLS region is highly structured, beyond what models or satellite instruments can capture, and that ChiWIS accurately captures these variations.

Differential absorption lidar measurements of atmospheric water vapor using a pseudonoise code modulated AlGaAs laser. Thesis

NASA Technical Reports Server (NTRS)

Rall, Jonathan A. R.

1994-01-01

Lidar measurements using pseudonoise code modulated AlGaAs lasers are reported. Horizontal path lidar measurements were made at night to terrestrial targets at ranges of 5 and 13 km with 35 mW of average power and integration times of one second. Cloud and aerosol lidar measurements were made to thin cirrus clouds at 13 km altitude with Rayleigh (molecular) backscatter evident up to 9 km. Average transmitter power was 35 mW and measurement integration time was 20 minutes. An AlGaAs laser was used to characterize spectral properties of water vapor absorption lines at 811.617, 816.024, and 815.769 nm in a multipass absorption cell using derivative spectroscopy techniques. Frequency locking of an AlGaAs laser to a water vapor absorption line was achieved with a laser center frequency stability measured to better than one-fifth of the water vapor Doppler linewidth over several minutes. Differential absorption lidar measurements of atmospheric water vapor were made in both integrated path and range-resolved modes using an externally modulated AlGaAs laser. Mean water vapor number density was estimated from both integrated path and range-resolved DIAL measurements and agreed with measured humidity values to within 6.5 percent and 20 percent, respectively. Error sources were identified and their effects on estimates of water vapor number density calculated.

Analysis of field measurements of carbon dioxide and water vapor fluxes

NASA Technical Reports Server (NTRS)

Verma, Shashi B.

1991-01-01

Analysis of the field measurements of carbon dioxide and water vapor fluxes is discussed. These data were examined in conjunction with reflectance obtained from helicopter mounted Modular Multiband Radiometer. These measurements are representative of the canopy scale (10 to 100 m)(exp 2) and provide a good basis for investigating the hypotheses/relationship potentially useful in remote sensing applications. All the micrometeorological data collected during FIFE-89 were processed and fluxes of CO2, water vapor, and sensible heat were calculated. Soil CO2 fluxes were also estimated. Employing these soil CO2 flux values, in conjunction with micrometeorological measurements, canopy photosynthesis is being estimated. A biochemical model of leaf photosynthesis was adapted to the prairie vegetation. The modeled leaf photosynthesis rates were scaled up to the canopy level. This model and a multiplicative stomatal conductance model are also used to calculate canopy conductance.

Lattice Boltzmann Simulation of Water Isotope Fractionation During Growth of Ice Crystals in Clouds

NASA Astrophysics Data System (ADS)

Lu, G.; Depaolo, D.; Kang, Q.; Zhang, D.

2006-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically- symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over-saturation, determines crystal morphology, there are no existing quantitative models that directly relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be a direct relationship between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D Lattice-Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. The input parameters needed are the isotope-dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the sticking coefficient (or accommodation coefficient) for ice is uncertain. The ratio D/k is a length that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions using a dimensionless Damkohler number

Development and Deployment of Mobile Emissions Laboratory for Continuous Long-Term Unattended Measurements of Greenhouse Gases, Fluxes, Isotopes and Pollutants

NASA Astrophysics Data System (ADS)

Gardner, A.; Baer, D. S.; Owano, T. G.; Provencal, R. A.; Gupta, M.; Parsotam, V.; Graves, P.; Goldstein, A.; Guha, A.

2010-12-01

Development and Deployment of Mobile Emissions Laboratory for Continuous Long-Term Unattended Measurements of Greenhouse Gases, Fluxes, Isotopes and Pollutants A. Gardner(1), D. Baer (1), T. Owano (1), R. Provencal (1), V. Parsotam (1), P. Graves (1), M. Gupta (1), Allen Goldstein (2), Abhinav Guha (2) (1) Los Gatos Research, 67 East Evelyn Avenue, Suite 3, Mountain View, CA 94041-1529 (2) Department of Environmental Science, Policy, and Management, University of California at Berkeley Quantifying the Urban Fossil Fuel Plume: Convergence of top-down and bottom-up approaches (Session A54). We report on the design, development and deployment of a novel Mobile Emissions Laboratory, consisting of innovative laser-based gas analyzers, for rapid measurements of multiple greenhouse gases and pollutants. Designed for real-time mobile and stationery emissions monitoring, the Mobile Emissions Laboratory was deployed at several locations during 2010, including CalNEX 2010, Caldecott Tunnel (Oakland, CA), and Altamont Landfill (Livermore, CA), to record real-time continuous measurements of isotopic CO2 (δ13C, CO2), methane (CH4), acetylene (C2H2), nitrous oxide (N2O), carbon monoxide (CO), and isotopic water vapor (H2O; δ18O, δ2H). The commercial gas analyzers are based on novel cavity-enhanced laser absorption spectroscopy. The portable analyzers provide measurements in real time, require about 150 watts (each) of power and do not need liquid nitrogen to operate. These instruments have been applied in the field for applications that require high data rates (for eddy correlation flux), wide dynamic range (e.g., for chamber flux and other applications with concentrations that can be 10-1000 times higher than typical ambient levels) and highest accuracy (atmospheric monitoring stations). The Mobile Emissions Laboratory, which contains onboard batteries for long-term unattended measurements without access to mains power, can provide regulatory agencies, monitoring stations

ELF and ALEX SURF WINTER WAVES: Lidar Intercomparison of Aerosol and Water Vapor Measurements in the Baltimore-Washington Metropolitan Area During the Winter Water Vapor Validation Experiments (WAVES) 2008 campaign.

NASA Astrophysics Data System (ADS)

Delgado, R.; Weldegaber, M.; Wilson, R. C.; McMillan, W.; McCann, K. J.; Woodman, M.; Demoz, B.; Adam, M.; Connell, R.; Venable, D.; Joseph, E.; Rabenhorst, S.; Twigg, L.; McGee, T.; Whiteman, D. N.; Hoff, R. M.

2008-12-01

Elastic and Raman lidar measurements were conducted to measure the vertical distribution of aerosols and water vapor during the Water Vapor Validation Experiments (WAVES) 2008 campaign by the University of Maryland Baltimore County (UMBC) Atmospheric Lidar Group at UMBC, at the same time as measurements at Howard University's Beltsville Research Station (26.5 km distant). The lidar profiles of atmospheric water vapor and aerosols allowed comparison for AURA/Aqua retrieval studies, by performing instrument accuracy assessments and data, generated by various independent active and passive remote sensing instruments for case studies of regional water vapor and aerosol sub-pixel variability. Integration of the lidar water vapor mixing ratios has been carried out to generate a column precipitable water vapor timeseries that can be compared to UMBC's SUOMINET station and Baltimore Bomem Atmospheric Emitted Radiance Interferometer (BBAERI). Changes in atmospheric aerosol concentration and water vapor mixing ratios due to meteorological events observed in the lidar timeseries have been correlated to the vertical temperature timeseries of BBAERI and to modeling of the air mass over the Baltimore-Washington metro area with the Weather Research and Forecasting (WRF) model.

Atomic vapor laser isotope separation of lead-210 isotope

DOEpatents

Scheibner, K.F.; Haynam, C.A.; Johnson, M.A.; Worden, E.F.

1999-08-31

An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207. 5 figs.

Atomic vapor laser isotope separation of lead-210 isotope

DOEpatents

Scheibner, Karl F.; Haynam, Christopher A.; Johnson, Michael A.; Worden, Earl F.

1999-01-01

An isotopically selective laser process and apparatus for removal of Pb-210 from natural lead that involves a one-photon near-resonant, two-photon resonant excitation of one or more Rydberg levels, followed by field ionization and then electrostatic extraction. The wavelength to the near-resonant intermediate state is counter propagated with respect to the second wavelength required to populate the final Rydberg state. This scheme takes advantage of the large first excited state cross section, and only modest laser fluences are required. The non-resonant process helps to avoid two problems: first, stimulated Raman Gain due to the nearby F=3/2 hyperfine component of Pb-207 and, second, direct absorption of the first transition process light by Pb-207.

Water vapor and cloud water measurements over Darwin during the STEP 1987 tropical mission

NASA Technical Reports Server (NTRS)

Kelly, K. K.; Proffitt, M. H.; Chan, K. R.; Loewenstein, M.; Podolske, J. R.; Strahan, E.; Wilson, J. C.; Kley, D.

1993-01-01

Measurements of stratospheric and upper tropospheric cloud water plus water vapor (total water) and water vapor were made with two Lyman alpha hygrometers as part of the STEP tropical experiment. The in situ measurements were made in the Darwin, Australia, area in January and February of 1987 on an ER-2 aircraft. Average stratospheric water vapor at a potential temperature of 375 K (the average value of Theta at the tropopause) was 2.4 parts per million by volume (ppmv). This water mixing ratio is below the 3.0 to 4.0 ppmv necessary to be consistent with the observed upper stratospheric dryness. Saturation with respect to ice and the potential for dehydration was observed up to Theta = 402 K.

Apparatus to measure the vapor pressure of slowly decomposing compounds from 1 Pa to 105 Pa

PubMed Central

Berg, Robert F.

2016-01-01

This article describes an apparatus and method for measuring vapor pressures in the range from 1 Pa to 105 Pa. Its three distinctive elements are : (1) the static pressure measurements were made with only a small temperature difference between the vapor and the condensed phase, (2) the sample was degassed in situ, and (3) the temperature range extended up to 200 °C. The apparatus was designed to measure metal-organic precursors, which often are toxic, pyrophoric, or unstable. Vapor pressures are presented for naphthalene, ferrocene, diethyl phthalate, and TEMAH (tetrakisethylmethylaminohafnium). Also presented are data for the temperature-dependent decomposition rate of TEMAH. PMID:27274567

The Discrepancy Between Measured and Modeled Downwelling Solar Irradiance at the Ground: Dependence on Water Vapor

NASA Technical Reports Server (NTRS)

Pilewski, P.; Rabbette, M.; Bergstrom, R.; Marquez, J.; Schmid, B.; Russell, P. B.

2000-01-01

Moderate resolution spectra of the downwelling solar irradiance at the ground in north central Oklahoma were measured during the Department of Energy Atmospheric Radiation Measurement Program Intensive Observation Period in the fall of 1997. Spectra obtained under-cloud-free conditions were compared with calculations using a coarse resolution radiative transfer model to examine the dependency of model-measurement bias on water vapor. It was found that the bias was highly correlated with water vapor and increased at a rate of 9 Wm per cm of water. The source of the discrepancy remains undetermined because of the complex dependencies of other variables, most notably aerosol optical depth, on water vapor.

The Discrepancy Between Measured and Modeled Downwelling Solar Irradiance at the Ground: Dependence on Water Vapor

NASA Technical Reports Server (NTRS)

Pilewskie, P.; Rabbette, M.; Bergstrom, R.; Marquez, J.; Schmid, B.; Russell, P. B.

2000-01-01

Moderate resolution spectra of the downwelling solar irradiance at the ground in north central Oklahoma were measured during the Department of Energy Atmospheric Radiation Measurement Program Intensive Observation Period in the fall of 1997. Spectra obtained under cloud-free conditions were compared with calculations using a coarse resolution radiative transfer model to examine the dependency of model-measurement bias on water vapor. It was found that the bias was highly correlated with water vapor and increased at a rate of 9 Wm(exp -2) per cm of water. The source of the discrepancy remains undetermined because of the complex dependencies of other variables, most notably aerosol optical depth, on water vapor.

Steady state fractionation of heavy noble gas isotopes in a deep unsaturated zone

USGS Publications Warehouse

Seltzer, Alan M.; Severinghaus, Jeffrey P.; Andraski, Brian J.; Stonestrom, David A.

2017-01-01

To explore steady state fractionation processes in the unsaturated zone (UZ), we measured argon, krypton, and xenon isotope ratios throughout a ∼110 m deep UZ at the United States Geological Survey (USGS) Amargosa Desert Research Site (ADRS) in Nevada, USA. Prior work has suggested that gravitational settling should create a nearly linear increase in heavy-to-light isotope ratios toward the bottom of stagnant air columns in porous media. Our high-precision measurements revealed a binary mixture between (1) expected steady state isotopic compositions and (2) unfractionated atmospheric air. We hypothesize that the presence of an unsealed pipe connecting the surface to the water table allowed for direct inflow of surface air in response to extensive UZ gas sampling prior to our first (2015) measurements. Observed isotopic resettling in deep UZ samples collected a year later, after sealing the pipe, supports this interpretation. Data and modeling each suggest that the strong influence of gravitational settling and weaker influences of thermal diffusion and fluxes of CO2 and water vapor accurately describe steady state isotopic fractionation of argon, krypton, and xenon within the UZ. The data confirm that heavy noble gas isotopes are sensitive indicators of UZ depth. Based on this finding, we outline a potential inverse approach to quantify past water table depths from noble gas isotope measurements in paleogroundwater, after accounting for fractionation during dissolution of UZ air and bubbles.

Preliminary investigation of electrothermal vaporization sample introduction for inductively coupled plasma time-of-flight mass spectrometry.

PubMed

Mahoney, P P; Ray, S J; Li, G; Hieftje, G M

1999-04-01

The coupling of an electrothermal vaporization (ETV) apparatus to an inductively coupled plasma time-of-flight mass spectrometer (ICP-TOFMS) is described. The ability of the ICP-TOFMS to produce complete elemental mass spectra at high repetition rates is experimentally demonstrated. A signal-averaging data acquisition board is employed to rapidly record complete elemental spectra throughout the vaporization stage of the ETV temperature cycle; a solution containing 34 elements is analyzed. The reduction of both molecular and atomic isobaric interferences through the temperature program of the furnace is demonstrated. Isobaric overlaps among the isotopes of cadmium, tin, and indium are resolved by exploiting differences in the vaporization characteristics of the elements. Figures of merit for the system are defined with several different data acquisition schemes capable of operating at the high repetition rate of the TOF instrument. With the use of both ion counting and a boxcar averager, the dynamic range is shown to be linear over a range of at least 6 orders of magnitude. A pair of boxcar averagers are used to measure the isotope ratio for silver with a precision of 1.9% RSD, despite a cycle-to-cycle precision of 19% RSD. Detection limits of 10-80 fg are calculated for seven elements, based upon a 10-microL injection.

Water stable isotope measurements of Antarctic samples by means of IRMS and WS-CRDS techniques

NASA Astrophysics Data System (ADS)

Michelini, Marzia; Bonazza, Mattia; Braida, Martina; Flora, Onelio; Dreossi, Giuliano; Stenni, Barbara

2010-05-01

of the sample in the box. In the WS-CRDS the path of laser is longer, producing higher-sensitivity measurements. The instrument is paired with an autosampler and can be used without it and the vaporizer to analyze directly the isotopic composition of the water vapour in the atmosphere. In addition, the instrument can be moved from the laboratory and also used for outdoor measurements. The more important improvements over traditional IRMS techniques are that WS-CRDS needs less sample in order to perform the analysis (<2 ul vs. 3/5 ml); that it doesn't need manipulation of the sample (like the gas/water equilibration techniques) and the analyses are faster. Coversely, memory effects may affect the measurements so there is the need to increase the number of injection to have a high precision measurement. The laboratory of Isotope Geochemistry of the Department of Geosciences has recently acquired a WS-CRDS system from PICARRO. The isotopic data obtained with this new method have been compared with the ones obtained by means of IRMS methods. An HDO device coupled with a Thermo Finnigan Delta Plus Advantage mass spectrometer has been used, using the well know CO2 and H2/water equilibration technique. At the moment of the writing of the abstract the mean difference between the values obtained using PICARRO and using the traditional IRMS method is of the order of 0.1 per mil for the ratio 18O/16O and 1.00 per mil for the ratio D/H, but further measurements are currently underway. O'Keef A., Deacon D.A.G., 1988. Cavity ring-down optical spectrometer for absorption measurements using pulsed laser sources, Rev. Sci. Instrum., 59, 2544.

Natural isotope correction of MS/MS measurements for metabolomics and (13)C fluxomics.

PubMed

Niedenführ, Sebastian; ten Pierick, Angela; van Dam, Patricia T N; Suarez-Mendez, Camilo A; Nöh, Katharina; Wahl, S Aljoscha

2016-05-01

Fluxomics and metabolomics are crucial tools for metabolic engineering and biomedical analysis to determine the in vivo cellular state. Especially, the application of (13)C isotopes allows comprehensive insights into the functional operation of cellular metabolism. Compared to single MS, tandem mass spectrometry (MS/MS) provides more detailed and accurate measurements of the metabolite enrichment patterns (tandem mass isotopomers), increasing the accuracy of metabolite concentration measurements and metabolic flux estimation. MS-type data from isotope labeling experiments is biased by naturally occurring stable isotopes (C, H, N, O, etc.). In particular, GC-MS(/MS) requires derivatization for the usually non-volatile intracellular metabolites introducing additional natural isotopes leading to measurements that do not directly represent the carbon labeling distribution. To make full use of LC- and GC-MS/MS mass isotopomer measurements, the influence of natural isotopes has to be eliminated (corrected). Our correction approach is analyzed for the two most common applications; (13)C fluxomics and isotope dilution mass spectrometry (IDMS) based metabolomics. Natural isotopes can have an impact on the calculated flux distribution which strongly depends on the substrate labeling and the actual flux distribution. Second, we show that in IDMS based metabolomics natural isotopes lead to underestimated concentrations that can and should be corrected with a nonlinear calibration. Our simulations indicate that the correction for natural abundance in isotope based fluxomics and quantitative metabolomics is essential for correct data interpretation. © 2015 Wiley Periodicals, Inc.

Electric Dipole Moment Measurements with Rare Isotopes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chupp, Timothy

The origin of matter is one of the deepest questions addressed by science and remains a mystery because our understanding of the Big Bang suggests that equal amounts of matter as antimatter would be created and annihilate leaving nothing from which stars, galaxies, planets and ultimately life as we know it was created. We know this is not the case in the universe, and so the explanation that the laws of physics can distinguish the difference of moving forward and backward in time and provide mechanisms that produce more matter that antimatter so that a little bit was left over.more » These same laws of physics affect our world today and would very slightly change the shape of an atom, stretching is along the direction of the spin of its nucleus. This subtle shape change has been searched in many systems - the neutron, atoms and molecules, but has not yet been detected, even as the motivation is strengthened by our understanding of their structure. We therefore look to new systems that have special features that make these effects stand out. Rare isotopes provide one possibility and specific radon atoms are our choice. We have developed techniques to make these measurements with short-lived radioactive atoms, studied the nuclei to provide deeper understanding of how these affect arise in such atoms (including radium) and developed new laser-based techniques to measure and control the magnetic fields necessary to perform these exquisitely sensitive measurements. In this work we have shown that radioactive radon atoms can be produced and transported to an apparatus that lines up the spins of the atoms. We have also shown that the nuclei of nearby radium are pear shaped and that the radon nuclei likely oscillate from one pear shape to its mirror reflection. We have also used the techniques which control nuclear spin to study the magnetic environment in a magnetically shielded room, which has the smallest magnetic field in a large volume in the universe. Measuring

A Portable, Field-Deployable Analyzer for Isotopic Water Measurements

NASA Astrophysics Data System (ADS)

Berman, E. S.; Gupta, M.; Huang, Y. W.; Lacelle, D.; McKay, C. P.; Fortson, S.

2015-12-01

Water stable isotopes have for many years been used to study the hydrological cycle, catchment hydrology, and polar climate among other applications. Typically, discrete water samples are collected and transported to a laboratory for isotope analysis. Due to the expense and labor associated with such sampling, isotope studies have generally been limited in scope and time-resolution. Field sampling of water isotopes has been shown in recent years to provide dense data sets with the increased time resolution illuminating substantially greater short term variability than is generally observed during discrete sampling. A truly portable instrument also opens the possibility to utilize the instrument as a tool for identifying which water samples would be particularly interesting for further laboratory investigation. To make possible such field measurements of liquid water isotopes, Los Gatos Research has developed a miniaturized, field-deployable liquid water isotope analyzer. The prototype miniature liquid water isotope analyzer (mini-LWIA) uses LGR's patented Off-Axis ICOS (Integrated Cavity Output Spectroscopy) technology in a rugged, Pelican case housing for easy transport and field operations. The analyzer simultaneously measures both δ2H and δ18O from liquid water, with both manual and automatic water introduction options. The laboratory precision for δ2H is 0.6 ‰, and for δ18O is 0.3 ‰. The mini-LWIA was deployed in the high Arctic during the summer of 2015 at Inuvik in the Canadian Northwest Territories. Samples were collected from Sachs Harbor, on the southwest coast of Banks Island, including buried basal ice from the Lurentide Ice Sheet, some ice wedges, and other types of ground ice. Methodology and water analysis results from this extreme field deployment will be presented.

Isotopically Enriched C-13 Diamond Anvil as a Stress Sensor in High Pressure Experiments

NASA Astrophysics Data System (ADS)

Vohra, Yogesh; Qiu, Wei; Kondratyev, Andreiy; Velisavljevic, Nenad; Baker, Paul

2004-03-01

The conventional high pressure diamond anvils were modified by growing an isotopically pure C-13 diamond layer by microwave plasma chemical vapor deposition using methane/hydrogen/oxygen chemistry. The isotopically pure C-13 nature of the culet of the diamond anvil was confirmed by the Raman spectroscopy measurements. This isotopically engineered diamond anvil was used against a natural abundance diamond anvil for high pressure experiments in a diamond anvil cell. Spatial resolved Raman spectroscopy was used to measure the stress induced shift in the C-13 layer as well as the undelying C-12 layer to ultra high pressures. The observed shift and splitiing of the diamond first order Raman spectrum was correlated with the stress distribution in the diamond anvil cell. The experimental results will be compared with the finite element modeling results using NIKE-2D software in order to create a mathematical relationship between sets of the following parameters: vertical (z axis) distance; horizontal (r axis) distance; max shear stress, and pressure. The isotopically enriched diamond anvils offer unique opportunities to measure stress distribution in the diamond anvil cell devices.

In-Situ Molecular Vapor Composition Measurements During Lyophilization.

PubMed

Liechty, Evan T; Strongrich, Andrew D; Moussa, Ehab M; Topp, Elizabeth; Alexeenko, Alina A

2018-04-11

Monitoring process conditions during lyophilization is essential to ensuring product quality for lyophilized pharmaceutical products. Residual gas analysis has been applied previously in lyophilization applications for leak detection, determination of endpoint in primary and secondary drying, monitoring sterilization processes, and measuring complex solvents. The purpose of this study is to investigate the temporal evolution of the process gas for various formulations during lyophilization to better understand the relative extraction rates of various molecular compounds over the course of primary drying. In this study, residual gas analysis is used to monitor molecular composition of gases in the product chamber during lyophilization of aqueous formulations typical for pharmaceuticals. Residual gas analysis is also used in the determination of the primary drying endpoint and compared to the results obtained using the comparative pressure measurement technique. The dynamics of solvent vapors, those species dissolved therein, and the ballast gas (the gas supplied to maintain a set-point pressure in the product chamber) are observed throughout the course of lyophilization. In addition to water vapor and nitrogen, the two most abundant gases for all considered aqueous formulations are oxygen and carbon dioxide. In particular, it is observed that the relative concentrations of carbon dioxide and oxygen vary depending on the formulation, an observation which stems from the varying solubility of these species. This result has implications on product shelf life and stability during the lyophilization process. Chamber process gas composition during lyophilization is quantified for several representative formulations using residual gas analysis. The advantages of the technique lie in its ability to measure the relative concentration of various species during the lyophilization process. This feature gives residual gas analysis utility in a host of applications from endpoint

Insights into Mechanistic Models for Evaporation of Organic Liquids in the Environment Obtained by Position-Specific Carbon Isotope Analysis.

PubMed

Julien, Maxime; Nun, Pierrick; Robins, Richard J; Remaud, Gérald S; Parinet, Julien; Höhener, Patrick

2015-11-03

Position-specific isotope effects (PSIEs) have been measured by isotope ratio monitoring (13)C nuclear magnetic resonance spectrometry during the evaporation of 10 liquids of different polarities under 4 evaporation modes (passive evaporation, air-vented evaporation, low pressure evaporation, distillation). The observed effects are used to assess the validity of the Craig-Gordon isotope model for organic liquids. For seven liquids the overall isotope effect (IE) includes a vapor-liquid contribution that is strongly position-specific in polar compounds but less so in apolar compounds and a diffusive IE that is not position-specific, except in the alcohols, ethanol and propan-1-ol. The diffusive IE is diminished under forced evaporation. The position-specific isotope pattern created by liquid-vapor IEs is manifest in five liquids, which have an air-side limitation for volatilization. For the alcohols, undefined processes in the liquid phase create additional PSIEs. Three other liquids with limitations on the liquid side have a lower, highly position-specific, bulk diffusive IE. It is concluded that evaporation of organic pollutants creates unique position-specific isotope patterns that may be used to assess the progress of remediation or natural attenuation of pollution and that the Craig-Gordon isotope model is valid for the volatilization of nonpolar organic liquids with air-side limitation of the volatilization rate.

A feasibility study of a microwave water vapor measurement from a space probe along an occultation path

NASA Technical Reports Server (NTRS)

Longbothum, R. L.

1975-01-01

Stratospheric and mesospheric water vapor measurements were taken using the microwave lines at 22 GHz (22.235 GHz) and 183 GHz (183.31 GHz). The resonant cross sections for both the 22 GHz and the 183 GHz lines were used to model the optical depth of atmospheric water vapor. The range of optical depths seen by a microwave radiometer through the earth's limb was determined from radiative transfer theory. Radiometer sensitivity, derived from signal theory, was compared with calculated optical depths to determine the maximum height to which water vapor can be measured using the following methods: passive emission, passive absorption, and active absorption. It was concluded that measurements using the 22 GHz line are limited to about 50 km whereas the 183 GHz line enables measurements up to and above 100 km for water vapor mixing ratios as low as 0.1 ppm under optimum conditions.

Performance of the Chicago Water Isotope Spectrometer in the UTLS during the Asian Monsoon

NASA Astrophysics Data System (ADS)

Gaeta, D. C.; Clouser, B.; Sarkozy, L.; Singer, C. E.; Moyer, E. J.

2017-12-01

The preferential condensation of water vapor isotopologues makes the isotopic composition of water vapor a useful tracer of the processes responsible for the distribution of water in the UTLS, but the UTLS also offers particular challenges for its measurement. We report here on the field performance of a new instrument designed for measurement of HDO and H2O in the UTLS region: the Chicago Water Isotope Spectrometer (Chi-WIS). Chi-WIS is a laser-based infrared absorption spectrometer at 2.65 μm that uses a high-reflectivity optical cavity to obtain 6 km of effective path length, allowing sensitive measurements of scarce molecules. During the 2017 StratoClim aircraft campaign in Kathmandu, Nepal, Chi-WIS flew aboard the M-55 Geophysica high-altitude research aircraft in a series of flights to probe the Asian Monsoon. Preliminary results show in-flight performance consistent with laboratory performance and the achievement of design targets necessary to reach UTLS science goals. Residual noise on spectra is stable across flights at 4-5x10-4 with 1 second averaging (i.e. absorption depth of .04-.05%); the instrument is robust in terms of alignment and shows no evidence of optical resonances. The resulting measurement precision is as expected from these characteristics. Because we use a relatively strong water line, the water vapor measurement is extremely precise: constant-altitude flight legs in the stratosphere at 4 ppm H2O show 1 s standard deviation 0.03 ppmv for 1 s averaging, and 0.08 ppbv for HDO with 10 s averaging. We show comparisons with other StratoClim instruments and examples of how these measurements resolve scientifically relevant atmospheric features.

Comparison of Water Vapor Measurements by Airborne Sun Photometer and Diode Laser Hygrometer on the NASA DC-8

DOE Office of Scientific and Technical Information (OSTI.GOV)

Livingston, J. M.; Schmid, Beat; Russell, P. B.

In January-February 2003 the 14-channel NASA Ames Airborne Tracking Sunphotometer 30 (AATS) and the NASA Langley/Ames Diode Laser Hygrometer (DLH) were flown on the NASA DC-8 aircraft. AATS measured column water vapor on the aircraft-to-sun path, while DLH measured local water vapor in the free stream between the aircraft fuselage and an outboard engine cowling. The AATS and DLH measurements were compared for two DC-8 vertical profiles by differentiating the AATS column measurement and/or integrating the DLH local measurement over the altitude range of each profile (7.7-10 km and 1.2-12.5 km). These comparisons extend, for the first time, tests ofmore » AATS water vapor retrievals to altitudes >~6 km and column contents <0.1 g cm-2. To our knowledge this is the first time suborbital spectroscopic water vapor measurements using the 940-nm band have been tested in conditions so high and dry. For both profiles layer water vapor (LWV) from AATS and DLH were highly correlated, with r2 0.998, rms difference 7.2% and bias (AATS minus DLH) 0.9%. For water vapor densities AATS and DLH had r2 0.968, rms difference 27.6%, and bias (AATS minus DLH) -4.2%. These results compare favorably with previous comparisons of AATS water vapor to in situ results for altitudes <~6 km, columns ~0.1 to 5 g cm-2 and densities ~0.1 to 17 g m-3.« less

O-stable Isotopes Distribution In Deep-sea Corals From Sims Measurements

NASA Astrophysics Data System (ADS)

Blamart, D.; Cuif, J.-P.; Juillet-Leclerc, A.

Urey's theoretical calculations (Urey, 1947) have predicted that the O-isotope fraction- ations between calcium carbonates and water should be large enough to be used as a paleothermometer. However, stable isotopes studies on aragonitic invertebrates includ- ing corals have also demonstrated departure of several per mil from O-equilibrium. Different tentative explanations have been proposed in the literature: (1) influence of the polymorphism form and chemical composition of the calcium carbonate (2) kinetic effects related to calcification process during rapid growth rate (3) metabolic effect due to respiration and photosynthesis. All these explanations are based on the assumption that the coral skeleton represents a structural homogeneous entity. Early microscopic studies of coral skeletons have suggested that coral skeletons are built by two different structures: (1) fibres and (2) centres of calcification confirmed by recent biominerali- sation studies. SIMS O-stable isotopes measurements have been performed on lines of centres of calcification and the surrounding aragonitic fibre on deep-sea coral (Lophe- lia Pertusa). Different transects of O-isotope distribution have been carried out in the septa and in the thick wall of Lophelia pertusa. O-isotopic values of the fibres of the septa and of the wall show a very large range of variation of around 10L' from -5 to +5L' (PDB). O-measurement performed on line of the centre of calcification from the inner part of the septa to the wall show a restricted range of variation which not exceed 1L'. O-values of the centres of calcification in the septa and in the wall are similar with a mean value of -2.9s0.3L'. Temperature derived from O values of the centre of cal- ´ cification are not consistant with the measured ones in situ indicating also a constant fractionation in this microstructure. Coupled with C-isotopes measurements O-isotope distribution should better constraint the growth mechanism, calcification process

In situ water vapor and ozone measurements in Lhasa and Kunming during the Asian summer monsoon

NASA Astrophysics Data System (ADS)

Bian, Jianchun; Pan, Laura L.; Paulik, Laura; Vömel, Holger; Chen, Hongbin; Lu, Daren

2012-10-01

The Asian summer monsoon (ASM) anticyclone circulation system is recognized to be a significant transport pathway for water vapor and pollutants to enter the stratosphere. The observational evidence, however, is largely based on satellite retrievals. We report the first coincident in situ measurements of water vapor and ozone within the ASM anticyclone. The combined water vapor and ozonesondes were launched from Kunming, China in August 2009 and Lhasa, China in August 2010. In total, 11 and 12 sondes were launched in Kunming and Lhasa, respectively. We present the key characteristics of these measurements, and provide a comparison to similar measurements from an equatorial tropical location, during the Tropical Composition, Cloud and Climate Coupling (TC4) campaign in July and August of 2007. Results show that the ASM anticyclone region has higher water vapor and lower ozone concentrations in the upper troposphere and lower stratosphere than the TC4 observations. The results also show that the cold point tropopause in the ASM region has a higher average height and potential temperature. The in situ observations therefore support the satellite-based conclusion that the ASM is an effective transport pathway for water vapor to enter stratosphere.

Measurements of Water Vapor Profiles with Compact DIAL in the Tokyo Metropolitan Area

NASA Astrophysics Data System (ADS)

Abo, Makoto; Sakai, Tetsu; Le Hoai, Phong Pham; Shibata, Yasukuni; Nagasawa, Chikao

2018-04-01

In recent years, the frequency of occurrence of locally heavy rainfall that can cause extensive damages, has been increasing in Japan. For early prediction of heavy rainfall, it is useful to measure the water vapor vertical distribution upwind cumulus convection beforehand. For that purpose, we have been developing compact water vapor differential absorption lidar (DIAL). We show the results of the measurements with lidar in summer when the local heavy rainfall frequently occurs in Japan. We also show the preliminary result of the assimilation of the lidar data to the numerical model and impact on the heavy rainfall prediction.

Characterization of AIRS temperature and water vapor measurement capability using correlative observations

NASA Technical Reports Server (NTRS)

Fetzer, Eric J.; Eldering, Annmarie; Lee, Sung-Yung

2005-01-01

In this presentation we address several fundamental issues in the measurement of temperature and water vapor by AIRS: accuracy, precision, vertical resolution and biases as a function of cloud amount. We use two correlative data sources. First we compare AIRS total water vapor with that from the Advanced microwave Sounding Radiometer for EOS (AMSR-E) instrument, also onboard the Aqua spacecraft. AMSRE uses a mature methodology with a heritage including the operational Special Sensor Microwave Imager (SSM/I) instruments. AIRS and AMSR-E observations are collocated and simultaneous, providing a very large data set for comparison: about 200,000 over-ocean matches daily. We show small cloud-dependent biases between AIRS and AMSR-E total water vapor for several oceanic regions. Our second correlative data source is several hundred dedicated radiosondes launched during AIRS overpasses.

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

NASA Astrophysics Data System (ADS)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

SOFIA Water Vapor Monitor Design

NASA Technical Reports Server (NTRS)

Cooper, R.; Roellig, T. L.; Yuen, L.; Shiroyama, B.; Meyer, A.; Devincenzi, D. (Technical Monitor)

2002-01-01

The SOFIA Water Vapor Monitor (WVM) is a heterodyne radiometer designed to determine the integrated amount of water vapor along the telescope line of sight and directly to the zenith. The basic technique that was chosen for the WVM uses radiometric measurements of the center and wings of the 183.3 GHz rotational line of water to measure the water vapor. The WVM reports its measured water vapor levels to the aircraft Mission Controls and Communication System (MCCS) while the SOFIA observatory is in normal operation at flight altitude. The water vapor measurements are also available to other scientific instruments aboard the observatory. The electrical, mechanical and software design of the WVM are discussed.

The influence of room temperature on Mg isotope measurements by MC-ICP-MS.

PubMed

Zhang, Xing-Chao; Zhang, An-Yu; Zhang, Zhao-Feng; Huang, Fang; Yu, Hui-Min

2018-03-24

We observed that the accuracy and precision of magnesium (Mg) isotope analyses could be affected if the room temperature oscillated during measurements. To achieve high quality Mg isotopic data, it is critical to evaluate how the unstable room temperature affects Mg isotope measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We measured the Mg isotopes for the reference material DSM-3 using MC-ICP-MS under oscillating room temperatures in spring. For a comparison, we also measured the Mg isotopes under stable room temperatures, which was achieved by the installation of an improved temperature control system in the laboratory. The δ 26 Mg values measured under oscillating room temperatures have a larger deviation (δ 26 Mg from -0.09 to 0.08‰, with average δ 26 Mg = 0.00 ± 0.08 ‰) than those measured under a stable room temperature (δ 26 Mg from -0.03 to 0.03‰, with average δ 26 Mg = 0.00 ± 0.02 ‰) using the same MC-ICP-MS system. The room temperature variation can influence the stability of MC-ICP-MS. Therefore, it is critical to keep the room temperature stable to acquire high precise and accurate isotopic data when using MC-ICP-MS, especially when using the sample-standard bracketing (SSB) correction method. This article is protected by copyright. All rights reserved.

Water vapor: An extraordinary terahertz wave source under optical excitation

NASA Astrophysics Data System (ADS)

Johnson, Keith; Price-Gallagher, Matthew; Mamer, Orval; Lesimple, Alain; Fletcher, Clark; Chen, Yunqing; Lu, Xiaofei; Yamaguchi, Masashi; Zhang, X.-C.

2008-09-01

In modern terahertz (THz) sensing and imaging spectroscopy, water is considered a nemesis to be avoided due to strong absorption in the THz frequency range. Here we report the first experimental demonstration and theoretical implications of using femtosecond laser pulses to generate intense broadband THz emission from water vapor. When we focused an intense laser pulse in water vapor contained in a gas cell or injected from a gas jet nozzle, an extraordinarily strong THz field from optically excited water vapor is observed. Water vapor has more than 50% greater THz generation efficiency than dry nitrogen. It had previously been assumed that the nonlinear generation of THz waves in this manner primarily involves a free-electron plasma, but we show that the molecular structure plays an essential role in the process. In particular, we found that THz wave generation from H2O vapor is significantly stronger than that from D2O vapor. Vibronic activities of water cluster ions, occurring naturally in water vapor, may possibly contribute to the observed isotope effect along with rovibrational contributions from the predominant monomers.

Natural Isotope Abundance in Metabolites: Techniques and Kinetic Isotope Effect Measurement in Plant, Animal, and Human Tissues.

PubMed

Tea, Illa; Tcherkez, Guillaume

2017-01-01

The natural isotope abundance in bulk organic matter or tissues is not a sufficient base to investigate physiological properties, biosynthetic mechanisms, and nutrition sources of biological systems. In fact, isotope effects in metabolism lead to a heterogeneous distribution of 2 H, 18 O, 13 C, and 15 N isotopes in metabolites. Therefore, compound-specific isotopic analysis (CSIA) is crucial to biological and medical applications of stable isotopes. Here, we review methods to implement CSIA for 15 N and 13 C from plant, animal, and human samples and discuss technical solutions that have been used for the conversion to CO 2 and N 2 for IRMS analysis, derivatization and isotope effect measurements. It appears that despite the flexibility of instruments used for CSIA, there is no universal method simply because the chemical nature of metabolites of interest varies considerably. Also, CSIA methods are often limited by isotope effects in sample preparation or the addition of atoms from the derivatizing reagents, and this implies that corrections must be made to calculate a proper δ-value. Therefore, CSIA has an enormous potential for biomedical applications, but its utilization requires precautions for its successful application. © 2017 Elsevier Inc. All rights reserved.

Process for producing enriched uranium having a .sup.235 U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, James A.; Hayden, Jr., Howard W.

1995-01-01

An uranium enrichment process capable of producing an enriched uranium, having a .sup.235 U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower .sup.235 U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF.sub.6 tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a .sup.235 U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % .sup.235 U; fluorinating this enriched metallic uranium isotopic mixture to form UF.sub.6 ; processing the resultant isotopic mixture of UF.sub.6 in a gaseous diffusion process to produce a final enriched uranium product having a .sup.235 U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low .sup.235 U content UF.sub.6 having a .sup.235 U content of about 0.71 wt. % of the total uranium content of the low .sup.235 U content UF.sub.6 ; and converting this low .sup.235 U content UF.sub.6 to metallic uranium for recycle to the atomic vapor laser isotope separation process.

Process for producing enriched uranium having a {sup 235}U content of at least 4 wt. % via combination of a gaseous diffusion process and an atomic vapor laser isotope separation process to eliminate uranium hexafluoride tails storage

DOEpatents

Horton, J.A.; Hayden, H.W. Jr.

1995-05-30

An uranium enrichment process capable of producing an enriched uranium, having a {sup 235}U content greater than about 4 wt. %, is disclosed which will consume less energy and produce metallic uranium tails having a lower {sup 235}U content than the tails normally produced in a gaseous diffusion separation process and, therefore, eliminate UF{sub 6} tails storage and sharply reduce fluorine use. The uranium enrichment process comprises feeding metallic uranium into an atomic vapor laser isotope separation process to produce an enriched metallic uranium isotopic mixture having a {sup 235} U content of at least about 2 wt. % and a metallic uranium residue containing from about 0.1 wt. % to about 0.2 wt. % {sup 235} U; fluorinating this enriched metallic uranium isotopic mixture to form UF{sub 6}; processing the resultant isotopic mixture of UF{sub 6} in a gaseous diffusion process to produce a final enriched uranium product having a {sup 235}U content of at least 4 wt. %, and up to 93.5 wt. % or higher, of the total uranium content of the product, and a low {sup 235}U content UF{sub 6} having a {sup 235}U content of about 0.71 wt. % of the total uranium content of the low {sup 235}U content UF{sub 6}; and converting this low {sup 235}U content UF{sub 6} to metallic uranium for recycle to the atomic vapor laser isotope separation process. 4 figs.

Dual Si and O Isotope Measurement of Lunar Samples Using IRMS

NASA Astrophysics Data System (ADS)

Banerjee, N.; Hill, P. J. A.; Osinski, G. R.

2016-12-01

The use of isotopic systems and their associated theoretical models have become an increasingly sophisticated tool for investigating the origin of planetary bodies in the solar system. It was originally hypothesized that evidence for the impact origin of Moon would manifest itself as an isotopic heterogeneity between lunar and terrestrial samples; however, most isotope systems show no difference between the bulk Earth and Moon. The stable isotopes of both silicon (Si) and oxygen (O) have been essential in further understanding planetary processes including core formation. Historically the analysis of the Si and O isotope ratios in terrestrial and extraterrestrial material has primarily been measured independent of each other through three main techniques: isotope ratio mass spectrometry (IRMS), secondary ion mass spectrometry (SIMS), and multi-collector inductively coupled plasma mass-spectrometry (MC-ICPMS). Each technique has its own strength and weakness in regards to resolution and precision; however, one of the main limiting factors in all three of these techniques rests on the requirement of multiple aliquots. As most literature focuses on the measurement of oxygen or silicon isotopes, this unique line allows for the precise analysis of Si and O isotopes from the same aliquot of bulk sample, which cannot be done with SIMS or ICP-MS analysis. To deal with this problem a unique laser line system has been developed in the Laboratory for Stable Isotope Science at Western University, Canada, that simultaneously extracts SiF4 and O2 from the same 1-2 mg aliquot. We present the application of analyzing both isotopic systems from the sample aliquot to Apollo, meteoritic, and terrestrial samples and its implication for the formation of the Moon. Preliminary results from this line suggest that although the O isotopes ratios are consistent with a homogenous Moon-Earth system, a difference is observed in Si isotopes between Apollo and terrestrial samples compared to

Monitoring water stable isotope composition in soils using gas-permeable tubing and infrared laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Rothfuss, Youri; Vereecken, Harry; Brüggemann, Nicolas

2013-04-01

The water stable isotopologues 1H2H16O and 1H218O are powerful tracers of processes occurring in nature. Their slightly different masses as compared to the most abundant water isotopologue (1H216O) affect their thermodynamic (e.g. during chemical equilibrium reactions or physical phase transitions with equilibration) and kinetic (liquid and vapor phases transport processes and chemical reactions without equilibration) properties. This results in measurable differences of the isotopic composition of water within or between the different terrestrial ecosystem compartments (i.e. sub-soil, soil, surface waters, plant, and atmosphere). These differences can help addressing a number of issues, among them water balance closure and flux partitioning from the soil-plant-atmosphere continuum at the field to regional scales. In soils particularly, the isotopic composition of water (δ2H and δ18O) provides qualitative information about whether water has only infiltrated or already been re-evaporated since the last rainfall event or about the location of the evaporation front. From water stable isotope composition profiles measured in soils, it is also possible, under certain hypotheses, to derive quantitative information such as soil evaporation flux and the identification of root water uptake depths. In addition, water stable isotopologues have been well implemented into physically based Soil-Vegetation-Atmosphere Transfer models (e.g. SiSPAT-Isotope; Soil-Litter iso; TOUGHREACT) and have demonstrated their potential. However, the main disadvantage of the isotope methodology is that, contrary to other soil state variables that can be monitored over long time periods, δ2H and δ18O are typically analyzed following destructive sampling. Here, we present a non-destructive method for monitoring soil liquid water δ2H and δ18O over a wide range of water availability conditions and temperatures by sampling and measuring water vapor equilibrated with soil water using gas

Isotopes in North American Rocky Mountain Snowpack 1993-2014

NASA Astrophysics Data System (ADS)

Anderson, Lesleigh; Berkelhammer, Max; Mast, M. Alisa

2016-01-01

We present ∼1300 new isotopic measurements (δ18O and δ2H) from a network of snowpack sites in the Rocky Mountains that have been sampled since 1993. The network includes 177 locations where depth-integrated snow samples are collected each spring near peak accumulation. At 57 of these locations snowpack samples were obtained for 10-21 years and their isotopic measurements provide unprecedented spatial and temporal documentation of snowpack isotope values at mid-latitudes. For environments where snowfall accounts for the majority of annual precipitation, snowmelt is likely to have the strongest influence on isotope values retained in proxy archives. In this first presentation of the dataset we (1) describe the basic features of the isotope values in relation to the Global Meteoric Water Line (GMWL), (2) evaluate space for time substitutions traditionally used to establish δ18O-temperature relations, (3) evaluate site-to-site similarities across the network and identify those that are the most regionally representative, (4) examine atmospheric circulation patterns for several years with spatially coherent isotope patterns, and (5) provide examples of the implications this new dataset has for interpreting paleoclimate records (Bison Lake, Colorado and Minnetonka Cave, Idaho). Results indicate that snowpack δ18O is rarely a simple proxy of temperature. Instead, it exhibits a high degree of spatial heterogeneity and temporal variance that reflect additional processes such as vapor transport and post-depositional modification. Despite these complexities we identify consistent climate-isotope patterns and regionally representative locations that serve to better define Holocene hydroclimate estimates and their uncertainty. Climate change has and will affect western U.S. snowpack and we suggest these changes can be better understood and anticipated by oxygen and hydrogen isotope-based reconstructions of Holocene hydroclimate using a process-based understanding of the

Measurements of upper atmosphere water vapor made in situ with a new moisture sensor

NASA Technical Reports Server (NTRS)

Chleck, D.

1979-01-01

A new thin-film aluminum oxide sensor, Aquamax II, has been developed for the measurement of stratospheric and upper tropospheric water vapor levels. The sensor is briefly described with attention given to its calibration and performance. Data obtained from six balloon flights are presented; almost all the results show a constant water vapor mixing ratio, in agreement with other data from midlatitude regions.

Spectroscopic metrology for isotope composition measurements and transfer standards

NASA Astrophysics Data System (ADS)

Anyangwe Nwaboh, Javis; Balslev-Harder, David; Kääriäinen, Teemu; Richmond, Craig; Manninen, Albert; Mohn, Joachim; Kiseleva, Maria; Petersen, Jan C.; Werhahn, Olav; Ebert, Volker

2017-04-01

The World Meteorological Organization (WMO) has identified greenhouse gases such as CO2, CH4 and N2O as critical for global climate monitoring. Other molecules such as CO that has an indirect effect of enhancing global warming are also monitored. WMO has stated compatibility goals for atmospheric concentration and isotope ratio measurements of these gases, e.g. 0.1 ppm for CO2 concentration measurements in the northern hemisphere and 0.01 ‰ for δ13C-CO2. For measurements of the concentration of greenhouse gases, gas analysers are typically calibrated with static gas standards e.g. traceable to the WMO scale or to the International System of Units (SI) through a national metrology institute. However, concentrations of target components, e.g. CO, in static gas standards have been observed to drift, and typically the gas matrix as well as the isotopic composition of the target component does not always reflect field gas composition, leading to deviations of the analyser response, even after calibration. The deviations are dependent on the measurement technique. To address this issue, part of the HIGHGAS (Metrology for high-impact greenhouse gases) project [1] focused on the development of optical transfer standards (OTSs) for greenhouse gases, e.g. CO2 and CO, potentially complementing gas standards. Isotope ratio mass spectrometry (IRMS) [2] is currently used to provide state-of-the-art high precision (in the 0.01 ‰ range) measurements for the isotopic composition of greenhouse gases. However, there is a need for field-deployable techniques such as optical isotope ratio spectroscopy (OIRS) that can be combined with metrological measurement methods. Within the HIGHGAS project, OIRS methods and procedures based on e.g. cavity enhanced spectroscopy (CES) and tunable diode laser absorption spectroscopy (TDLAS), matched to metrological principles have been established for the measurement of 13C/12C and 18O/16O ratios in CO2, 15N/14N ratios in N2O, and 13C/12C and 2H

Vapor sensors using porous silicon-based optical interferometers

NASA Astrophysics Data System (ADS)

Gao, Ting

The ability to detect or monitor various gases is important for many applications. Smaller, more portable, lower power, and less expensive gas sensors are needed. Porous silicon (PS) has attracted attention for use in such devices due to its unique optical and electronic properties and its large surface area. This thesis describes the preparation and characteristics of vapor sensors using thin PS Fabry-Perot films. The average refractive index of the PS layer increases when the PS film is exposed to analyte vapors, causing the optical fringes to shift to longer wavelengths. Two methods for monitoring the shifts in these optical fringes are explored in this thesis. The first technique measures the reflection spectrum using a white light source, and the second measures the intensity of reflected light using a low-power red diode laser source. The latter method offers a simple, low-cost and reliable transduction mechanism for vapor sensing. A vapor sensor with a detection limit of 250 ppb and a wide dynamic range (five orders of magnitude) is demonstrated. The effect of the PS film thickness and porosity on sensitivity are systematically studied. A model based on the Bruggeman approximation and capillary condensation is proposed to explain this sensing behavior. Two approaches to improve the sensitivity of the PS sensors are explored. In the first, porous Si is chemically modified and the investigation shows that the sensing response varies with different surface properties. In a second study, thin polymer layers are coated on the porous Si substrate to selectively filter solvent vapors. This bi-layer approach is also applied to porous Si layers that have luminescent quantum structures. These latter structures sense adsorbates based on quenching of luminescence from the quantum-confined silicon nanostructures. In the course of this thesis, an anomalous response of ozone-oxidized PS films to water vapor was discovered. The effect was studied by optical interferometry

Molecular-Flow Properties of RIB Type Vapor-Transport Systems Using a Fast-Valve

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alton, Gerald D; Bilheux, Hassina Z; Zhang, Y.

2014-01-01

The advent of the fast-valve device, described previously, permits measurement of molecular-flow times of chemically active or inactive gaseous species through radioactive ion beam (RIB) target ion source systems, independent of size, geometry and materials of construction. Thus, decay losses of short-half-life RIBs can be determined for a given target/vapor-transport system in advance of on-line operation, thereby ascertaining the feasibility of the system design for successful processing of a given isotope. In this article, molecular-flow-time theory and experimentally measured molecular-flow time data are given for serial- and parallel-coupled Ta metal RIB vapor-transport systems similar to those used at ISOL basedmore » RIB facilities. In addition, the effect of source type on the molecular-flow time properties of a given system is addressed, and a chemical passivation method for negating surface adsorption enthalpies for chemically active gaseous species on Ta surfaces is demonstrated.« less

Lifetime measurement of neutron-rich even-even molybdenum isotopes

NASA Astrophysics Data System (ADS)

Ralet, D.; Pietri, S.; Rodríguez, T.; Alaqeel, M.; Alexander, T.; Alkhomashi, N.; Ameil, F.; Arici, T.; Ataç, A.; Avigo, R.; Bäck, T.; Bazzacco, D.; Birkenbach, B.; Boutachkov, P.; Bruyneel, B.; Bruce, A. M.; Camera, F.; Cederwall, B.; Ceruti, S.; Clément, E.; Cortés, M. L.; Curien, D.; De Angelis, G.; Désesquelles, P.; Dewald, M.; Didierjean, F.; Domingo-Pardo, C.; Doncel, M.; Duchêne, G.; Eberth, J.; Gadea, A.; Gerl, J.; Ghazi Moradi, F.; Geissel, H.; Goigoux, T.; Goel, N.; Golubev, P.; González, V.; Górska, M.; Gottardo, A.; Gregor, E.; Guastalla, G.; Givechev, A.; Habermann, T.; Hackstein, M.; Harkness-Brennan, L.; Henning, G.; Hess, H.; Hüyük, T.; Jolie, J.; Judson, D. S.; Jungclaus, A.; Knoebel, R.; Kojouharov, I.; Korichi, A.; Korten, W.; Kurz, N.; Labiche, M.; Lalović, N.; Louchart-Henning, C.; Mengoni, D.; Merchán, E.; Million, B.; Morales, A. I.; Napoli, D.; Naqvi, F.; Nyberg, J.; Pietralla, N.; Podolyák, Zs.; Pullia, A.; Prochazka, A.; Quintana, B.; Rainovski, G.; Reese, M.; Recchia, F.; Reiter, P.; Rudolph, D.; Salsac, M. D.; Sanchis, E.; Sarmiento, L. G.; Schaffner, H.; Scheidenberger, C.; Sengele, L.; Singh, B. S. Nara; Singh, P. P.; Stahl, C.; Stezowski, O.; Thoele, P.; Valiente Dobon, J. J.; Weick, H.; Wendt, A.; Wieland, O.; Winfield, J. S.; Wollersheim, H. J.; Zielinska, M.; PreSPEC Collaboration

2017-03-01

Background: In the neutron-rich A ≈100 mass region, rapid shape changes as a function of nucleon number as well as coexistence of prolate, oblate, and triaxial shapes are predicted by various theoretical models. Lifetime measurements of excited levels in the molybdenum isotopes allow the determination of transitional quadrupole moments, which in turn provides structural information regarding the predicted shape change. Purpose: The present paper reports on the experimental setup, the method that allowed one to measure the lifetimes of excited states in even-even molybdenum isotopes from mass A =100 up to mass A =108 , and the results that were obtained. Method: The isotopes of interest were populated by secondary knock-out reaction of neutron-rich nuclei separated and identified by the GSI fragment separator at relativistic beam energies and detected by the sensitive PreSPEC-AGATA experimental setup. The latter included the Lund-York-Cologne calorimeter for identification, tracking, and velocity measurement of ejectiles, and AGATA, an array of position sensitive segmented HPGe detectors, used to determine the interaction positions of the γ ray enabling a precise Doppler correction. The lifetimes were determined with a relativistic version of the Doppler-shift-attenuation method using the systematic shift of the energy after Doppler correction of a γ -ray transition with a known energy. This relativistic Doppler-shift-attenuation method allowed the determination of mean lifetimes from 2 to 250 ps. Results: Even-even molybdenum isotopes from mass A =100 to A =108 were studied. The decays of the low-lying states in the ground-state band were observed. In particular, two mean lifetimes were measured for the first time: τ =29 .7-9.1+11.3 ps for the 4+ state of 108Mo and τ =3 .2-0.7+0.7 ps for the 6+ state of 102Mo. Conclusions: The reduced transition strengths B (E 2 ) , calculated from lifetimes measured in this experiment, compared to beyond

Optoacoustic measurements of water vapor absorption at selected CO laser wavelengths in the 5-micron region

NASA Technical Reports Server (NTRS)

Menzies, R. T.; Shumate, M. S.

1976-01-01

Measurements of water vapor absorption were taken with a resonant optoacoustical detector (cylindrical pyrex detector, two BaF2 windows fitted into end plates at slight tilt to suppress Fabry-Perot resonances), for lack of confidence in existing spectral tabular data for the 5-7 micron region, as line shapes in the wing regions of water vapor lines are difficult to characterize. The measurements are required for air pollution studies using a CO laser, to find the differential absorption at the wavelengths in question due to atmospheric constituents other than water vapor. The design and performance of the optoacoustical detector are presented. Effects of absorption by ambient NO are considered, and the fixed-frequency discretely tunable CO laser is found suitable for monitoring urban NO concentrations in a fairly dry climate, using the water vapor absorption data obtained in the study.

The influence of water vapor on atmospheric exchange measurements with an ICOS* based Laser absorption analyzer

NASA Astrophysics Data System (ADS)

Bunk, Rüdiger; Quan, Zhi; Wandel, Matthias; Yi, Zhigang; Bozem, Heiko; Kesselmeier, Jürgen

2014-05-01

Carbonyl sulfide and carbon monoxide are both atmospheric trace gases of high interest. Recent advances in the field of spectroscopy have enabled instruments that measure the concentration of the above and other trace gases very fast and with good precision. Increasing the effective path length by reflecting the light between two mirrors in a cavity, these instruments reach impressive sensitivities. Often it is possible to measure the concentration of more than one trace gas at the same time. The OCS/CO2 Analyzer by LGR (Los Gatos Research, Inc.) measures the concentration of water vapor [H2O], carbonyl sulfide [COS], carbon dioxide [CO2] and carbon monoxide [CO] simultaneously. For that the cavity is saturated with light, than the attenuation of light is measured as in standard absorption spectroscopy. The instrument proved to be very fast with good precision and to be able to detect even very low concentrations, especially for COS (as low as 30ppt in the case of COS). However, we observed a rather strong cross sensitivity to water vapor. Altering the water vapor content of the sampled air with two different methods led to a change in the perceived concentration of COS, CO and CO2. This proved especially problematic for enclosure (cuvette) measurements, where the concentrations of one of the above species in an empty cuvette are compared to the concentration of another cuvette containing a plant whose exchange of trace gases with the atmosphere is of interest. There, the plants transpiration leads to a large difference in water vapor content between the cuvettes and that in turn produces artifacts in the concentration differences between the cuvettes for the other above mentioned trace gases. For CO, simultaneous measurement with a UV-Emission Analyzer (AL 5002, Aerolaser) and the COS/CO Analyzer showed good agreement of perceived concentrations as long as the sample gas was dry and an increasing difference in perceived concentration when the sample gas was

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II? quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Separation of copper, iron, and zinc from complex aqueous solutions for isotopic measurement

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ridley, W.I.; Wolf, R.; Lamothe, P.J.; Adams, M.

2007-01-01

The measurement of Cu, Fe, and Zn isotopes in natural samples may provide valuable information about biogeochemical processes in the environment. However, the widespread application of stable Cu, Fe, and Zn isotope chemistry to natural water systems remains limited by our ability to efficiently separate these trace elements from the greater concentrations of matrix elements. In this study, we present a new method for the isolation of Cu, Fe, and Zn from complex aqueous solutions using a single anion-exchange column with hydrochloric acid media. Using this method we are able to quantitatively separate Cu, Fe, and Zn from each other and from matrix elements in a single column elution. Elution of the elements of interest, as well as all other elements, through the anion-exchange column is a function of the speciation of each element in the various concentrations of HCl. We highlight the column chemistry by comparing our observations with published studies that have investigated the speciation of Cu, Fe, and Zn in chloride solutions. The functionality of the column procedure was tested by measuring Cu, Fe, and Zn isotopes in a variety of stream water samples impacted by acid mine drainage. The accuracy and precision of Zn isotopic measurements was tested by doping Zn-free stream water with the Zn isotopic standard. The reproducibility of the entire column separation process and the overall precision of the isotopic measurements were also evaluated. The isotopic results demonstrate that the Cu, Fe, and Zn column separates from the tested stream waters are of sufficient purity to be analyzed directly using a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), and that the measurements are fully-reproducible, accurate, and precise. Although limited in scope, these isotopic measurements reveal significant variations in ??65Cu (- 1.41 to + 0.30???), ??56Fe (- 0.56 to + 0.34???), and ??66Zn (0.31 to 0.49???) among samples collected from different

Equilibrium stable-isotope fractionation of thallium and mercury

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2005-12-01

In this study first-principles quantum mechanical and empirical force-field models are used to estimate equilibrium mass-dependent isotopic fractionations among a variety of thallium and mercury compounds. High-precision MC-ICP-MS measurements have recently uncovered evidence of stable isotope fractionation for many elements, including 2-4‰ variability in the isotopic compositions of thallium[1] (atomic no. 81) and mercury[2] (atomic no. 80). The observed thallium- and mercury-isotope fractionations are remarkable, given that the magnitude of isotopic fractionation typically decreases as atomic number increases[3]. Stable isotope measurements could improve our understanding of geochemical and biogeochemical cycling of both elements, but little is known about the mechanisms driving these fractionations. A better understanding of the chemical processes controlling stable isotope compositions could help maximize the utility of these new geochemical tracers. Standard equilibrium stable isotope fractionation theory holds that the energy driving fractionation comes from isotopic effects on vibrational frequencies, which have generally not been measured. In the present study both quantum-mechanical and empirical force fields are used to estimate unknown frequencies. Results suggest that thallium and mercury fractionations of ≥ 0.5‰ are likely during the relevant redox reactions Tl+ ↔ Tl3+ and HgO ↔ Hg2+. Methyl-mercury and mercury-halide compounds like CH3HgCl will have ~ 1‰ higher 202Hg/198Hg than atomic vapor at room temperature. Fractionations between coexisting Hg2+ species appear to be much smaller, however. 205Tl/203Tl in Tl(H2O)_63+ is predicted to be ~0.5‰ higher than in coexisting Tl+-bearing substances. This result is in qualitative agreement with data from ferromanganese crusts [1], suggesting that Tl3+ in manganese-oxides will have higher 205Tl/203Tl than aqueous Tl+. Equilibrium fractionations for both elements are much smaller than the observed

Comparison of Columnar Water Vapor Measurements During The Fall 1997 ARM Intensive Observation Period: Optical Methods

NASA Technical Reports Server (NTRS)

Schmid, Beat; Michalsky, J.; Slater, D.; Barnard, J.; Halthore, R.; Liljegren, J.; Holben, B.; Eck, T.; Livingston, J.; Russell, P.;

Remote measurement of high preeruptive water vapor emissions at Sabancaya volcano by passive differential optical absorption spectroscopy

NASA Astrophysics Data System (ADS)

Kern, Christoph; Masias, Pablo; Apaza, Fredy; Reath, Kevin A.; Platt, Ulrich

2017-05-01

Water (H2O) is by far the most abundant volcanic volatile species and plays a predominant role in driving volcanic eruptions. However, numerous difficulties associated with making accurate measurements of water vapor in volcanic plumes have limited their use as a diagnostic tool. Here we present the first detection of water vapor in a volcanic plume using passive visible-light differential optical absorption spectroscopy (DOAS). Ultraviolet and visible-light DOAS measurements were made on 21 May 2016 at Sabancaya Volcano, Peru. We find that Sabancaya's plume contained an exceptionally high relative water vapor abundance 6 months prior to its November 2016 eruption. Our measurements yielded average sulfur dioxide (SO2) emission rates of 800-900 t/d, H2O emission rates of around 250,000 t/d, and an H2O/SO2 molecular ratio of 1000 which is about an order of magnitude larger than typically found in high-temperature volcanic gases. We attribute the high water vapor emissions to a boiling-off of Sabancaya's hydrothermal system caused by intrusion of magma to shallow depths. This hypothesis is supported by a significant increase in the thermal output of the volcanic edifice detected in infrared satellite imagery leading up to and after our measurements. Though the measurement conditions encountered at Sabancaya were very favorable for our experiment, we show that visible-light DOAS systems could be used to measure water vapor emissions at numerous other high-elevation volcanoes. Such measurements would provide observatories with additional information particularly useful for forecasting eruptions at volcanoes harboring significant hydrothermal systems.

The role of pre-event canopy storage in throughfall and stemflow by using isotopic tracers

Treesearch

S.T. Allen; J.R. Brooks; R.F. Keim; B.J. Bond; J.J. McDonnell

2014-01-01

Stable isotopes can be a valuable tool for tracing the redistribution, storage, and evaporation of water associated with canopy interception of rainfall. Isotopic differences between throughfall and rainfall have been attributed to three mechanisms: evaporative fractionation, isotopic exchange with ambient vapor, and temporal redistribution. We demonstrate the...

An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry.

PubMed

Rua-Ibarz, Ana; Bolea-Fernandez, Eduardo; Vanhaecke, Frank

2016-01-01

Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision ≤0.006% relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the

Ionization cross section, pressure shift and isotope shift measurements of osmium

NASA Astrophysics Data System (ADS)

Hirayama, Yoshikazu; Mukai, Momo; Watanabe, Yutaka; Oyaizu, Michihiro; Ahmed, Murad; Kakiguchi, Yutaka; Kimura, Sota; Miyatake, Hiroari; Schury, Peter; Wada, Michiharu; Jeong, Sun-Chan

2017-11-01

In-gas-cell laser resonance ionization spectroscopy of neutral osmium atoms was performed with the use of a two-color two-step laser resonance ionization technique. Saturation curves for the ionization scheme were measured, and the ionization cross section was experimentally determined by solving the rate equations for the ground, intermediate and ionization continuum populations. The pressure shift and pressure broadening in the resonance spectra of the excitation transition were measured. The electronic factor {F}247 for the transition {λ }1=247.7583 nm to the intermediate state was deduced from the measured isotope shifts of stable {}{188,189,{190,192}}Os isotopes. The efficient ionization scheme, pressure shift, nuclear isotope shift and {F}247 are expected to be useful for applications of laser ion sources to unstable nuclei and for nuclear spectroscopy based on laser ionization techniques.

Assessing the Temperature Dependence of Narrow-Band Raman Water Vapor Lidar Measurements: A Practical Approach

NASA Technical Reports Server (NTRS)

Whiteman, David N.; Venable, Demetrius D.; Walker, Monique; Cardirola, Martin; Sakai, Tetsu; Veselovskii, Igor

2013-01-01

Narrow-band detection of the Raman water vapor spectrum using the lidar technique introduces a concern over the temperature dependence of the Raman spectrum. Various groups have addressed this issue either by trying to minimize the temperature dependence to the point where it can be ignored or by correcting for whatever degree of temperature dependence exists. The traditional technique for performing either of these entails accurately measuring both the laser output wavelength and the water vapor spectral passband with combined uncertainty of approximately 0.01 nm. However, uncertainty in interference filter center wavelengths and laser output wavelengths can be this large or larger. These combined uncertainties translate into uncertainties in the magnitude of the temperature dependence of the Raman lidar water vapor measurement of 3% or more. We present here an alternate approach for accurately determining the temperature dependence of the Raman lidar water vapor measurement. This alternate approach entails acquiring sequential atmospheric profiles using the lidar while scanning the channel passband across portions of the Raman water vapor Q-branch. This scanning is accomplished either by tilt-tuning an interference filter or by scanning the output of a spectrometer. Through this process a peak in the transmitted intensity can be discerned in a manner that defines the spectral location of the channel passband with respect to the laser output wavelength to much higher accuracy than that achieved with standard laboratory techniques. Given the peak of the water vapor signal intensity curve, determined using the techniques described here, and an approximate knowledge of atmospheric temperature, the temperature dependence of a given Raman lidar profile can be determined with accuracy of 0.5% or better. A Mathematica notebook that demonstrates the calculations used here is available from the lead author.

Effects of acidification on the isotopic ratios of Neotropical otter tooth dentin.

PubMed

Carrasco, Thayara S; Botta, Silvina; Machado, Rodrigo; Colares, Elton P; Secchi, Eduardo R

2018-05-30

Stable carbon and nitrogen isotope ratios are widely used in ecological studies providing important information on the trophic ecology and habitat use of consumers. However, some factors may lead to isotopic variability, which makes difficult the interpretation of data, such as the presence of inorganic carbon in mineralized tissues. In order to remove the inorganic carbon, acidification is a commonly used treatment. The effects of two methods of acidification were tested: (i) dentin acidification with 10% HCl using the 'drop-by-drop' technique, and (ii) dentin acidification in an 'HCl atmosphere', by exposing the dentin to vaporous 30% hydrochloric acid. Results were compared with untreated subsamples. The stable carbon and nitrogen ratios of untreated and acidified subsamples were measured using an elemental analyzer coupled to an isotope ratio mass spectrometer. The nitrogen isotopic ratios were statistically different between the two acidification treatments, but no significant changes in carbon isotopic ratios were found in acidified and untreated samples. The results indicated that acidification had no effect on carbon isotopic ratios of Neotropical otter tooth dentin, while introducing a source of error in nitrogen isotopic ratios. Therefore, we conclude that acidification is an unnecessary step for C and N stable isotope analysis. Copyright © 2018 John Wiley & Sons, Ltd.

A Feasibility Study for Simultaneous Measurements of Water Vapor and Precipitation Parameters using a Three-frequency Radar

NASA Technical Reports Server (NTRS)

Meneghini, R.; Liao, L.; Tian, L.

2005-01-01

The radar return powers from a three-frequency radar, with center frequency at 22.235 GHz and upper and lower frequencies chosen with equal water vapor absorption coefficients, can be used to estimate water vapor density and parameters of the precipitation. A linear combination of differential measurements between the center and lower frequencies on one hand and the upper and lower frequencies on the other provide an estimate of differential water vapor absorption. The coupling between the precipitation and water vapor estimates is generally weak but increases with bandwidth and the amount of non-Rayleigh scattering of the hydrometeors. The coupling leads to biases in the estimates of water vapor absorption that are related primarily to the phase state and the median mass diameter of the hydrometeors. For a down-looking radar, path-averaged estimates of water vapor absorption are possible under rain-free as well as raining conditions by using the surface returns at the three frequencies. Simulations of the water vapor attenuation retrieval show that the largest source of error typically arises from the variance in the measured radar return powers. Although the error can be mitigated by a combination of a high pulse repetition frequency, pulse compression, and averaging in range and time, the radar receiver must be stable over the averaging period. For fractional bandwidths of 20% or less, the potential exists for simultaneous measurements at the three frequencies with a single antenna and transceiver, thereby significantly reducing the cost and mass of the system.

Evaluation of the combined measurement uncertainty in isotope dilution by MC-ICP-MS.

PubMed

Fortunato, G; Wunderli, S

2003-09-01

The combination of metrological weighing, the measurement of isotope amount ratios by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) and the use of high-purity reference materials are the cornerstones to achieve improved results for the amount content of lead in wine by the reversed isotope dilution technique. Isotope dilution mass spectrometry (IDMS) and reversed IDMS have the potential to be a so-called primary method, with which close comparability and well-stated combined measurement uncertainties can be obtained. This work describes the detailed uncertainty budget determination using the ISO-GUM approach. The traces of lead in wine were separated from the matrix by ion exchange chromatography after HNO(3)/H(2)O(2) microwave digestion. The thallium isotope amount ratio ( n((205)Tl)/ n((203)Tl)) was used to correct for mass discrimination using an exponential model approach. The corrected lead isotope amount ratio n((206)Pb)/ n((208)Pb) for the isotopic standard SRM 981 measured in our laboratory was compared with ratio values considered to be the least uncertain. The result has been compared in a so-called pilot study "lead in wine" organised by the CCQM (Comité Consultatif pour la Quantité de Matière, BIPM, Paris; the highest measurement authority for analytical chemical measurements). The result for the lead amount content k(Pb) and the corresponding expanded uncertainty U given by our laboratory was:k(Pb)=1.329 x 10-10mol g-1 (amount content of lead in wine)U[k(Pb)]=1.0 x 10-12mol g-1 (expanded uncertainty U=kxuc, k=2)The uncertainty of the main influence parameter of the combined measurement uncertainty was determined to be the isotope amount ratio R(206,B) of the blend between the enriched spike and the sample.

LASE measurements of water vapor, aerosol, and cloud distribution in hurricane environments and their role in hurricane development

NASA Technical Reports Server (NTRS)

Mahoney, M. J.; Ismail, S.; Browell, E. V.; Ferrare, R. A.; Kooi, S. A.; Brasseur, L.; Notari, A.; Petway, L.; Brackett, V.; Clayton, M.;

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

NASA Astrophysics Data System (ADS)

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; Hartig, K. C.; Phillips, M. C.

2018-06-01

Rapid, in-field, and non-contact isotopic analysis of solid materials is extremely important to a large number of applications, such as nuclear nonproliferation monitoring and forensics, geochemistry, archaeology, and biochemistry. Presently, isotopic measurements for these and many other fields are performed in laboratory settings. Rapid, in-field, and non-contact isotopic analysis of solid material is possible with optical spectroscopy tools when combined with laser ablation. Laser ablation generates a transient vapor of any solid material when a powerful laser interacts with a sample of interest. Analysis of atoms, ions, and molecules in a laser-produced plasma using optical spectroscopy tools can provide isotopic information with the advantages of real-time analysis, standoff capability, and no sample preparation requirement. Both emission and absorption spectroscopy methods can be used for isotopic analysis of solid materials. However, applying optical spectroscopy to the measurement of isotope ratios from solid materials presents numerous challenges. Isotope shifts arise primarily due to variation in nuclear charge distribution caused by different numbers of neutrons, but the small proportional nuclear mass differences between nuclei of various isotopes lead to correspondingly small differences in optical transition wavelengths. Along with this, various line broadening mechanisms in laser-produced plasmas and instrumental broadening generated by the detection system are technical challenges frequently encountered with emission-based optical diagnostics. These challenges can be overcome by measuring the isotope shifts associated with the vibronic emission bands from molecules or by using the techniques of laser-based absorption/fluorescence spectroscopy to marginalize the effect of instrumental broadening. Absorption and fluorescence spectroscopy probe the ground state atoms existing in the plasma when it is cooler, which inherently provides narrower

ICP-MS for isotope ratio measurement

USDA-ARS?s Scientific Manuscript database

The use of stable isotopes in mineral nutrition research has become a fundamental aspect of conducting this research. A gradual transition has occurred, now virtually complete, from radioactive isotope studies to those using stable isotopes. Although primarily used in human research, mineral stable ...

Water vapor measurement system in global atmospheric sampling program, appendix

NASA Technical Reports Server (NTRS)

Englund, D. R.; Dudzinski, T. J.

1982-01-01

The water vapor measurement system used in the NASA Global Atmospheric Sampling Program (GASP) is described. The system used a modified version of a commercially available dew/frostpoint hygrometer with a thermoelectrically cooled mirror sensor. The modifications extended the range of the hygrometer to enable air sample measurements with frostpoint temperatures down to -80 C at altitudes of 6 to 13 km. Other modifications were made to permit automatic, unattended operation in an aircraft environment. This report described the hygrometer, its integration with the GASP system, its calibration, and operational aspects including measurement errors. The estimated uncertainty of the dew/frostpoint measurements was + or - 1.7 Celsius.

Raman lidar and sun photometer measurements of aerosols and water vapor during the ARM RCS experiment

NASA Technical Reports Server (NTRS)

Ferrare, R. A.; Whiteman, D. N.; Melfi, S. H.; Evans, K. D.; Holben, B. N.

1995-01-01

The first Atmospheric Radiation Measurement (ARM) Remote Cloud Study (RCS) Intensive Operations Period (IOP) was held during April 1994 at the Southern Great Plains (SGP) Cloud and Radiation Testbed (CART) site near Lamont, Oklahoma. This experiment was conducted to evaluate and calibrate state-of-the-art, ground based remote sensing instruments and to use the data acquired by these instruments to validate retrieval algorithms developed under the ARM program. These activities are part of an overall plan to assess general circulation model (GCM) parameterization research. Since radiation processes are one of the key areas included in this parameterization research, measurements of water vapor and aerosols are required because of the important roles these atmospheric constituents play in radiative transfer. Two instruments were deployed during this IOP to measure water vapor and aerosols and study their relationship. The NASA/Goddard Space Flight Center (GSFC) Scanning Raman Lidar (SRL) acquired water vapor and aerosol profile data during 15 nights of operations. The lidar acquired vertical profiles as well as nearly horizontal profiles directed near an instrumented 60 meter tower. Aerosol optical thickness, phase function, size distribution, and integrated water vapor were derived from measurements with a multiband automatic sun and sky scanning radiometer deployed at this site.

Isotopes in North American Rocky Mountain snowpack 1993–2014

USGS Publications Warehouse

Anderson, Lesleigh; Max Berkelhammer,; Mast, M. Alisa

2015-01-01

We present ∼1300 new isotopic measurements (δ18O and δ2H) from a network of snowpack sites in the Rocky Mountains that have been sampled since 1993. The network includes 177 locations where depth-integrated snow samples are collected each spring near peak accumulation. At 57 of these locations snowpack samples were obtained for 10–21 years and their isotopic measurements provide unprecedented spatial and temporal documentation of snowpack isotope values at mid-latitudes. For environments where snowfall accounts for the majority of annual precipitation, snowmelt is likely to have the strongest influence on isotope values retained in proxy archives. In this first presentation of the dataset we (1) describe the basic features of the isotope values in relation to the Global Meteoric Water Line (GMWL), (2) evaluate space for time substitutions traditionally used to establish δ18O-temperature relations, (3) evaluate site-to-site similarities across the network and identify those that are the most regionally representative, (4) examine atmospheric circulation patterns for several years with spatially coherent isotope patterns, and (5) provide examples of the implications this new dataset has for interpreting paleoclimate records (Bison Lake, Colorado and Minnetonka Cave, Idaho). Results indicate that snowpack δ18O is rarely a simple proxy of temperature. Instead, it exhibits a high degree of spatial heterogeneity and temporal variance that reflect additional processes such as vapor transport and post-depositional modification. Despite these complexities we identify consistent climate-isotope patterns and regionally representative locations that serve to better define Holocene hydroclimate estimates and their uncertainty. Climate change has and will affect western U.S. snowpack and we suggest these changes can be better understood and anticipated by oxygen and hydrogen isotope-based reconstructions of Holocene hydroclimate using a process-based understanding of the

Laser ablation inductively coupled plasma mass spectrometry for direct isotope ratio measurements on solid samples

NASA Astrophysics Data System (ADS)

Pickhardt, Carola; Dietze, Hans-Joachim; Becker, J. Sabine

2005-04-01

Isotope ratio measurements have been increasingly used in quite different application fields, e.g., for the investigation of isotope variation in nature, in geoscience (geochemistry and geochronology), in cosmochemistry and planetary science, in environmental science, e.g., in environmental monitoring, or by the application of the isotope dilution technique for quantification purposes using stable or radioactive high-enriched isotope tracers. Due to its high sensitivity, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is today a challenging mass spectrometric technique for the direct determination of precise and accurate isotope ratios in solid samples. In comparison to laser ablation quadrupole ICP-MS (LA-ICP-QMS), laser ablation coupled to a double-focusing sector field ICP-MS (LA-ICP-SFMS) with single ion detection offers a significant improvement of sensitivity at low mass resolution, whereby isotope ratios can be measured with a precision to 0.1% relative standard deviation (R.S.D.). In LA-ICP-SFMS, many disturbing isobaric interferences of analyte and molecular ions can be separated at the required mass resolution (e.g., 40Ar16O+ and 56Fe+ for iron isotope ratio measurements). The precision on isotope ratio measurements was improved by one order of magnitude via the simultaneous detection of mass-separated ion currents of isotopes using multiple ion collectors in LA-ICP-MS (LA-MC-ICP-MS). The paper discusses the state of the art, the challenges and limits in isotope ratio measurements by LA-ICP-MS using different instrumentations at the trace and ultratrace level in different fields of application as in environmental and biological research, geochemistry and geochronology with respect to their precision and accuracy.

Remote measurement of high preeruptive water vapor emissions at Sabancaya volcano by passive differential optical absorption spectroscopy

USGS Publications Warehouse

Kern, Christoph; Masias, Pablo; Apaza, Fredy; Reath, Kevin; Platt, Ulrich

2017-01-01

Water (H2O) is by far the most abundant volcanic volatile species and plays a predominant role in driving volcanic eruptions. However, numerous difficulties associated with making accurate measurements of water vapor in volcanic plumes have limited their use as a diagnostic tool. Here we present the first detection of water vapor in a volcanic plume using passive visible-light differential optical absorption spectroscopy (DOAS). Ultraviolet and visible-light DOAS measurements were made on 21 May 2016 at Sabancaya Volcano, Peru. We find that Sabancaya's plume contained an exceptionally high relative water vapor abundance 6 months prior to its November 2016 eruption. Our measurements yielded average sulfur dioxide (SO2) emission rates of 800–900 t/d, H2O emission rates of around 250,000 t/d, and an H2O/SO2 molecular ratio of 1000 which is about an order of magnitude larger than typically found in high-temperature volcanic gases. We attribute the high water vapor emissions to a boiling-off of Sabancaya's hydrothermal system caused by intrusion of magma to shallow depths. This hypothesis is supported by a significant increase in the thermal output of the volcanic edifice detected in infrared satellite imagery leading up to and after our measurements. Though the measurement conditions encountered at Sabancaya were very favorable for our experiment, we show that visible-light DOAS systems could be used to measure water vapor emissions at numerous other high-elevation volcanoes. Such measurements would provide observatories with additional information particularly useful for forecasting eruptions at volcanoes harboring significant hydrothermal systems.

Observation of the 162Dy-164Dy Isotope Shift for the 0 → 16 717.79 cm-1 Optical Transition.

PubMed

Nardin Barreta, Luiz Felipe; Victor, Alessandro Rogério; Bueno, Patrícia; Dos Santos, Jhonatha Ricardo; da Silveira, Carlos Alberto Barbosa; Neri, José Wilson; Neto, Jonas Jakutis; Sbampato, Maria Esther; Destro, Marcelo Geraldo

2017-08-01

In this work, we report a newly observed isotope shift between 162 Dy and 164 Dy isotopes for the 0 → 16 717.79 cm -1 (598.003 nm) optical transition. We compared the newly observed results against two other lines (597.452 nm and 598.859 nm), which we measured in this work, and were already reported in the literature. The newly observed 162-164 Dy isotope shift, shows at least a 20% larger isotope shift than the isotope shifts for the other two lines investigated. The larger 162-164 isotope shift observed for the 598.003 nm line could lead to an increased isotope selectivity for atomic vapor laser isotope separation (AVLIS). Hence, this line could be a good choice for application in AVLIS. Experimental data available in the literature for the 597.452 nm and 598.859 nm lines, enabled us to perform simulations of spectra for both lines, in order to confirm the accuracy of our experimental measurements.

Hydrogen isotope systematics of phase separation in submarine hydrothermal systems: Experimental calibration and theoretical models

USGS Publications Warehouse

Berndt, M.E.; Seal, R.R.; Shanks, Wayne C.; Seyfried, W.E.

1996-01-01

Hydrogen isotope fractionation factors were measured for coexisting brines and vapors formed by phase separation of NaCl/H2O fluids at temperatures ranging from 399-450??C and pressures from 277-397 bars. It was found that brines are depleted in D compared to coexisting vapors at all conditions studied. The magnitude of hydrogen isotope fractionation is dependent on the relative amounts of Cl in the two phases and can be empirically correlated to pressure using the following relationship: 1000 ln ??(vap-brine) = 2.54(??0.83) + 2.87(??0.69) x log (??P), where ??(vap-brine) is the fractionation factor and ??P is a pressure term representing distance from the critical curve in the NaCl/H2O system. The effect of phase separation on hydrogen isotope distribution in subseafloor hydrothermal systems depends on a number of factors, including whether phase separation is induced by heating at depth or by decompression of hydrothermal fluids ascending to the seafloor. Phase separation in most subseafloor systems appears to be a simple process driven by heating of seawater to conditions within the two-phase region, followed by segregation and entrainment of brine or vapor into a seawater dominated system. Resulting vent fluids exhibit large ranges in Cl concentration with no measurable effect on ??D. Possible exceptions to this include hydrothermal fluids venting at Axial and 9??N on the East Pacific Rise. High ??D values of low Cl fluids venting at Axial are consistent with phase separation taking place at relatively shallow levels in the oceanic crust while negative ??D values in some low Cl fluids venting at 9??N suggest involvement of a magmatic fluid component or phase separation of D-depleted brines derived during previous hydrothermal activity.

Paschen-Back effects and Rydberg-state diamagnetism in vapor-cell electromagnetically induced transparency

NASA Astrophysics Data System (ADS)

Ma, L.; Anderson, D. A.; Raithel, G.

2017-06-01

We report on rubidium vapor-cell Rydberg electromagnetically induced transparency (EIT) in a 0.7 T magnetic field where all involved levels are in the hyperfine Paschen-Back regime, and the Rydberg state exhibits a strong diamagnetic interaction. Signals from both 85Rb and 87Rb are present in the EIT spectra. Isotope-mixed Rb cells allow us to measure the field strength to within a ±0.12 % relative uncertainty. The measured spectra are in excellent agreement with the results of a Monte Carlo calculation and indicate unexpectedly large Rydberg-level dephasing rates. Line shifts and broadenings due to magnetic-field inhomogeneities are included in the model.

Adsorption isotope effects of water on mesoporous silica and alumina with implications for the land-vegetation-atmosphere system

NASA Astrophysics Data System (ADS)

Lin, Ying; Horita, Juske; Abe, Osamu

2018-02-01

Soil water dynamics within a vadose (unsaturated) zone is a key component in the hydrologic cycle, especially in arid regions. In applying the Craig-Gordon evaporation model to obtain isotopic compositions of soil water and the evaporated vapor in land-surface models (LSMs), it has been assumed that the equilibrium isotope fractionation factors between soil water and water vapor, α(2H) and α(18O), are identical to those between liquid and vapor of bulk water. Isotope effects in water condensation arise from intermolecular hydrogen bonding in the condensed phase and the appearance of hindered rotation/translation. Hydrogen bonding between water molecules and pore surface hydroxyl groups influences adsorption isotope effects. To test whether equilibrium fractionation factors between soil water and water vapor are identical to those between liquid and vapor of bulk water and to evaluate the influence of pore size and chemical composition upon adsorption isotope effects, we extended our previous experiments of a mesoporous silica (15 nm) to two other mesoporous materials, a silica (6 nm) and an alumina (5.8 nm). Our results demonstrated that α(2H) and α(18O) between adsorbed water and water vapor are 1.057 and 1.0086 for silica (6 nm) and 1.041 and 1.0063 for alumina (5.8 nm), respectively, at saturation pressure (po), which are smaller than 1.075 and 1.0089, respectively, between liquid and vapor phases of free water at 30 °C and that the differences exaggerate at low water contents. However, the profiles of α values with relative pressures (p/po) for these three materials differ due to the differences in chemical compositions and pore sizes. Empirical formula relating α(2H) and α(18O) values to the proportions of filled pores (f) are developed for potential applications to natural soils. Our results from triple oxygen isotope analyses demonstrated that the isotope fractionation does not follow a canonical law. For the silica (15 nm), fractionation exponents

Paleotemperatures derived from the EPICA Dome-C core based on isotopic diffusion in the firn pack.

NASA Astrophysics Data System (ADS)

Gkinis, V.; Johnsen, S. J.; Vinther, B.; Sheldon, S.; Ritz, C.; Masson-Delmotte, V.

2009-04-01

Water isotope ratios as measured from ice core samples have been used as a proxy for past temperatures. Based i.a. on a Rayleigh fractionation process they record the cloud temperature during snow formation. However, changes in the temperature and humidity of the vapor source can also affect the isotopic signal of the polar precipitation, thus inducing isotopic artifacts. Furthermore, for the case of the Antarctic ice cap, temperature inversions frequently occur during snow formation. As a result, the cloud temperature as recorded by the water isotopes can differ significantly from the temperature at the surface. After the deposition of snow and until pore close off, a diffusive process occurs in the pore space of the firn pack, mixing water vapor from different layers and smoothing the isotopic profiles. The smoothing depends only on the resulting diffusion length. This process is temperature dependent and it presents a slightly different rate between the two isotopic species of water, H218O and HD16O. This is because the fractionation factors as defined for these two isotopic species have a different dependence on temperature. In this study we present a temperature reconstruction based on the different diffusion rates of H218O and HD16O water molecules in firn. The advantage of such an approach is that the temperatures estimated represent the actual conditions in the firn stack. As a result, we can surpass the artifacts that can possibly disrupt the use of the classical technique. We will present temperature estimations as extracted from two high resolution (2.5 cm) data sets, from the EPICA Dome C deep core focused on the Holoene Climatic Optimum and the Last Glacial Maximum and compare them with results obtained with the classical slope method as well as constrains imposed by the measured temperature profile. We will also address the problems of spectral power estimation for determining the diffusion lengths.

Existing and emerging technologies for measuring stable isotope labelled retinol in biological samples: isotope dilution analysis of body retinol stores.

PubMed

Preston, Tom

2014-01-01

This paper discusses some of the recent improvements in instrumentation used for stable isotope tracer measurements in the context of measuring retinol stores, in vivo. Tracer costs, together with concerns that larger tracer doses may perturb the parameter under study, demand that ever more sensitive mass spectrometric techniques are developed. GCMS is the most widely used technique. It has high sensitivity in terms of sample amount and uses high resolution GC, yet its ability to detect low isotope ratios is limited by background noise. LCMSMS may become more accessible for tracer studies. Its ability to measure low level stable isotope tracers may prove superior to GCMS, but it is isotope ratio MS (IRMS) that has been designed specifically for low level stable isotope analysis through accurate analysis of tracer:tracee ratios (the tracee being the unlabelled species). Compound-specific isotope analysis, where GC is interfaced to IRMS, is gaining popularity. Here, individual 13C-labelled compounds are separated by GC, combusted to CO2 and transferred on-line for ratiometric analysis by IRMS at the ppm level. However, commercially-available 13C-labelled retinol tracers are 2 - 4 times more expensive than deuterated tracers. For 2H-labelled compounds, GC-pyrolysis-IRMS has now become more generally available as an operating mode on the same IRMS instrument. Here, individual compounds are separated by GC and pyrolysed to H2 at high temperature for analysis by IRMS. It is predicted that GC-pyrolysis-IRMS will facilitate low level tracer procedures to measure body retinol stores, as has been accomplished in the case of fatty acids and amino acids. Sample size requirements for GC-P-IRMS may exceed those of GCMS, but this paper discusses sample preparation procedures and predicts improvements, particularly in the efficiency of sample introduction.

Portable vapor diffusion coefficient meter

DOEpatents

Ho, Clifford K [Albuquerque, NM

2007-06-12

An apparatus for measuring the effective vapor diffusion coefficient of a test vapor diffusing through a sample of porous media contained within a test chamber. A chemical sensor measures the time-varying concentration of vapor that has diffused a known distance through the porous media. A data processor contained within the apparatus compares the measured sensor data with analytical predictions of the response curve based on the transient diffusion equation using Fick's Law, iterating on the choice of an effective vapor diffusion coefficient until the difference between the predicted and measured curves is minimized. Optionally, a purge fluid can forced through the porous media, permitting the apparatus to also measure a gas-phase permeability. The apparatus can be made lightweight, self-powered, and portable for use in the field.

Comparison of Columnar Water Vapor Measurements During The Fall 1997 ARM Intensive Observation Period: Solar Transmittance Methods

NASA Technical Reports Server (NTRS)

Schmid, B.; Michalsky, J. J.; Slater, D. W.; Barnard, J. C.; Halthore, R. N.; Liljegren, J. C.; Holben, B. N.; Eck, T. F.; Livingston, J. M.; Russell, P. B.

2000-01-01

In the fall of 1997, during an Intensive Observation Period (IOP), the Atmospheric Radiation Measurement (ARM) program conducted a study of water vapor abundance measurement at its Southern Great Plains (SGP) site. Among a large number of instruments, four sun-tracking radiometers were present to measure the columnar water vapor (CWV). All four solar radiometers retrieve CWV by measuring total solar transmittance in the 0.94-gm water vapor absorption band and subtracting contributions due to Rayleigh, ozone and aerosol transmittances. The aerosol optical depth comparisons among the same four radiometers has been presented elsewhere (Geophys. Res. Lett., 26, 17, 2725-2728, 1999). We have used three different methods to retrieve CWV. In a first round of comparison no attempt was made to standardize on the same radiative transfer model and its underlying water vapor spectroscopy. In the second round of comparison we used the same line-by-line code (which includes recently corrected H2O spectroscopy) to retrieve CAN from all four suntracking radiometers. This decreased the mean CWV by 8% or 13%. The spread of 8% in the solar radiometer results found when using the same model is an indication of the other-than-model uncertainties involved in determining CWV from solar transmittance measurements with current instrumentation.

CART Raman Lidar Aerosol and Water Vapor Measurements in the Vicinity of Clouds

NASA Technical Reports Server (NTRS)

Clayton, Marian B.; Ferrare, Richard A.; Turner, David; Newsom, Rob; Sivaraman, Chitra

2008-01-01

Aerosol and water vapor profiles acquired by the Raman lidar instrument located at the Climate Research Facility (CRF) at Southern Great Plains (SGP) provide data necessary to investigate the atmospheric variability in the vicinity of clouds near the top of the planetary boundary layer (PBL). Recent CARL upgrades and modifications to the routine processing algorithms afforded the necessarily high temporal and vertical data resolutions for these investigations. CARL measurements are used to investigate the behavior of aerosol backscattering and extinction and their correlation with water vapor and relative humidity.

Advances in Multicollector ICPMS for precise and accurate isotope ratio measurements of Uranium isotopes

NASA Astrophysics Data System (ADS)

Bouman, C.; Lloyd, N. S.; Schwieters, J.

2011-12-01

The accurate and precise determination of uranium isotopes is challenging, because of the large dynamic range posed by the U isotope abundances and the limited available sample material. Various mass spectrometric techniques are used for the measurement of U isotopes, where TIMS is the most accepted and accurate one. Multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) can offer higher productivity compared to TIMS, but is traditionally limited by low efficiency of sample utilisation. This contribution will discuss progress in MC-ICPMS for detecting 234U, 235U, 236U and 238U in various uranium reference materials from IRMM and NBL. The Thermo Scientific NEPTUNE Plus with Jet Interface offers a modified dry plasma ICP interface using a large interface pump combined with a special set of sample and skimmer cones giving ultimate sensitivity for all elements across the mass range. For uranium, an ion yield of > 3 % was reported previously [1]. The NEPTUNE Plus also offers Multi Ion Counting using discrete dynode electron multipliers as well as two high abundance-sensitivity filters to discriminate against peak tailing effects on 234U and 236U originating from the major uranium beams. These improvements in sensitivity and dynamic range allow accurate measurements of 234U, 235U and 236U abundances on very small samples and at low concentration. In our approach, minor U isotopes 234U and 236U were detected on ion counters with high abundance sensitivity filters, whereas 235U and 238U were detected on Faraday Cups using a high gain current amplifier (10e12 Ohm) for 235U. Precisions and accuracies for 234U and 236U were down to ~1%. For 235U, subpermil levels were reached.

Optimization of post-run corrections for water stable isotope measurements by laser spectroscopy

NASA Astrophysics Data System (ADS)

van Geldern, Robert; Barth, Johannes A. C.

2013-04-01

Light stable isotope analyses of hydrogen and oxygen of water are used in numerous aquatic studies from various scientific fields. The advantage of using stable isotope ratios is that water molecules serve as ubiquitous and already present natural tracers. Traditionally, the samples were analyzed in the laboratory by isotope ratio mass spectrometry (IRMS). Within recent years these analyses have been revolutionized by the development of new isotope ratio laser spectroscopy (IRIS) systems that are said to be cheaper, more robust and mobile compared to IRMS. Although easier to operate, laser systems also need thorough calibration with international reference materials and raw data need correction for analytical effects. A major issue in systems that use liquid injection via a vaporizer module is the memory effect, i.e. the carry-over from the previous analyzed sample in a sequence. This study presents an optimized and simple post-run correction procedure for liquid water injection developed for a Picarro water analyzer. The Excel(TM) template will rely exclusively on standard features implemented in MS Office without the need to run macros, additional code written in Visual Basic for Applications (VBA) or to use a database-related software such as MS Access or SQL Server. These protocols will maximize precision, accuracy and sample throughput via an efficient memory correction. The number of injections per unknown sample can be reduced to 4 or less. This procedure meets the demands of faster throughput with reduced costs per analysis. Procedures were verified by an international proficiency test and traditional IRMS techniques. The template is available free for scientific use from the corresponding author or the journals web site (van Geldern and Barth, 2012). References van Geldern, R. and Barth, J.A.C. (2012) Limnol. Oceanogr. Methods 10:1024-1036 [doi: 10.4319/lom.2012.10.1024

Measurement of Turbulent Water Vapor Fluxes from Lightweight Unmanned Aircraft Systems

NASA Astrophysics Data System (ADS)

Thomas, R. M.; Ramanathan, V.; Nguyen, H.; Lehmann*, K.

2010-12-01

Scientists at the Center for Clouds, Chemistry and Climate (C4) at the Scripps Institution of Oceanography have successfully used Unmanned Aircraft Systems (UASs) for measurements of radiation fluxes, aerosol concentrations and cloud microphysical properties. Building on this success, a payload to measure water vapor fluxes using the eddy covariance (EC) technique has been recently developed and tested. To our knowledge this is the first UAS turbulent flux system to incorporate high-frequency water vapor measurements. The driving aim of the water vapor flux system’s development is to investigate ‘atmospheric rivers’ in the north-western Pacific Ocean, these can lead to sporadic yet extreme rainfall and flooding events upon landfall in California. Such a flux system may also be used to investigate other weather events (e.g. the formation of hurricanes) and offers a powerful aerosol-cloud-radiative forcing investigative tool when combined with the existing aerosol/radiation and cloud microphysics UAS payloads. The atmospheric vertical wind component (w) is derived by this system at up to 100Hz using data from a GPS/Inertial Measurement Unit (GPS/IMU) combined with a fast-response gust probe mounted on the UAV. Measurements of w are then combined with equally high frequency water vapor data (collected using a Campbell Scientific Krypton Hygrometer) to calculate latent heat fluxes (λE). Two test flights were conducted at the NASA Dryden test facility on 27th May 2010, located in the Mojave Desert. Horizontal flight legs were recorded at four altitudes between 1000-2500 masl within the convective boundary layer. Preliminary data analysis indicates averaged spectral data follow the theoretical -5/3 slope , and extrapolation of the flux profile to the surface resulted in λE of 1.6 W m-2; in good agreement with 1.0 W m-2 λE measured by NOAA from a surface tower using standard flux techniques. The system performance during the Dryden test, as well as subsequent

Profiling of Atmospheric Water Vapor from the SSM/T-2 Radiometric Measurements

NASA Technical Reports Server (NTRS)

Wang, J. R.

2000-01-01

An advantage of using the millimeter-wave measurements for water vapor profiling is the ability to probe beyond a moderate cloud cover. Such a capability has been demonstrated from an airborne MIR (Millimeter-wave Imaging Radiometer) flight over the Pacific Ocean during an intense observation period of TOGA/COARE (Tropical Ocean Global Atmosphere/ Couple Ocean Atmospheric Response Experiment) in early 1993. A Cloud Lidar System (CLS) and MODIS Airborne Simulator (MAS) were on board the same aircraft to identify the presence of clouds and cloud type. The retrieval algorithm not only provides output of a water vapor profile, but also the cloud liquid water and approximate cloud altitude required to satisfy convergence of the retrieval. The validity of these cloud parameters has not been verified previously. In this document, these cloud parameters are compared with those derived from concurrent measurements from the CLS and AMPR (Advanced Microwave Precipitation Radiometer).

Comparison of methods for the measurement of mist and vapor from light mineral oil-based metalworking fluids.

PubMed

Simpson, Andrew T

2003-11-01

The measurement of oil mist derived from metalworking fluids formulated with light mineral oils can be highly inaccurate when using traditional filter sampling. This is due to evaporation of oil from the filter. In this work the practicability of an alternative approach measuring total oil mist and vapor was investigated. Combinations of inhalable particle samplers with backup sorbent vapor traps and standard vapor sampling on pumped and diffusive sorbent tubes were evaluated with gravimetric, infrared spectroscopic, and gas chromatographic analytical methods against the performance requirements of European Standard EN 482. An artificial aerosol was used to compare the methods against a reference method of filter sampler in series with three impingers. Multi-orifice samplers were used with standard 8-mm diameter charcoal tubes at 2 L/min without any signs of channelling or significant breakthrough, as were conical inhalable samplers with XAD-2 tubes at 1 L/min. Most combinations of samplers had a bias of less than 3 percent, but solitary pumped charcoal tubes underestimated total oil by 13 percent. Diffusive sampling was affected by impaction of mist particles and condensation of oil vapor. Gravimetric analysis of filters revealed significant potential sample loss during storage, with 4 percent being lost after one day when stored at room temperature and 2 percent when refrigerated. Samples left overnight in the balance room to equilibrate lost 24 percent. Infrared spectroscopy gave more precise results for vapor than gas chromatography (p = 0.002). Gas chromatography was less susceptible to bias from contaminating solvent vapors than infrared spectroscopy, but was still vulnerable to petroleum distillates. Under the specific test conditions (one oil type and mist particle size), all combinations of methods examined complied with the requirements of European Standard EN 484. Total airborne oil can be measured accurately; however, care must be taken to avoid

Single Frequency, Pulsed Laser Diode Transmitter for Dial Water Vapor Measurements at 935nm

NASA Technical Reports Server (NTRS)

Switzer, Gregg W.; Cornwell, Donald M., Jr.; Krainak, Michael A.; Abshire, James B.; Rall, Johnathan A. R.

1998-01-01

We report a tunable, single frequency, narrow linewidth, pulsed laser diode transmitter at 935.68nm for remote sensing of atmospheric water vapor. The transmitter consists of a CW, tunable, external cavity diode laser whose output is amplified 2OdB using a tapered diode amplifier. The output is pulsed for range resolved DIAL lidar by pulsing the drive current to the diode amplifier at 4kHz with a .5% duty cycle. The output from the transmitter is 36OnJ/pulse and is single spatial mode. It maintains a linewidth of less than 25MHz as its wavelength is tuned across the water vapor absorption line at 935.68nm. The transmitter design and its use in a water vapor measurement will be discussed.

Partitioning water and carbon fluxes in a Mediterranean oak woodland using stable oxygen isotopes

NASA Astrophysics Data System (ADS)

Dubbert, Maren; Piayda, Arndt; Cuntz, Matthias; Correia, Alexandra; Silva, Filipe Costa e.; Pereira, Joao; Werner, Christiane

2014-05-01

Water is a key factor driving ecosystem productivity, especially in water-limited ecosystems. A separation of the component fluxes is needed to gain a functional understanding on the development of net ecosystem water fluxes and their coupling with biogeochemical cycles. Oxygen isotope signatures are valuable tracers for water movements within the ecosystem because of the distinct isotopic compositions of water in soil and vegetation. In the past, determination of isotopic signatures of evaporative or transpirational fluxes has been challenging since measurements of water vapor isotopes were difficult to obtain using cold-trap methods, delivering data with low time resolution. Recent developments in laser spectroscopy now enable direct high frequency measurements of the isotopic composition of atmospheric water vapor (δv), evapotranspiration (δET), and its components and allow validations of common modeling approaches for estimating δE and δT based on Craig and Gordon (1965). Here, a novel approach was used, combining a custom build flow-through gas-exchange branch chamber with a Cavity Ring-Down Spectrometer in a Mediteranean cork-oak woodland where two vegetation layers respond differently to drought: oak-trees (Quercus suber L.) avoid drought due to their access to ground water while herbaceous plants survive the summer as seeds. We aimed at 1) testing the Craig and Gordon equation for soil evaporation against directly measured δE and 2) quantifying the role of non-steady-state transpiration under natural conditions. Thirdly, we used this approach to quantify the impact of the understory herbaceous vegetation on ecosystem carbon and water fluxes throughout the year and disentangle how ET components of the ecosystem relate to carbon dioxide exchange. We present one year data comparing modeled and measured stable oxygen isotope signatures (δ18O) of soil evaporation, confirming that the Craig and Gordon equation leads to good agreement with measured δ18O of

Intra-event isotope and raindrop size data of tropical rain reveal effects concealed by event averaged data

NASA Astrophysics Data System (ADS)

Managave, S. R.; Jani, R. A.; Narayana Rao, T.; Sunilkumar, K.; Satheeshkumar, S.; Ramesh, R.

2016-08-01

Evaporation of rain is known to contribute water vapor, a potent greenhouse gas, to the atmosphere. Stable oxygen and hydrogen isotopic compositions (δ18O and, δD, respectively) of precipitation, usually measured/presented as values integrated over rain events or monthly mean values, are important tools for detecting evaporation effects. The slope ~8 of the linear relationship between such time-averaged values of δD and δ18O (called the meteoric water line) is widely accepted as a proof of condensation under isotopic equilibrium and absence of evaporation of rain during atmospheric fall. Here, through a simultaneous investigation of the isotopic and drop size distributions of seventeen rain events sampled on an intra-event scale at Gadanki (13.5°N, 79.2°E), southern India, we demonstrate that the evaporation effects, not evident in the time-averaged data, are significantly manifested in the sub-samples of individual rain events. We detect this through (1) slopes significantly less than 8 for the δD-δ18O relation on intra-event scale and (2) significant positive correlations between deuterium excess ( d-excess = δD - 8*δ18O; lower values in rain indicate evaporation) and the mass-weighted mean diameter of the raindrops ( D m ). An estimated ~44 % of rain is influenced by evaporation. This study also reveals a signature of isotopic equilibration of rain with the cloud base vapor, the processes important for modeling isotopic composition of precipitation. d-excess values of rain are modified by the post-condensation processes and the present approach offers a way to identify the d-excess values least affected by such processes. Isotope-enabled global circulation models could be improved by incorporating intra-event isotopic data and raindrop size dependent isotopic effects.

Microwave Limb Sounder/El Niño Watch - Water Vapor Measurement, October, 1997

NASA Image and Video Library

1997-10-30

This image shows atmospheric water vapor in Earth upper troposphere, about 10 kilometers 6 miles above the surface, as measured by NASA Microwave Limb Sounder MLS instrument flying aboard the Upper Atmosphere Research Satellite.

Recent advances in understanding atmospheric CO based on stable isotope measurements

NASA Astrophysics Data System (ADS)

Popa, Maria Elena; Naus, Stijn; Ferrero Lopez, Noelia; Vijverberg, Sem; de Leeuw, Selma; Röckmann, Thomas

2017-04-01

Carbon monoxide (CO) plays an important role for atmospheric chemistry and for carbon cycling in the atmosphere. Via its reaction with the OH radical it influences concentrations of many other trace gases, it is an important precursor for O3 formation, and its oxidation leads to the formation of about 1 Pg C per year of CO2. The natural and anthropogenic sources of CO are subject to relatively large temporal changes due to natural variability (e.g. biomass burning), industrial activity and mitigation measures (e.g. fossil fuel burning), variations in precursor compounds (e.g. CH4 and VOC) and variations in the abundance of the OH radical in the atmosphere, which are difficult to quantify. Isotope measurements can be used to distinguish between the effects of individual sources and sinks to put tighter constrains on its budget, but the isotopic characterization of the CO sources is in many cases still based on a few relatively old measurements that did not allow to account for dependence on parameters. We will present an update of the isotopic composition of several sources and removal processes of CO that have been carried out in the past years with the automated continuous-flow IRMS system at Utrecht University. This includes: - the previously unknown isotopic composition of direct biogenic CO emissions - a surprisingly large variability in the isotopic composition of CO emitted by different vehicles and single vehicles under various driving conditions - previously very poorly investigated signatures, like the fractionation in the removal of CO by soils, and its interaction with CO that is simultaneously emitted from soil. These results from process specific investigations will be linked to recent atmospheric measurements at various locations.

Seasonal and ENSO Influences on the Stable Isotopic Composition of Galápagos Precipitation

NASA Astrophysics Data System (ADS)

Martin, N. J.; Conroy, J. L.; Noone, D.; Cobb, K. M.; Konecky, B. L.; Rea, S.

2018-01-01

The origin of stable isotopic variability in precipitation over time and space is critical to the interpretation of stable isotope-based paleoclimate proxies. In the eastern equatorial Pacific, modern stable isotope measurements in precipitation (δ18Op and δDp) are sparse and largely unevaluated in the literature, although insights from such analyses would benefit the interpretations of several regional isotope-based paleoclimate records. Here we present a new 3.5 year record of daily-resolved δ18Op and δDp from Santa Cruz, Galápagos. With a prior 13 year record of monthly δ18Op and δDp from the island, these new data reveal controls on the stable isotopic composition of regional precipitation on event to interannual time scales. Overall, we find Galápagos δ18Op is significantly correlated with precipitation amount on daily and monthly time scales. The majority of Galápagos rain events are drizzle, or garúa, derived from local marine boundary layer vapor, with corresponding high δ18Op values due to the local source and increased evaporation and equilibration of smaller drops with boundary layer vapor. On monthly time scales, only precipitation in very strong, warm season El Niño months has substantially lower δ18Op values, as the sea surface temperature threshold for deep convection (28°C) is only surpassed at these times. The 2015/2016 El Niño event did not produce strong precipitation or δ18Op anomalies due to the short period of warm SST anomalies, which did not extend into the peak of the warm season. Eastern Pacific proxy isotope records may be biased toward periods of high rainfall during strong to very strong El Niño events.

Comparison of Water Vapor Measurements from Ground-based and Space-based GPS Atmospheric Remote Sensing Techniques

NASA Astrophysics Data System (ADS)

Colon-Pagan, Ian; Kuo, Ying-Hwa

2008-10-01

In this study, we compare precipitable water vapor (PWV) values from ground-based GPS water vapor sensing and COSMIC radio occultation (RO) measurements over the Caribbean Sea, Gulf of Mexico, and United States regions as well as global analyses from NCEP and ECMWF models. The results show good overall agreement; however, the PWV values estimated by ground-based GPS receivers tend to have a slight dry bias for low PWV values and a slight wet bias for higher PWV values, when compared with GPS RO measurements and global analyses. An application of a student T-test indicates that there is a significant difference between both ground- and space-based GPS measured datasets. The dry bias associated with space-based GPS is attributed to the missing low altitude data, where the concentration of water vapor is large. The close agreements between space-based and global analyses are due to the fact that these global analyses assimilate space-based GPS RO data from COSMIC, and the retrieval of water vapor profiles from space-based technique requires the use of global analyses as the first guess. This work is supported by UCAR SOARS and a grant from the National Oceanic and Atmospheric Administration, Educational Partnership Program under the cooperative agreement NA06OAR4810187.

Portable Cavity Ringdown Spectrometer for Methane Isotope Ratio Measurements

NASA Astrophysics Data System (ADS)

Bostrom, G.; Rice, A.; Atkinson, D.

2008-12-01

Close to 45% (244 Tg/yr) of the methange (CH4) in the atmosphere is produced in anaerobic soil conditions (wetlands and rice paddies). Under aerobic soil conditions, bacteria oxidize CH4 to produce CO2 and H2O. Both production and oxidation rates depend on soil composition, nutrient loadings, water content, and plant conditions, but these dependencies are not well characterized. Measurements of CH4 isotope ratios can provide a better understanding of CH4 processes in natural and man- made ecosystems. Here we present progress on the development of a field deployable instrument capable of making precision 13CH4/12CH4 and CH3D/ CH4 isotope ratio measurements of CH4. Moving the instrument out of the lab and into the field will significantly improve the spatial and temporal resolution of data and enhance the study of plant-soil-atmosphere CH4 source and sink processes. Our instrument is a Near-IR (1280-1340 nm) tunable diode laser Cavity Ringdown Spectroscopy (CRDS) system. CRDS is a technique in which the laser injects energy into a high finesse cavity by tuning to one of the cavity resonant modes, resulting in a buildup of energy. At some threshold intra-cavity intensity the injection is stopped, and the intensity decays exponentially due to losses such as absorption by molecules. If the laser is tuned to an absorption line of a sample gas, the concentration of the molecule is proportional to the decay constant (according to the Beer-Lambert law)--scanning over a frequency range produces an absorption spectrum. Currently our system has a resolution of 150 MHz scanning over a 30 GHz (0.2 nm) region, allowing us to resolve peaks at pressures of 100 torr. Using combinations of CH4 standard (natural isotopic abundance) and a 99% pure 13CH4 standard, we identified several lines in the CH4 HITRAN Database that we attribute to 13CH4. We use these and 12CH4 lines within the same region to measure 13CH4 concentration, 12CH4 concentration, and the isotope ratio (13C/12C and D

Uranium Isotopic Ratio Measurements of U3O8 Reference Materials by Atom Probe Tomography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fahey, Albert J.; Perea, Daniel E.; Bartrand, Jonah AG

2016-01-01

We report results of measurements of isotopic ratios obtained with atom probe tomography on U3O8 reference materials certified for their isotopic abundances of uranium. The results show good agreement with the certified values. High backgrounds due to tails from adjacent peaks complicate the measurement of the integrated peak areas as well as the fact that only oxides of uranium appear in the spectrum, the most intense of which is doubly charged. In addition, lack of knowledge of other instrumental parameters, such as the dead time, may bias the results. Isotopic ratio measurements can be performed at the nanometer-scale with themore » expectation of sensible results. The abundance sensitivity and mass resolving power of the mass spectrometer are not sufficient to compete with magnetic-sector instruments but are not far from measurements made by ToF-SIMS of other isotopic systems. The agreement of the major isotope ratios is more than sufficient to distinguish most anthropogenic compositions from natural.« less

Spacecraft measurements of the elemental and isotopic composition of solar energetic particles

NASA Technical Reports Server (NTRS)

Mewaldt, R. A.

1980-01-01

Within the past few years, instruments flown on satellites and space probes have made significant progress in measuring the elemental and isotopic composition of energetic heavy nuclei accelerated in solar flares. These new observations are discussed, focusing on: (1) the energy dependence of the elemental composition at energies not greater than 1 MeV/nucleon; (2) flare to flare variations in the composition; and (3) comparisons of the average solar particle abundances (Z not less than 2 and not greater than 28) with other measures of the solar composition, including photospheric, coronal, and solar wind observations. These comparisons have led to the suggestion that solar flares sample the composition of the corona. Isotopic measurements of heavy solar flare nuclei have recently added a new dimension to these studies. In particular, the isotopic composition of solar flare neon has been found to be significantly different from that measured in the solar wind, but consistent with the meteoritic component neon-A.

Mass spectrometric measurements of the isotopic anatomies of molecules (Invited)

NASA Astrophysics Data System (ADS)

Eiler, J. M.; Krumwiede, D.; Schlueter, H.

2013-12-01

Site-specific and multiple isotopic substitutions in molecular structures potentially provide an extraordinarily rich set of constraints on their sources, conditions of formation, reaction and transport histories, and perhaps other issues. Examples include carbonate ';clumped isotope' thermometry, clumped isotope measurements of CO2, O2, and, recently, methane, ethane and N2O; site-specific 15N measurements in N2O and 13C and D analyses of fatty acids, sugars, cellulose, food products, and, recently, n-alkanes. Extension of the principles behind these tools to the very large number of isotopologues of complex molecules could potentially lead to new uses of isotope chemistry, similar to proteomics, metabolomics and genomics in their complexity and depth of detail (';isotomics'?). Several technologies are potentially useful for this field, including ';SNIF-NMR', gas source mass spectrometry and IR absorption spectroscopy. However, all well established methods have restrictive limits in the sizes of samples, types of analyzes, and the sorts of isotopologues that can be measured with useful precision. We will present an overview of several emerging instruments and techniques of high-resolution gas source mass spectrometry that may enable study of a large proportion of the isotopologues of a wide range of volatile and semi-volatile compounds, including many organics, with precisions and sample sizes suitable for a range of applications. A variety of isotopologues can be measured by combining information from the Thermo 253 Ultra (a new high resolution, multi-collector gas source mass spectrometer) and the Thermo DFS (a very high resolution single collector, but used here on a novel mode to achieve ~per mil precision ratio measurements), sometimes supplemented by conventional bulk isotopic measurements. It is possible to design methods in which no one of these sources of data meaningfully constrain abundances of specific isotopologues, but their combination fully and

X-ray diffraction characterization of epitaxial CVD diamond films with natural and isotopically modified compositions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prokhorov, I. A., E-mail: igor.prokhorov@mail.ru; Voloshin, A. E.; Ralchenko, V. G.

2016-11-15

Comparative investigations of homoepitaxial diamond films with natural and modified isotopic compositions, grown by chemical vapor deposition (CVD) on type-Ib diamond substrates, are carried out using double-crystal X-ray diffractometry and topography. The lattice mismatch between the substrate and film is precisely measured. A decrease in the lattice constant on the order of (Δa/a){sub relax} ∼ (1.1–1.2) × 10{sup –4} is recorded in isotopically modified {sup 13}C (99.96%) films. The critical thicknesses of pseudomorphic diamond films is calculated. A significant increase in the dislocation density due to the elastic stress relaxation is revealed by X-ray topography.

Kinetic Requirements for the Measurement of Mesospheric Water Vapor at 6.8 (microns) under Non-LTE Conditions

NASA Technical Reports Server (NTRS)

Zhou, Daniel K.; Mlynczak, Martin G.; Lopez-Puertas, Manuel; Russell, James M., III

1999-01-01

We present accuracy requirements for specific kinetic parameters used to calculate the populations and vibrational temperatures of the H2O(010) and H2O(020) states in the terrestrial mesosphere. The requirements are based on rigorous simulations of the retrieval of mesospheric water vapor profiles from measurements of water vapor infrared emission made by limb scanning instruments on orbiting satellites. Major improvements in the rate constants that describe vibration-to- vibration exchange between the H2O(010) and 02(1) states are required in addition to improved specification of the rate of quenching Of O2(1) by atomic oxygen (0). It is also necessary to more accurately determine the yield of vibrationally excited O2(l) resulting from ozone photolysis. A contemporary measurement of the rate of quenching of H2O(010) by N2 and O2 is also desirable. These rates are either highly uncertain or have never before been measured at atmospheric temperatures. The suggested improvements are necessary for the interpretation of water vapor emission measurements at 6.8 microns to be made from a new spaceflight experiment in less than 2 years. The approach to retrieving water vapor under non-LTE conditions is also presented.

Apparatus for isotopic alteration of mercury vapor

DOEpatents

Grossman, Mark W.; George, William A.; Marcucci, Rudolph V.

1988-01-01

An apparatus for enriching the isotopic Hg content of mercury is provided. The apparatus includes a reactor, a low pressure electric discharge lamp containing a fill including mercury and an inert gas. A filter is arranged concentrically around the lamp. In a preferred embodiment, constant mercury pressure is maintained in the filter by means of a water-cooled tube that depends from it, the tube having a drop of mercury disposed in it. The reactor is arranged around the filter, whereby radiation from said lamp passes through the filter and into said reactor. The lamp, the filter and the reactor are formed of a material which is transparent to ultraviolet light.

Can Lightning Produce Significant Levels of Mass-Independent Oxygen Isotopic Fractionation in Nebular Dust?

NASA Technical Reports Server (NTRS)

Nuth, Joseph A.; Paquette, John A.; Farquhar, Adam

2012-01-01

Based on recent evidence that oxide grains condensed from a plasma will contain oxygen that is mass independently fractionated compared to the initial composition of the vapor, we present a first attempt to evaluate the potential magnitude of this effect on dust in the primitive solar nebula. This assessment relies on previous studies of nebular lightning to provide reasonable ranges of physical parameters to form a very simple model to evaluate the plausibility that lightning could affect a significant fraction of nebular dust and that such effects could cause a significant change in the oxygen isotopic composition of solids in the solar nebula over time. If only a small fraction of the accretion energy is dissipated as lightning over the volume of the inner solar nebula, then a large fraction of nebular dust will be exposed to lightning. If the temperature of such bolts is a few percent of the temperatures measured in terrestrial discharges, then dust will vaporize and recondense in an ionized environment. Finally, if only a small average decrease is assumed in the O-16 content of freshly condensed dust, then over the last 5 million years of nebular accretion the average delta O-17 of the dust could increase by more than 30 per mil. We conclude that it is possible that the measured " slope 1" oxygen isotope line measured in meteorites and their components represents a time-evolution sequence of nebular dust over the last several million years of nebular evolution O-16-rich materials formed first, then escaped further processing as the average isotopic composition of the dust graduaUy became increasingly depleted in O-16 .

Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim

NASA Technical Reports Server (NTRS)

Matzel, J. E. P.; Simon, J. I.; Hutcheon, I. D.; Jacobsen, B.; Simon, S. B.; Grossman, L.

2013-01-01

Ca-, Al-rich inclusions (CAIs) from CV chondrites commonly show oxygen isotope heterogeneity among different mineral phases within individual inclusions reflecting the complex history of CAIs in both the solar nebula and/or parent bodies. The degree of isotopic exchange is typically mineral-specific, yielding O-16-rich spinel, hibonite and pyroxene and O-16-depleted melilite and anorthite. Recent work demonstrated large and systematic variations in oxygen isotope composition within the margin and Wark-Lovering rim of an Allende Type A CAI. These variations suggest that some CV CAIs formed from several oxygen reservoirs and may reflect transport between distinct regions of the solar nebula or varying gas composition near the proto-Sun. Oxygen isotope compositions of CAIs from other, less-altered chondrites show less intra-CAI variability and 16O-rich compositions. The record of intra-CAI oxygen isotope variability in CM chondrites, which commonly show evidence for low-temperature aqueous alteration, is less clear, in part because the most common CAIs found in CM chondrites are mineralogically simple (hibonite +/- spinel or spinel +/- pyroxene) and are composed of minerals less susceptible to O-isotopic exchange. No measurements of the oxygen isotope compositions of rims on CAIs in CM chondrites have been reported. Here, we present oxygen isotope data from a rare, Type A CAI from the Murchison meteorite, MUM-1. The data were collected from melilite, hibonite, perovskite and spinel in a traverse into the interior of the CAI and from pyroxene, melilite, anorthite, and spinel in the Wark-Lovering rim. Our objectives were to (1) document any evidence for intra-CAI oxygen isotope variability; (2) determine the isotopic composition of the rim minerals and compare their composition(s) to the CAI interior; and (3) compare the MUM-1 data to oxygen isotope zoning profiles measured from CAIs in other chondrites.

High-precision measurement of (186)Os/(188)Os and (187)Os/(188)Os: isobaric oxide corrections with in-run measured oxygen isotope ratios.

PubMed

Chu, Zhu-Yin; Li, Chao-Feng; Chen, Zhi; Xu, Jun-Jie; Di, Yan-Kun; Guo, Jing-Hui

2015-09-01

We present a novel method for high precision measurement of (186)Os/(188)Os and (187)Os/(188)Os ratios, applying isobaric oxide interference correction based on in-run measurements of oxygen isotopic ratios. For this purpose, we set up a static data collection routine to measure the main Os(16)O3(-) ion beams with Faraday cups connected to conventional 10(11) amplifiers, and (192)Os(16)O2(17)O(-) and (192)Os(16)O2(18)O(-) ion beams with Faraday cups connected to 10(12) amplifiers. Because of the limited number of Faraday cups, we did not measure (184)Os(16)O3(-) and (189)Os(16)O3(-) simultaneously in-run, but the analytical setup had no significant influence on final (186)Os/(188)Os and (187)Os/(188)Os data. By analyzing UMd, DROsS, an in-house Os solution standard, and several rock reference materials, including WPR-1, WMS-1a, and Gpt-5, the in-run measured oxygen isotopic ratios were proven to present accurate Os isotopic data. However, (186)Os/(188)Os and (187)Os/(188)Os data obtained with in-run O isotopic compositions for the solution standards and rock reference materials show minimal improvement in internal and external precision, compared to the conventional oxygen correction method. We concluded that, the small variations of oxygen isotopes during OsO3(-) analytical sessions are probably not the main source of error for high precision Os isotopic analysis. Nevertheless, use of run-specific O isotopic compositions is still a better choice for Os isotopic data reduction and eliminates the requirement of extra measurements of the oxygen isotopic ratios.

δ2H isotopic flux partitioning of evapotranspiration over a grass field following a water pulse and subsequent dry down

NASA Astrophysics Data System (ADS)

Good, Stephen P.; Soderberg, Keir; Guan, Kaiyu; King, Elizabeth G.; Scanlon, Todd M.; Caylor, Kelly K.

2014-02-01

The partitioning of surface vapor flux (FET) into evaporation (FE) and transpiration (FT) is theoretically possible because of distinct differences in end-member stable isotope composition. In this study, we combine high-frequency laser spectroscopy with eddy covariance techniques to critically evaluate isotope flux partitioning of FET over a grass field during a 15 day experiment. Following the application of a 30 mm water pulse, green grass coverage at the study site increased from 0 to 10% of ground surface area after 6 days and then began to senesce. Using isotope flux partitioning, transpiration increased as a fraction of total vapor flux from 0% to 40% during the green-up phase, after which this ratio decreased while exhibiting hysteresis with respect to green grass coverage. Daily daytime leaf-level gas exchange measurements compare well with daily isotope flux partitioning averages (RMSE = 0.0018 g m-2 s-1). Overall the average ratio of FT to FET was 29%, where uncertainties in Keeling plot intercepts and transpiration composition resulted in an average of uncertainty of ˜5% in our isotopic partitioning of FET. Flux-variance similarity partitioning was partially consistent with the isotope-based approach, with divergence occurring after rainfall and when the grass was stressed. Over the average diurnal cycle, local meteorological conditions, particularly net radiation and relative humidity, are shown to control partitioning. At longer time scales, green leaf area and available soil water control FT/FET. Finally, we demonstrate the feasibility of combining isotope flux partitioning and flux-variance similarity theory to estimate water use efficiency at the landscape scale.

Preliminary results of an aircraft system based on near-IR diode lasers for continuous measurements of the concentration of methane, carbon dioxide, water and its isotopes

NASA Astrophysics Data System (ADS)

Nadezhdinsky, A. I.; Ponurovsky, Ya. Ya.; Shapovalov, Y. P.; Popov, I. P.; Stavrovsky, D. B.; Khattatov, V. U.; Galaktionov, V. V.; Kuzmichev, A. S.

2012-11-01

The Federal Agency for Hydrometeorology of the Russian Federation created the flying laboratory on board the passenger airplane Yak-42D for geophysical monitoring of the environment, including aircraft measurements of vertical concentrations of greenhouse gases in the troposphere. Within the limits of this project, General Physics Institute of the Russian Academy of Science developed airborne tunable diode laser spectrometer (TDLS) on the basis of diode lasers of a near-IR range for measurement of the altitude profiles of CO2, CH4, H2O and its isotopes. TDLS complex was integrated aboard in standard 19-in. rack. Air samples, taken over an aircraft on the pipeline, were injected into the optical cell. Using the system of inflow and heating, the air was set laminar with a flowrate of 0.2 l/s at a reduced pressure of 100 mbar for detecting narrow absorption lines of water vapor isotopes. For registration of the absorption spectra and for the measurement of greenhouse gas concentrations in online mode, modulation-correlation technique was used. Diode laser spectrometer output data were transferred to the airborne central computer. Sensitivity of TDLS measurements was 20-30 ppm for water, 3-4 ppm for CO2 and 20-25 ppb for CH4. Time of one-unit measurement is about 30 ms.

Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS

NASA Technical Reports Server (NTRS)

Morgan, Leah E.; Lloyd, Nicholas S.; Ellam, Robert M.; Simon, Justin I.

2012-01-01

Potassium isotopic (K-41/K-39) compositions are notoriously difficult to measure. TIMS measurements are hindered by variable fractionation patterns throughout individual runs and too few isotopes to apply an internal spike method for instrumental mass fractionation corrections. Internal fractionation corrections via the K-40/K-39 ratio can provide precise values but assume identical K-40/K-39 ratios (e.g. 0.05% (1sigma) in [1]); this is appropriate in some cases (e.g. identifying excess K-41) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25% precisions (1sigma) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as Ar-38H(+) and Ar-40H(+) and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2% (1sigma, e.g. [3]). Although these precisions may be acceptable for some concentration determinations, they do not resolve isotopic variation in terrestrial materials. Here we present data from a series of measurements made on the Thermo Scientific NEPTUNE Plus multi-collector ICP-MS that demonstrate the ability to make K-41/K-39 ratio measurements with 0.07% precisions (1sigma). These data, collected on NIST K standards, indicate the potential for MC-ICP-MS measurements to look for K isotopic variations at the sub-permil level. The NEPTUNE Plus can sufficiently resolve 39K and 41K from the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma and high-resolution mode. Measurements were made on small but flat, interference-free, plateaus (ca. 50 ppm by mass width for K-41). Although ICP-MS does not yield accurate K-41/K-39 values due to significant instrumental mass fractionation (ca. 6%), this bias can be sufficiently stable over the time required for several measurements so that relative K-41/K-39 values can be precisely determined via sample

Precision mass measurements of neutron-rich Co isotopes beyond N =40

NASA Astrophysics Data System (ADS)

Izzo, C.; Bollen, G.; Brodeur, M.; Eibach, M.; Gulyuz, K.; Holt, J. D.; Kelly, J. M.; Redshaw, M.; Ringle, R.; Sandler, R.; Schwarz, S.; Stroberg, S. R.; Sumithrarachchi, C. S.; Valverde, A. A.; Villari, A. C. C.

2018-01-01

The region near Z =28 and N =40 is a subject of great interest for nuclear structure studies due to spectroscopic signatures in 68Ni suggesting a subshell closure at N =40 . Trends in nuclear masses and their derivatives provide a complementary approach to shell structure investigations via separation energies. Penning trap mass spectrometry has provided precise measurements for a number of nuclei in this region; however, a complete picture of the mass surfaces has so far been limited by the large uncertainty remaining for nuclei with N >40 along the iron (Z =26 ) and cobalt (Z =27 ) chains because these species are not available from traditional isotope separator online rare isotope facilities. The Low-Energy Beam and Ion Trap Facility at the National Superconducting Cyclotron Laboratory is the first and only Penning trap mass spectrometer coupled to a fragmentation facility and therefore presents the unique opportunity to perform precise mass measurements of these elusive isotopes. Here we present the first Penning trap measurements of Co,6968, carried out at this facility. Some ambiguity remains as to whether the measured values are ground-state or isomeric-state masses. A detailed discussion is presented to evaluate this question and to motivate future work. In addition, we perform ab initio calculations of ground-state and two-neutron separation energies of cobalt isotopes with the valence-space in-medium similarity renormalization group approach based on a particular set of two- and three-nucleon forces that predict saturation in infinite matter. We discuss the importance of these measurements and calculations for understanding the evolution of nuclear structure near 68Ni.

STABLE ISOTOPE GEOCHEMISTRY OF THERMAL FLUIDS FROM LASSEN VOLCANIC NATIONAL PARK, CALIFORNIA.

USGS Publications Warehouse

Janik, Cathy J.; Nehring, Nancy L.; Truesdell, Alfred H.

1983-01-01

In the Lassen vapor-dominated geothermal system, surface manifestations of thermal fluids at high elevations (1800-2500 m) include superheated and drowned fumaroles, steam-heated acid-sulfate hot springs, and low-chloride bicarbonate springs. Neutral high-chloride hot water discharges at lower elevations. Deuterium and oxygen-18 data establish genetic connections between these fluids and with local meteoric waters. Steam from the highest temperature fumarole at Bumpass Hell and water from the highest chloride hot spring have isotopic compositions corresponding to vapor-liquid equilibrium at 235 degree C. Carbon and sulfur isotope data suggest that the CO//2 and H//2S in the system did not entirely originate from magmatic sources, but probably include contributions from thermal metamorphism of marine sedimentary rocks. Observations suggest that carbon and sulfur isotope variations are useful indicators of gas reactions and flow paths in geothermal systems. Refs.

[Measurements of stable isotopes in atmospheric CO2 and H2O by open-path Fourier transform infrared spectrometry].

PubMed

Wang, Wei; Liu, Wen-Qing; Zhang, Tian-Shu

2013-08-01

The development of spectroscopic techniques has offered continuous measurement of stable isotopes in the ambient air. The method of measuring environmental stable isotopes based on Fourier transform infrared spectrometry (FTIR) is described. In order to verify the feasibility of the method for continuous measurement of the stable isotopes, an open-path FTIR system was used to measure stable isotopes of CO2 and H2O in ambient air directly in a seven-day field experiment, including 12CO2, 3CO2, H2 16O and HD16 O. Also, the time course of carbon isotopic ratio delta13 C and deuterium isotope composition deltaD was calculated. The measurement precision is about 1.08 per thousand for delta13 C and 1.32 per thousand for deltaD. The measured stable isotopes of CO2 and H2O were analyzed on different time scales by Keeling plot methods, and the deuterium isotopic ratios of evapotranspiration were determined. The results of the field experiment demonstrate the potential of the open-path FTIR system for continuous measurement of stable isotopes in the air.

Thermal Conductivity Measurement of an Electron-Beam Physical-Vapor-Deposition Coating

PubMed Central

Slifka, A. J.; Filla, B. J.

2003-01-01

An industrial ceramic thermal-barrier coating designated PWA 266, processed by electron-beam physical-vapor deposition, was measured using a steady-state thermal conductivity technique. The thermal conductivity of the mass fraction 7 % yttria-stabilized zirconia coating was measured from 100 °C to 900 °C. Measurements on three thicknesses of coatings, 170 μm, 350 μm, and 510 μm resulted in thermal conductivity in the range from 1.5 W/(m·K) to 1.7 W/(m·K) with a combined relative standard uncertainty of 20 %. The thermal conductivity is not significantly dependent on temperature. PMID:27413601

Thermal Conductivity Measurement of an Electron-Beam Physical-Vapor-Deposition Coating.

PubMed

Slifka, A J; Filla, B J

2003-01-01

An industrial ceramic thermal-barrier coating designated PWA 266, processed by electron-beam physical-vapor deposition, was measured using a steady-state thermal conductivity technique. The thermal conductivity of the mass fraction 7 % yttria-stabilized zirconia coating was measured from 100 °C to 900 °C. Measurements on three thicknesses of coatings, 170 μm, 350 μm, and 510 μm resulted in thermal conductivity in the range from 1.5 W/(m·K) to 1.7 W/(m·K) with a combined relative standard uncertainty of 20 %. The thermal conductivity is not significantly dependent on temperature.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conroy, Jessica L; Cobb, Kim M; Noone, David

The objective of this field campaign was to investigate climatic controls on the stable isotopic composition of water vapor, precipitation, and seawater in the western tropical Pacific. Simultaneous measurements of the stable isotopic composition of vapor and precipitation from April 28 to May 8, 2013, at the Manus Tropical Western Pacific Atmospheric Radiation Measurement site, provided several key insights into the nature of the climate signal archived in precipitation and vapor isotope ratios. We observed a large shift from lower to higher isotopic values in vapor and precipitation because of the passage of a mesoscale convective system west of themore » site and a transition from a regional stormy period into a more quiescent period. During the quiescent period, the stable isotopic composition of vapor and precipitation indicated the predominance of oceanic evaporation in determining the isotopic composition of boundary-layer vapor and local precipitation. There was not a consistent relationship between intra-event precipitation amount at the site and the stable isotopic composition of precipitation, thus challenging simplified assumptions about the isotopic “amount effect” in the tropics on the time scale of individual storms. However, some storms did show an amount effect, and deuterium excess values in precipitation had a significant relationship with several meteorological variables, including precipitation, temperature, relative humidity, and cloud base height across all measured storms. The direction of these relationships points to condensation controls on precipitation deuterium excess values on intra-event time scales. The relationship between simultaneous measurements of vapor and precipitation isotope ratios during precipitation events indicates the ratio of precipitation-to-vapor isotope ratios can diagnose precipitation originating from a vapor source unique from boundary-layer vapor and rain re-evaporation.« less

Vapor-based interferometric measurement of local evaporation rate and interfacial temperature of evaporating droplets.

PubMed

Dehaeck, Sam; Rednikov, Alexey; Colinet, Pierre

2014-03-04

The local evaporation rate and interfacial temperature are two quintessential characteristics for the study of evaporating droplets. Here, it is shown how one can extract these quantities by measuring the vapor concentration field around the droplet with digital holographic interferometry. As a concrete example, an evaporating freely receding pending droplet of 3M Novec HFE-7000 is analyzed at ambient conditions. The measured vapor cloud is shown to deviate significantly from a pure-diffusion regime calculation, but it compares favorably to a new boundary-layer theory accounting for a buoyancy-induced convection in the gas and the influence upon it of a thermal Marangoni flow. By integration of the measured local evaporation rate over the interface, the global evaporation rate is obtained and validated by a side-view measurement of the droplet shape. Advective effects are found to boost the global evaporation rate by a factor of 4 as compared to the diffusion-limited theory.

Water vapor profiling using microwave radiometry

NASA Technical Reports Server (NTRS)

Wang, J. R.; Wilheit, T. T.

1988-01-01

Water vapor is one of the most important constituents in the Earth's atmosphere. Its spatial and temporal variations affect a wide spectrum of meteorological phenomena ranging from the formation of clouds to the development of severe storms. The passive microwave technique offers an excellent means for water vapor measurements. It can provide both day and night coverage under most cloud conditions. Two water vapor absorption features, at 22 and 183 GHz, were explored in the past years. The line strengths of these features differ by nearly two orders of magnitude. As a consequence, the techniques and the final products of water vapor measurements are also quite different. The research effort in the past few years was to improve and extend the retrieval algorithm to the measurements of water vapor profiles under cloudy conditions. In addition, the retrieval of total precipitable water using 183 GHz measurements, but in a manner analogous to the use of 22 GHz measurements, to increase measurement sensitivity for atmospheres of very low moisture content was also explored.

New approaches to the Moon's isotopic crisis

PubMed Central

Melosh, H. J.

2014-01-01

Recent comparisons of the isotopic compositions of the Earth and the Moon show that, unlike nearly every other body known in the Solar System, our satellite's isotopic ratios are nearly identical to the Earth's for nearly every isotopic system. The Moon's chemical make-up, however, differs from the Earth's in its low volatile content and perhaps in the elevated abundance of oxidized iron. This surprising situation is not readily explained by current impact models of the Moon's origin and offers a major clue to the Moon's formation, if we only could understand it properly. Current ideas to explain this similarity range from assuming an impactor with the same isotopic composition as the Earth to postulating a pure ice impactor that completely vaporized upon impact. Several recent proposals follow from the suggestion that the Earth–Moon system may have lost a great deal of angular momentum during early resonant interactions. The isotopic constraint may be the most stringent test yet for theories of the Moon's origin. PMID:25114301

A critical review of measurements of water vapor absorption in the 840 to 1100 cm(-1) spectral region

NASA Technical Reports Server (NTRS)

Grant, William B.

1987-01-01

A set of eleven measurements of the water vapor continuum absorption in the 840 to 1100 sq cm spectral region is reviewed and compared with spectral models maintained by the Air Force Geophysics Laboratory. The measurements were made in four different ways: spectrometer with a White cell, CO2 laser with a White cell, CO2 laser with a spectrophone, and broadband radiation source over a long atmospheric path. Where possible, the data were selected at a water vapor partial pressure of ten torr buffered to 760 torr with N2 or synthetic air and a temperature of between 296 and 300 K. The intercomparison of the data leads to several observations and conclusions. First, there are four sets of laboratory data taken with nitrogen as the buffer gas which generally agree well mutually and with AFGL's HITRAN code. Second, there is one set of laboratory data that shows that using air as the buffer gas gives a few percent decrease in the water vapor continuum compared with using nitrogen as the buffer gas. Third, the atmospheric long-path measurements for water vapor partial pressure below about 12 torr are roughly grouped within 20 percent of the HITRAN values. Fourth, there are three sets of spectrophone data for water vapor in synthetic air which are significantly higher than any of the other measurements. This discrepancy is attributed to the effects of impurity gases in the cell.

Purdue Rare Isotope Measurement Laboratory

NASA Astrophysics Data System (ADS)

Caffee, M.; Elmore, D.; Granger, D.; Muzikar, P.

2002-12-01

The Purdue Rare Isotope Measurement Laboratory (PRIME Lab) is a dedicated research and service facility for accelerator mass spectrometry. AMS is an ultra-sensitive analytical technique used to measure low levels of long-lived cosmic-ray-produced and anthropogenic radionuclides, and rare trace elements. We measure 10Be (T1/2 = 1.5 My), 26Al (.702 My), 36Cl (.301 My), and 129I (16 My), in geologic samples. Applications include dating the cosmic-ray-exposure time of rocks on Earth's surface, determining rock and sediment burial ages, measuring the erosion rates of rocks and soils, and tracing and dating ground water. We perform sample preparation and separation chemistries for these radio-nuclides for our internal research activities and for those external researchers not possessing this capability. Our chemical preparation laboratories also serve as training sites for members of the geoscience community developing these techniques at their institutions. Research at Purdue involves collaborators among members of the Purdue Departments of Physics, Earth and Atmospheric Sciences, Chemistry, Agronomy, and Anthropology. We also collaborate and serve numerous scientists from other institutions. We are currently in the process of modernizing the facility with the goals of higher precision for routinely measured radio-nuclides, increased sample throughput, and the development of new measurement capabilities for the geoscience community.

VAPOR PRESSURES AND HEATS OF VAPORIZATION OF PRIMARY COAL TARS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eric M. Suuberg; Vahur Oja

1997-07-01

This project had as its main focus the determination of vapor pressures of coal pyrolysis tars. It involved performing measurements of these vapor pressures and from them, developing vapor pressure correlations suitable for use in advanced pyrolysis models (those models which explicitly account for mass transport limitations). This report is divided into five main chapters. Each chapter is a relatively stand-alone section. Chapter A reviews the general nature of coal tars and gives a summary of existing vapor pressure correlations for coal tars and model compounds. Chapter B summarizes the main experimental approaches for coal tar preparation and characterization whichmore » have been used throughout the project. Chapter C is concerned with the selection of the model compounds for coal pyrolysis tars and reviews the data available to us on the vapor pressures of high boiling point aromatic compounds. This chapter also deals with the question of identifying factors that govern the vapor pressures of coal tar model materials and their mixtures. Chapter D covers the vapor pressures and heats of vaporization of primary cellulose tars. Chapter E discusses the results of the main focus of this study. In summary, this work provides improved understanding of the volatility of coal and cellulose pyrolysis tars. It has resulted in new experimentally verified vapor pressure correlations for use in pyrolysis models. Further research on this topic should aim at developing general vapor pressure correlations for all coal tars, based on their molecular weight together with certain specific chemical characteristics i.e. hydroxyl group content.« less

Calcium isotope systematics at hydrothermal conditions: Mid-ocean ridge vent fluids and experiments in the CaSO4-NaCl-H2O system

NASA Astrophysics Data System (ADS)

Scheuermann, Peter P.; Syverson, Drew D.; Higgins, John A.; Pester, Nicholas J.; Seyfried, William E.

2018-04-01

Two sets of hydrothermal experiments were performed to explore Ca isotope fractionation and exchange rates at hydrothermal conditions (410-450 °C, 31.0-50.0 MPa). The first set of experiments determined the magnitude of vapor-liquid Ca isotope fractionation and anhydrite solubility in the CaSO4-NaCl-H2O system. The data indicate no statistical difference between the Ca isotopic composition of coexisting vapor and liquid. The second set of experiments utilized an anomalous 43Ca spike to determine the rate of Ca exchange between fluid and anhydrite as a function of total dissolved Ca concentration. Results show that the rate of exchange increases with dissolved Ca concentrations (12-23 mM/kg), but no change in exchange rate is observed when the Ca concentration increases from 23 to 44 mM/kg Ca. 74-142 days are required to achieve 90% anhydrite-fluid Ca isotope exchange at the conditions investigated, while only several hours are necessary for vapor-liquid isotopic equilibrium. The lack of vapor-liquid Ca isotope fractionation in our experiments is consistent with δ44Ca of mid-ocean ridge hydrothermal vent fluids that remain constant, regardless of chlorinity. Moreover, the narrow range of end member fluid δ44Ca, -0.98 to -1.13‰ (SW), is largely indistinguishable from MORB δ44Ca, suggesting that neither phase separation nor fluid-rock interactions at depth significantly fractionate Ca isotopes in modern high-temperature mid-ocean ridge hydrothermal systems.

Vapor spill monitoring method

DOEpatents

Bianchini, Gregory M.; McRae, Thomas G.

1985-01-01

Method for continuous sampling of liquified natural gas effluent from a spill pipe, vaporizing the cold liquified natural gas, and feeding the vaporized gas into an infrared detector to measure the gas composition. The apparatus utilizes a probe having an inner channel for receiving samples of liquified natural gas and a surrounding water jacket through which warm water is flowed to flash vaporize the liquified natural gas.

Noncatalytic thermocouple coatings produced with chemical vapor deposition for flame temperature measurements.

PubMed

Bahlawane, N; Struckmeier, U; Kasper, T S; Osswald, P

2007-01-01

Chemical vapor deposition (CVD) and metal-organic chemical vapor deposition (MOCVD) have been employed to develop alumina thin films in order to protect thermocouples from catalytic overheating in flames and to minimize the intrusion presented to the combustion process. Alumina films obtained with a CVD process using AlCl(3) as the precursor are dense, not contaminated, and crystallize in the corundum structure, while MOCVD using Al(acetyl acetone)(3) allows the growth of corundum alumina with improved growth rates. These films, however, present a porous columnar structure and show some carbon contamination. Therefore, coated thermocouples using AlCl(3)-CVD were judged more suitable for flame temperature measurements and were tested in different fuels over a typical range of stoichiometries. Coated thermocouples exhibit satisfactory measurement reproducibility, no temporal drifts, and do not suffer from catalytic effects. Furthermore, their increased radiative heat loss (observed by infrared spectroscopy) allows temperature measurements over a wider range when compared to uncoated thermocouples. A flame with a well-known temperature profile established with laser-based techniques was used to determine the radiative heat loss correction to account for the difference between the apparent temperature measured by the coated thermocouple and the true flame temperature. The validity of the correction term was confirmed with temperature profile measurements for several flames previously studied in different laboratories with laser-based techniques.

DoE optimization of a mercury isotope ratio determination method for environmental studies.

PubMed

Berni, Alex; Baschieri, Carlo; Covelli, Stefano; Emili, Andrea; Marchetti, Andrea; Manzini, Daniela; Berto, Daniela; Rampazzo, Federico

2016-05-15

By using the experimental design (DoE) technique, we optimized an analytical method for the determination of mercury isotope ratios by means of cold-vapor multicollector ICP-MS (CV-MC-ICP-MS) to provide absolute Hg isotopic ratio measurements with a suitable internal precision. By running 32 experiments, the influence of mercury and thallium internal standard concentrations, total measuring time and sample flow rate was evaluated. Method was optimized varying Hg concentration between 2 and 20 ng g(-1). The model finds out some correlations within the parameters affect the measurements precision and predicts suitable sample measurement precisions for Hg concentrations from 5 ng g(-1) Hg upwards. The method was successfully applied to samples of Manila clams (Ruditapes philippinarum) coming from the Marano and Grado lagoon (NE Italy), a coastal environment affected by long term mercury contamination mainly due to mining activity. Results show different extents of both mass dependent fractionation (MDF) and mass independent fractionation (MIF) phenomena in clams according to their size and sampling sites in the lagoon. The method is fit for determinations on real samples, allowing for the use of Hg isotopic ratios to study mercury biogeochemical cycles in complex ecosystems. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of a new candidate isotopic reference material for natural Pb using primary measurement method.

PubMed

Nonose, Naoko; Suzuki, Toshihiro; Shin, Ki-Cheol; Miura, Tsutomu; Hioki, Akiharu

2017-06-29

A lead isotopic standard solution with natural abundance has been developed by applying a mixture of a solution of enriched 208 Pb and a solution of enriched 204 Pb ( 208 Pb- 204 Pb double spike solution) as bracketing method. The amount-of-substance ratio of 208 Pb: 204 Pb in this solution is accurately measured by applying EDTA titrimetry, which is one of the primary measurement methods, to each enriched Pb isotope solution. Also metal impurities affecting EDTA titration and minor lead isotopes contained in each enriched Pb isotope solution are quantified by ICP-SF-MS. The amount-of-substance ratio of 208 Pb: 204 Pb in the 208 Pb- 204 Pb double spike solution is 0.961959 ± 0.000056 (combined standard uncertainty; k = 1). Both the measurement of lead isotope ratios in a candidate isotopic standard solution and the correction of mass discrimination in MC-ICP-MS are carried out by coupling of a bracketing method with the 208 Pb- 204 Pb double spike solution and a thallium internal addition method, where thallium solution is added to the standard and the sample. The measured lead isotope ratios and their expanded uncertainties (k = 2) in the candidate isotopic standard solution are 18.0900 ± 0.0046 for 206 Pb: 204 Pb, 15.6278 ± 0.0036 for 207 Pb: 204 Pb, 38.0626 ± 0.0089 for 208 Pb: 204 Pb, 2.104406 ± 0.00013 for 208 Pb: 206 Pb, and 0.863888 ± 0.000036 for 207 Pb: 206 Pb. The expanded uncertainties are about one half of the stated uncertainty for NIST SRM 981, for 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, or one eighth, for 208 Pb: 206 Pb and 207 Pb: 206 Pb, The combined uncertainty consists of the uncertainties due to lead isotope ratio measurements and the remaining time-drift effect of mass discrimination in MC-ICP-MS, which is not removed by the coupled correction method. In the measurement of 208 Pb: 204 Pb, 207 Pb: 204 Pb and 206 Pb: 204 Pb, the latter contribution is two or three times larger than the former. When the coupling of

Carbon Isotopic Measurements of Amino Acids in Stardust-Returned Samples

NASA Technical Reports Server (NTRS)

Elsila, Jamie

2009-01-01

NASA's Stardust spacecraft returned to Earth samples from comet 81P/Wild 2 in January 2006. Preliminary examinations revealed the presence of a suite of organic compounds including several amines and amino acids, but the origin of these compounds could not be identified. Here, we present the carbon isotopic ratios of glycine and e-aminocaproic acid (EACA), the two most abundant amino acids, in Stardust-returned foil samples measured by gas chromatography-combustion-isotope ratio mass spectrometry coupled with quadrupole mass spectrometry (GC-CAMS/IRMS).

Paired measurements of K and Mg isotopes and clay authigenesis in marine sediments

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Dunlea, A. G.; Higgins, J. A.

2016-12-01

Despite its importance as a major sink for seawater K and Mg, estimates of clay authigenesis in marine sediments remain poorly constrained. Previous work on Mg isotope fractionation during clay formation has revealed a preferential uptake of 26Mg, yielding authigenic clay products with potentially distinct δ26Mg compared to the detrital component. In a similar manner, we aim to quantify the K isotope fractionation during authigenic clay formation and to use paired δ26Mg and δ41K measurements as proxies for the identification and quantification of authigenic clays in shallow and deep marine sedimentary systems. To better understand the behavior of paired Mg and K isotopes during authigenic clay formation in marine sediments, we measured δ26Mg and δ41K values of pore-fluids and sediments from ODP/IODP sites 1052, U1395, U1403 and U1366. We find that while pore-fluid K concentrations at sites 1052, U1395 and U1403 all decline with depth, δ41K profiles differ significantly. These differences might be a result of a complex interplay between clay authigenesis, sedimentation rate, and fractionation of K isotopes during diffusion. Results from 1-D diffusion-advection-reaction models suggest that, in contrast to Mg, diffusion may play an important role in determining the overall K isotope fractionation during clay authigenesis in sites with low-sedimentation rates. Sites with high sedimentation rates may act as close systems where diffusion is negligible. In such cases, K uptake can be modeled as a Rayleigh distillation process and K isotope fractionation can be estimated. Measurements of δ26Mg and δ41K of pore-fluids from site U1395 and bulk sediments from U1366 suggest that paired measurements of these isotopic systems in siliciclastic marine sediments can provide new insights into rates of marine clay authigenesis, a globally important but understudied component of many geochemical cycles.

Airborne water vapor DIAL research: System development and field measurements

NASA Technical Reports Server (NTRS)

Higdon, Noah S.; Browell, Edward V.; Ponsardin, Patrick; Chyba, Thomas H.; Grossmann, Benoist E.; Butler, Carolyn F.; Fenn, Marta A.; Mayor, Shane D.; Ismail, Syed; Grant, William B.

1992-01-01

This paper describes the airborne differential absorption lidar (DIAL) system developed at the NASA Langley Research Center for remote measurement of water vapor (H2O) and aerosols in the lower atmosphere. The airborne H2O DIAL system was flight tested aboard the NASA Wallops Flight Facility (WFF) Electra aircraft in three separate field deployments between 1989 and 1991. Atmospheric measurements were made under a variety of atmospheric conditions during the flight tests, and several modifications were implemented during this development period to improve system operation. A brief description of the system and major modifications will be presented, and the most significant atmospheric observations will be described.

High temporal resolution measurements of the isotopic composition of CH4 at the Lutjewad station, The Netherlands

NASA Astrophysics Data System (ADS)

Röckmann, Thomas; van der Veen, Carina; Chen, Huilin; Scheeren, Bert

2017-04-01

Isotope measurements can help constraining the atmospheric budget of the greenhouse gas methane (CH4) because different sources emit CH4 with slightly different isotopic composition. In the past, high precision isotope measurements have primarily been carried out by isotope ratio mass spectrometry on flask samples that are usually collected at relatively low temporal resolution. We have recently developed a fully automated gas chromatography - isotope ratio mass spectrometry system (GC-IRMS) for autonomous and unattended CH4 isotope measurements (δD and δ13C) in the field. The first deployment at the Cabauw Experimental Site for Atmospheric Research (CESAR) indicated that CH4 emissions from fossil fuel sources are overestimated in this region [1]. To further exploit the potential of this approach, the in situ system has been installed in November 2016 at the Lutjewad atmospheric monitoring and sampling site in the North of the Netherlands. This site is expected to sample also emissions from the large Groningen gas fields. The isotope measurements are expected to allow distinguishing these emissions from the agricultural emissions, which are also strong in this region. We will present the results from these ongoing measurements of δD and δ13C in CH4.. 1. Röckmann, T., et al., In situ observations of the isotopic composition of methane at the Cabauw tall tower site, Atmos. Chem. Phys., 2016. 16: 10469-10487.

Leaf water enrichment of stable water isotopes (δ18O and δD) in a mature oil palm plantation in Jambi province, Indonesia.

NASA Astrophysics Data System (ADS)

Bonazza, Mattia; Tjoa, Aiyen; Knohl, Alexander

2017-04-01

During the last few decades, Indonesia experienced rapid and large scale land-use change towards intensively managed crops, one of them is oil palm. This transition results in warmer and dryer conditions in microclimate. The impacts on the hydrological cycle and on water-use by plants are, however, not yet completely clear. Water stable isotopes are useful tracers of the hydrological processes and can provide means to partition evapotranspiration into evaporation and transpiration. A key parameter, however, is the enrichment of water stable isotope in plant tissue such as leaves that can provide estimates on the isotopic composition of transpiration. Here we present the results of a field campaign conducted in a mature oil palm plantation in Jambi province, Indonesia. We combined continuous measurements of water vapor isotopic composition and mixing ratio with isotopic analysis of water stored in different pools like oil palm leaves, epiphytes, trunk organic matter and soil collected over a three days period. Leaf enrichment varied from -2 ‰ to 10 ‰ relative to source (ground) water. The temporal variability followed Craig and Gordon model predictions for leaf water enrichment. An improved agreement was reached after considering the Péclet effect with an appropriate value of the characteristic length (L). Measured stomatal conductance (gs) on two different sets of leaves (top and bottom canopy) was mainly controlled by radiation (photosynthetically active radiation) and vapor pressure deficit. We assume that this control could be explained in conditions where soil water content is not representing a limiting factor. Understanding leaf water enrichment provides one step towards partitioning ET.

High temperature measurement of water vapor absorption

NASA Technical Reports Server (NTRS)

Keefer, Dennis; Lewis, J. W. L.; Eskridge, Richard

1985-01-01

An investigation was undertaken to measure the absorption coefficient, at a wavelength of 10.6 microns, for mixtures of water vapor and a diluent gas at high temperature and pressure. The experimental concept was to create the desired conditions of temperature and pressure in a laser absorption wave, similar to that which would be created in a laser propulsion system. A simplified numerical model was developed to predict the characteristics of the absorption wave and to estimate the laser intensity threshold for initiation. A non-intrusive method for temperature measurement utilizing optical laser-beam deflection (OLD) and optical spark breakdown produced by an excimer laser, was thoroughly investigated and found suitable for the non-equilibrium conditions expected in the wave. Experiments were performed to verify the temperature measurement technique, to screen possible materials for surface initiation of the laser absorption wave and to attempt to initiate an absorption wave using the 1.5 kW carbon dioxide laser. The OLD technique was proven for air and for argon, but spark breakdown could not be produced in helium. It was not possible to initiate a laser absorption wave in mixtures of water and helium or water and argon using the 1.5 kW laser, a result which was consistent with the model prediction.

Stable Isotope Measurements of Carbon Dioxide, Methane, and Hydrogen Sulfide Gas Using Frequency Modulation Spectroscopy

NASA Astrophysics Data System (ADS)

Nowak-Lovato, K.

2014-12-01

Seepage from enhanced oil recovery, carbon storage, and natural gas sites can emit trace gases such as carbon dioxide, methane, and hydrogen sulfide. Trace gas emission at these locations demonstrate unique light stable isotope signatures that provide information to enable source identification of the material. Light stable isotope detection through surface monitoring, offers the ability to distinguish between trace gases emitted from sources such as, biological (fertilizers and wastes), mineral (coal or seams), or liquid organic systems (oil and gas reservoirs). To make light stable isotope measurements, we employ the ultra-sensitive technique, frequency modulation spectroscopy (FMS). FMS is an absorption technique with sensitivity enhancements approximately 100-1000x more than standard absorption spectroscopy with the advantage of providing stable isotope signature information. We have developed an integrated in situ (point source) system that measures carbon dioxide, methane and hydrogen sulfide with isotopic resolution and enhanced sensitivity. The in situ instrument involves the continuous collection of air and records the stable isotope ratio for the gas being detected. We have included in-line flask collection points to obtain gas samples for validation of isotopic concentrations using our in-house isotope ratio mass spectroscopy (IRMS). We present calibration curves for each species addressed above to demonstrate the sensitivity and accuracy of the system. We also show field deployment data demonstrating the capabilities of the system in making live dynamic measurements from an active source.

Absolute measurements and certified reference material for iron isotopes using multiple-collector inductively coupled mass spectrometry.

PubMed

Zhou, Tao; Zhao, Motian; Wang, Jun; Lu, Hai

2008-01-01

Two enriched isotopes, 99.94 at.% 56Fe and 99.90 at.% 54Fe, were blended under gravimetric control to prepare ten synthetic isotope samples whose 56Fe isotope abundances ranged from 95% to 20%. For multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements typical polyatomic interferences were removed by using Ar and H2 as collision gas and operating the MC-ICP-MS system in soft mode. Thus high-precision measurements of the Fe isotope abundance ratios were accomplished. Based on the measurement of the synthetic isotope abundance ratios by MC-ICP-MS, the correction factor for mass discrimination was calculated and the results were in agreement with results from IRMM014. The precision of all ten correction factors was 0.044%, indicating a good linearity of the MC-ICP-MS method for different isotope abundance ratio values. An isotopic reference material was certified under the same conditions as the instrument was calibrated. The uncertainties of ten correction factors K were calculated and the final extended uncertainties of the isotopic certified Fe reference material were 5.8363(37) at.% 54Fe, 91.7621(51) at.% 56Fe, 2.1219(23) at.% 57Fe, and 0.2797(32) at.% 58Fe.

Stratospheric water vapor measurements at Thule, Greenland, by means of a new 22 GHz spectrometer

NASA Astrophysics Data System (ADS)

Mevi, Gabriele; Muscari, Giovanni; Mari, Massimo; Meloni, Daniela; Di Iorio, Tatiana; Pace, Giandomenico; di Sarra, Alcide; Cacciani, Marco

2017-04-01

A new 22 GHz water vapor spectrometer, VESPA-22 (water Vapour Emission Spectrometer for Polar Atmosphere), was installed in July 2016 at the Thule High Arctic Atmospheric Observatory (THAAO) located at Thule Air Base (76.5° N, 68.8° W), Greenland, and participated in the intensive measurement campaign of the Study of the water VApour in the polar AtmosPhere (SVAAP) project. After the campaign VESPA-22 has continued to carry out measurements in an autonomous mode and has now obtained more than 6 months of data. VESPA-22 was designed and built at the Istituto Nazionale di Geofisica and Vulcanologia (INGV) and measures the 22.235 GHz water vapor emission line with a bandwidth of 500 MHz and a frequency resolution of 31 kHz. The collected spectra are inverted using an optimal estimation algorithm in order to retrieve water vapour vertical profiles from about 26 to 72 km with a vertical resolution varying from 4 to 7.5 km. The spectrometer can produce 2 to 4 vertical profiles a day, depending on season and weather conditions. VESPA-22 also measures the atmospheric optical depth at 22 GHz and can therefore provide an estimate of precipitable water vapor (PWV) with a temporal resolution of few minutes. The instrument is calibrated every 30 minutes using noise diodes and tipping curves, and requires a calibration with liquid nitrogen (LN2) only once every few months. We will present water vapor stratospheric profiles over Thule obtained during an almost complete yearly cycle. The retrieved profiles have been compared with the Aura/MLS H2O dataset. During autumn 2016 the two datasets show a mean difference of less than 5% and a correlation coefficient of about 0.9 at all altitudes between 26 to 60 km.

Water Vapor Measurements by Howard University Raman Lidar during the WAVES 2006 Campaign

NASA Technical Reports Server (NTRS)

Adam, M.; Demoz, B. B.; Whiteman, D. N.; Venable, D. D.; Joseph E.; Gambacorta, A.; Wei, J.; Shephard, M. W.; Miloshevich, L. M.; Barnet, C. D.;

LASE measurements of water vapor and aerosol profiles during the Plains Elevated Convection at Night (PECAN) field experiment

NASA Astrophysics Data System (ADS)

Nehrir, A. R.; Ferrare, R. A.; Kooi, S. A.; Butler, C. F.; Notari, A.; Hair, J. W.; Collins, J. E., Jr.; Ismail, S.

2015-12-01

The Lidar Atmospheric Sensing Experiment (LASE) system was deployed on the NASA DC-8 aircraft during the Plains Elevated Convection At Night (PECAN) field experiment, which was conducted during June-July 2015 over the central and southern plains. LASE is an active remote sensor that employs the differential absorption lidar (DIAL) technique to measure range resolved profiles of water vapor and aerosols above and below the aircraft. The DC-8 conducted nine local science flights from June 30- July 14 where LASE sampled water vapor and aerosol fields in support of the PECAN primary science objectives relating to better understanding nocturnal Mesoscale Convective Systems (MCSs), Convective Initiation (CI), the Low Level Jet (LLJ), bores, and to compare different airborne and ground based measurements. LASE observed large spatial and temporal variability in water vapor and aerosol distributions in advance of nocturnal MCSs, across bores resulting from MCS outflow boundaries, and across the LLJ associated with the development of MCSs and CI. An overview of the LASE data collected during the PECAN field experiment will be presented where emphasis will be placed on variability of water vapor profiles in the vicinity of severe storms and intense convection in the central and southern plains. Preliminary comparisons show good agreement between coincident LASE and radiosonde water vapor profiles. In addition, an advanced water vapor DIAL system being developed at NASA Langley will be discussed.

First total-absorption spectroscopy measurement on the neutron-rich Cu isotopes

NASA Astrophysics Data System (ADS)

Naqvi, F.; Spyrou, A.; Liddick, S. N.; Larsen, A. C.; Guttormsen, M.; Bleuel, D. L.; Campo, L. C.; Couture, A.; Crider, B. P.; Dombos, A. C.; Ginter, T.; Lewis, R.; Mosby, S.; Perdikakis, G.; Prokop, C. P.; Quinn, S. J.; Renstrom, T.; Rubio, B.; Siem, S.

2015-10-01

The first beta-decay studies of 73-71Cu isotopes using the Total Absorption Spectroscopy (TAS) will be reported. The Cu isotopes have one proton outside the Z = 28 shell and hence are good candidates to probe the single-particle structure in the region.Theories predict weakening of the Z = 28 shell gap due to the tensor interaction between the valence πν single-particle orbitals. Comparing the beta-decay strength distributions in the daughter Zn isotopes to the theoretical calculations will provide a stringent test of the predictions. The experiment was performed at the National Superconducting Cyclotron Laboratory (NSCL) employing the TAS technique with the Summing NaI(Tl) detector, while beta decays were measured in the NSCL beta-counting system. The experimentally obtained total absorption spectra for the neutron-rich Cu isotopes will be presented and the implications of the extracted beta-feeding intensities will be discussed.

Laser-Based Measurements of OH, Temperature, and Water Vapor Concentration in a Hydrocarbon-Fueled Scramjet (POSTPRINT)

DTIC Science & Technology

2008-07-01

hours. The detector signals are post-processed with a software lock-in amplifier to recover the WMS-1f and WMS-2f signals. The TDLAS sensor utilizes...Figure 6. Schematic of TDLAS sensor for temperature and water vapor concentration. Fiber Diode lasers Grating Fiber Detectors Demultiplexer Multiplexer...within the combustor. Tunable diode laser- based absorption spectroscopy ( TDLAS ) is used to measure water vapor concentration and static temperature near

Spectroscopic Measurement of LEAD-204 Isotope Shift and LEAD-205 Nuclear Spin.

NASA Astrophysics Data System (ADS)

Schonberger, Peter

The isotope shift of ('204)Pb and the nuclear spin of 1.4 x 10('7)-y ('205)Pb was determined from a high -resolution optical measurement of the 6p('2) ('3)P(,o) -6p7s('3)P(,1)('o) 283.3-nm resonance line. The value of the shift, relative to ('208)Pb is -140.2(8) x 10('-3)cm(' -1), the negative sign indicating a shift to lower wave numbers. The precision is 3-4 times greater than that of previous measurements. The spin of ('205)Pb l = 5/2 was obtained from the measurement of the relative intensities of its three hyperfine components. This method of absorption spectroscopy determination of ground state nuclear spin is applicable to any stable or longlived isotope. High resolution optical absorption spectra were obtained with a 25.4cm diffraction grating in a 9.1m focal length Czerny-Turner spectrometer. A signal-averaging scanning technique was used to record the spectra. Increased precision in the isotope shift measurement was attained by using separated isotope samples of ('204)Pb and ('207)Pb. A controlled amount of the later was incorporated in the absorption cell to provide internal calibration by its 6p7s ('3)P(,1)('o) hfs separation. Absorption spectra were recorded for several optical thicknesses of the absorber. A single spin value of increased precision was derived from the entire set of combined data.

Methods of Measuring Vapor Pressures of Lubricants With Their Additives Using TGA and/or Microbalances

NASA Technical Reports Server (NTRS)

Scialdone, John J.; Miller, Michael K.; Montoya, Alex F.

1996-01-01

The life of a space system may be critically dependent on the lubrication of some of its moving parts. The vapor pressure, the quantity of the available lubricant, the temperature and the exhaust venting conductance passage are important considerations in the selection and application of a lubricant. In addition, the oil additives employed to provide certain properties of low friction, surface tension, antioxidant and load bearing characteristics, are also very important and need to be known with regard to their amounts and vapor pressures. This paper reports on the measurements and analyses carried out to obtain those parameters for two often employed lubricants, the Apiezon(TM)-C and the Krytox(TM) AB. The measurements were made employing an electronic microbalance and a thermogravimetric analyzer (TGA) modified to operate in a vacuum. The results have been compared to other data on these oils when available. The identification of the mass fractions of the additives in the oil and their vapor pressures as a function of the temperature were carried out. These may be used to estimate the lubricant life given its quantity and the system vent exhaust conductance. It was found that the Apiezon(TM)-C has three main components with different rates of evaporation while the Krytox(TM) did not indicate any measurable additive.

Properties of water vapor relevant to its measurement in the stratosphere and mesosphere

NASA Technical Reports Server (NTRS)

Longbothum, R. L.

1974-01-01

The literature on the concentrations of water vapor in the stratosphere and mesosphere was studied. It is estimated that the concentrations in these lie in the range from 0.1 ppm to 10 ppm. A survey was made of the scattering and radiative transfer properties of water vapor and the background constituents to determine the physical properties of importance to measurements of concentrations. It was determined that absorption and emission properties provide significant increases in sensitivity compared with the various scattering phenomena considered. Microwave absorption in the region of 22 GHz and 183 GHz and infrared absorption in the vibrational rotational band systems seem to be the most attractive techniques. Various experimental configurations are analyzed and compared.

The SPARC water vapor assessment II: intercomparison of satellite and ground-based microwave measurements

NASA Astrophysics Data System (ADS)

Nedoluha, Gerald E.; Kiefer, Michael; Lossow, Stefan; Gomez, R. Michael; Kämpfer, Niklaus; Lainer, Martin; Forkman, Peter; Christensen, Ole Martin; Oh, Jung Jin; Hartogh, Paul; Anderson, John; Bramstedt, Klaus; Dinelli, Bianca M.; Garcia-Comas, Maya; Hervig, Mark; Murtagh, Donal; Raspollini, Piera; Read, William G.; Rosenlof, Karen; Stiller, Gabriele P.; Walker, Kaley A.

2017-12-01

As part of the second SPARC (Stratosphere-troposphere Processes And their Role in Climate) water vapor assessment (WAVAS-II), we present measurements taken from or coincident with seven sites from which ground-based microwave instruments measure water vapor in the middle atmosphere. Six of the ground-based instruments are part of the Network for the Detection of Atmospheric Composition Change (NDACC) and provide datasets that can be used for drift and trend assessment. We compare measurements from these ground-based instruments with satellite datasets that have provided retrievals of water vapor in the lower mesosphere over extended periods since 1996. We first compare biases between the satellite and ground-based instruments from the upper stratosphere to the upper mesosphere. We then show a number of time series comparisons at 0.46 hPa, a level that is sensitive to changes in H2O and CH4 entering the stratosphere but, because almost all CH4 has been oxidized, is relatively insensitive to dynamical variations. Interannual variations and drifts are investigated with respect to both the Aura Microwave Limb Sounder (MLS; from 2004 onwards) and each instrument's climatological mean. We find that the variation in the interannual difference in the mean H2O measured by any two instruments is typically ˜ 1%. Most of the datasets start in or after 2004 and show annual increases in H2O of 0-1 % yr-1. In particular, MLS shows a trend of between 0.5 % yr-1 and 0.7 % yr-1 at the comparison sites. However, the two longest measurement datasets used here, with measurements back to 1996, show much smaller trends of +0.1 % yr-1 (at Mauna Loa, Hawaii) and -0.1 % yr-1 (at Lauder, New Zealand).

Measurement of Enzyme Isotope Effects.

PubMed

Kholodar, Svetlana A; Ghosh, Ananda K; Kohen, Amnon

2017-01-01

Enzyme isotope effects, or the kinetic effects of "heavy" enzymes, refer to the effect of isotopically labeled protein residues on the enzyme's activity or physical properties. These effects are increasingly employed in the examination of the possible contributions of protein dynamics to enzyme catalysis. One hypothesis assumed that isotopic substitution of all 12 C, 14 N, and nonexchangeable 1 H by 13 C, 15 N, and 2 H, would slow down protein picosecond to femtosecond dynamics without any effect on the system's electrostatics following the Born-Oppenheimer approximation. It was suggested that reduced reaction rates reported for several "heavy" enzymes accords with that hypothesis. However, numerous deviations from the predictions of that hypothesis were also reported. Current studies also attempt to test the role of individual residues by site-specific labeling or by labeling a pattern of residues on activity. It appears that in several systems the protein's fast dynamics are indeed reduced in "heavy" enzymes in a way that reduces the probability of barrier crossing of its chemical step. Other observations, however, indicated that slower protein dynamics are electrostatically altered in isotopically labeled enzymes. Interestingly, these effects appear to be system dependent, thus it might be premature to suggest a general role of "heavy" enzymes' effect on catalysis. © 2017 Elsevier Inc. All rights reserved.

The Sensitivity of Atmospheric Water Isotopes to Entrainment and Precipitation Efficiency in a Bulk Plume Model of Convection

NASA Astrophysics Data System (ADS)

Duan, S.; Wright, J. S.; Romps, D. M.

2016-12-01

Atmospheric water isotopes have been proposed as potentially powerful constraints on the physics of convective clouds and parameterizations of convective processes in models. We have previously derived an analytical model of water vapor (H2O) and one of its heavy isotopes (HDO) in convective environments based on a bulk-plume convective water budget in radiative convective equilibrium. This analytical model provides a useful starting point for examining the joint responses of water vapor and its isotopic composition to changes in convective parameters; however, certain idealistic assumptions are required to make the model analytically solvable. Here, we develop a more flexible numerical framework that enables a wider range of model configurations and includes additional isotopic tracers. This model provides a bridge between Rayleigh distillation, which is simple but inflexible, and more complicated convection schemes and cloud resolving models, which are more realistic but also more difficult to perturb and interpret. Application of realistic in-cloud water profiles in our model produces vertical distributions of δD that qualitatively match satellite observations from the Tropospheric Emission Spectrometer (TES). We test the sensitivity of water vapor and its isotopic composition to a wide range of perturbations in the model parameters and their vertical profiles. In this presentation, we focus especially on establishing constraints for convective entrainment and precipitation efficiency. We conclude by discussing the potential application of this model as part of a larger water isotope toolkit for use with offline diagnostics provided by reanalyses and GCMs.

Precise and traceable carbon isotope ratio measurements by multicollector ICP-MS: what next?

PubMed

Santamaria-Fernandez, Rebeca

2010-06-01

This article reviews recent developments in the use of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) to provide high-precision carbon isotope ratio measurements. MC-ICP-MS could become an alternative method to isotope ratio mass spectrometry (IRMS) for rapid carbon isotope ratio determinations in organic compounds and characterisation and certification of isotopic reference materials. In this overview, the advantages, drawbacks and potential of the method for future applications are critically discussed. Furthermore, suggestions for future improvements in terms of precision and sensitivity are made. No doubt, this is an exciting analytical challenge and, as such, hurdles will need to be cleared.

Piezoelectric trace vapor calibrator

NASA Astrophysics Data System (ADS)

Verkouteren, R. Michael; Gillen, Greg; Taylor, David W.

2006-08-01

The design and performance of a vapor generator for calibration and testing of trace chemical sensors are described. The device utilizes piezoelectric ink-jet nozzles to dispense and vaporize precisely known amounts of analyte solutions as monodisperse droplets onto a hot ceramic surface, where the generated vapors are mixed with air before exiting the device. Injected droplets are monitored by microscope with strobed illumination, and the reproducibility of droplet volumes is optimized by adjustment of piezoelectric wave form parameters. Complete vaporization of the droplets occurs only across a 10°C window within the transition boiling regime of the solvent, and the minimum and maximum rates of trace analyte that may be injected and evaporated are determined by thermodynamic principles and empirical observations of droplet formation and stability. By varying solution concentrations, droplet injection rates, air flow, and the number of active nozzles, the system is designed to deliver—on demand—continuous vapor concentrations across more than six orders of magnitude (nominally 290fg/lto1.05μg/l). Vapor pulses containing femtogram to microgram quantities of analyte may also be generated. Calibrated ranges of three explosive vapors at ng/l levels were generated by the device and directly measured by ion mobility spectrometry (IMS). These data demonstrate expected linear trends within the limited working range of the IMS detector and also exhibit subtle nonlinear behavior from the IMS measurement process.

A hydrogen gas-water equilibration method produces accurate and precise stable hydrogen isotope ratio measurements in nutrition studies

USDA-ARS?s Scientific Manuscript database

Stable hydrogen isotope methodology is used in nutrition studies to measure growth, breast milk intake, and energy requirement. Isotope ratio MS is the best instrumentation to measure the stable hydrogen isotope ratios in physiological fluids. Conventional methods to convert physiological fluids to ...

Measurement of longitudinal sulfur isotopic variations by laser ablation MC-ICP-MS in single human hair strands.

PubMed

Santamaria-Fernandez, Rebeca; Giner Martínez-Sierra, Justo; Marchante-Gayón, J M; García-Alonso, J Ignacio; Hearn, Ruth

2009-05-01

A new method for the measurement of longitudinal variations of sulfur isotope amount ratios in single hair strands using a laser ablation system coupled to a multicollector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) is reported here for the first time. Ablation parameters have been optimized for the measurement of sulfur isotope ratios in scalp human hair strands of 80-120-microm thickness and different washing procedures have been evaluated. The repeatability of the method has been tested and the ability to measure sulfur isotopic variations in 1,000-microm-long hair segments has been evaluated. A horse hair sample previously characterized for carbon and nitrogen isotope ratios in an interlaboratory study has been characterized by LA-MC-ICP-MS to be used as an in-house standard for the bracketing of human hair strands. (34)S/(32)S isotope amount ratios have been measured and corrected for instrumental mass bias adopting the external standardization approach using National Institute of Standards and Technology (NIST) RM8553 and full uncertainty budgets have been calculated using the Kragten approach. Results are reported as both (34)S/(32)S isotope amount ratios and deltaS(V-CDT) values (sulfur isotopic differences relative to a reference sample expressed in the Vienna Canyon Diablo Troilite (V-CDT) scale) calculated using NIST RM8553, NIST RM8554, and NIST RM8556 to anchor results to the V-CDT scale. The main advantage of the new method versus conventional gas source isotope ratio mass spectrometry measurements is that longitudinal variations in sulfur isotope amount ratios can be resolved. Proof of concept is shown with human scalp hair strands from three individuals, two UK residents and one traveler (long periods of time abroad). The method enables monitoring of longitudinal isotope ratio variations in single hair strands. Absolute ratios are reported and delta(34)S(V-CDT) values are plotted for comparison. Slight variations of <1.2 per

Natural Ca Isotope Composition of Urine as a Rapid Measure of Bone Mineral Balance

NASA Astrophysics Data System (ADS)

Skulan, J.; Gordon, G. W.; Morgan, J.; Romaniello, S. J.; Smith, S. M.; Anbar, A. D.

2011-12-01

Naturally occurring stable Ca isotope variations in urine are emerging as a powerful tool to detect changes in bone mineral balance. Bone formation depletes soft tissue of light Ca isotopes while bone resorption releases isotopically light Ca into soft tissue. Previously published work found that variations in Ca isotope composition could be detected at 4 weeks of bed rest in a 90-day bed rest study (data collected at 4, 8 and 12 weeks). A new 30-day bed rest study involved 12 patients on a controlled diet, monitored for 7 days prior to bed rest and 7 days post bed rest. Samples of urine, blood and food were collected throughout the study. Four times daily blood samples and per void urine samples were collected to monitor diurnal or high frequency variations. An improved chemical purification protocol, followed by measurement using multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) allowed accurate and precise determinations of mass-dependent Ca isotope variations in these biological samples to better than ±0.2% (δ44/42Ca) on <25 μg of Ca. Results from this new study show that Ca isotope ratios shift in a direction consistent with net bone loss after just 7 days, long before detectible changes in bone density by X-ray measurements occur. Consistent with this interpretation, the Ca isotope variations track changes observed in N-teleopeptide, a bone resorption biomarker. Bone-specific alkaline phosphatase, a bone formation biomarker, is unchanged over this period. Ca isotopes can in principle be used to quantify net changes in bone mass. Using a mass-balance model, our results indicate an average loss of 0.62 ± 0.16 % in bone mass over the course of this 30-day study. This is consistent with the rate of bone loss in longer-term studies as seen by X-ray measurements. This Ca isotope technique should accelerate the pace of discovery of new treatments for bone disease and provide novel insights into the dynamics of bone metabolism.

Simulation of carbon isotope discrimination of the terrestrial biosphere

NASA Astrophysics Data System (ADS)

Suits, N. S.; Denning, A. S.; Berry, J. A.; Still, C. J.; Kaduk, J.; Miller, J. B.; Baker, I. T.

2005-03-01

We introduce a multistage model of carbon isotope discrimination during C3 photosynthesis and global maps of C3/C4 plant ratios to an ecophysiological model of the terrestrial biosphere (SiB2) in order to predict the carbon isotope ratios of terrestrial plant carbon globally at a 1° resolution. The model is driven by observed meteorology from the European Centre for Medium-Range Weather Forecasts (ECMWF), constrained by satellite-derived Normalized Difference Vegetation Index (NDVI) and run for the years 1983-1993. Modeled mean annual C3 discrimination during this period is 19.2‰; total mean annual discrimination by the terrestrial biosphere (C3 and C4 plants) is 15.9‰. We test simulation results in three ways. First, we compare the modeled response of C3 discrimination to changes in physiological stress, including daily variations in vapor pressure deficit (vpd) and monthly variations in precipitation, to observed changes in discrimination inferred from Keeling plot intercepts. Second, we compare mean δ13C ratios from selected biomes (Broadleaf, Temperate Broadleaf, Temperate Conifer, and Boreal) to the observed values from Keeling plots at these biomes. Third, we compare simulated zonal δ13C ratios in the Northern Hemisphere (20°N to 60°N) to values predicted from high-frequency variations in measured atmospheric CO2 and δ13C from terrestrially dominated sites within the NOAA-Globalview flask network. The modeled response to changes in vapor pressure deficit compares favorably to observations. Simulated discrimination in tropical forests of the Amazon basin is less sensitive to changes in monthly precipitation than is suggested by some observations. Mean model δ13C ratios for Broadleaf, Temperate Broadleaf, Temperate Conifer, and Boreal biomes compare well with the few measurements available; however, there is more variability in observations than in the simulation, and modeled δ13C values for tropical forests are heavy relative to observations

WVR-GPS comparison measurements and calibration of the 20-32 GHz tropospheric water vapor absorption model.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keihm, S. J.; Bar-Server, Y.; Liljegren, J. C.

2002-06-01

Collocated measurements of opacity (from water vapor radiometer brightness temperatures) and wet path delay (from ground-based tracking of global positioning satellites) are used to constrain the model of atmospheric water vapor absorption in the 20-32 GHz band. A differential approach is presented in which the slope of opacity-versus-wet delay data is used as the absorption model constraint. This technique minimizes the effects of radiometric calibration errors and oxygen model uncertainties in the derivation of a best-fit vapor absorption model. A total of approximately five months of data was obtained from two experiment sites. At the Cloud and Radiation Testbed (CART)more » site near Lamont, Oklahoma, three independent water vapor radiometers (WVRs) provided near-continuous opacity measurements over the interval July-September 1998. At the NASA/Goldstone tracking station in the California desert two WVRs; obtained opacity data over the September-October 1997 interval. At both sites a Global Positioning Satellite (GPS) receiver and surface barometer obtained the data required for deriving the zenith wet delays over the same time frames. Measured values of the opacity-versus-wet delay slope parameter were obtained at four WVR frequencies (20.7, 22.2, 23.8, and 31.4 GHz) and compared with predictions of four candidate absorption models referenced in the literature. With one exception, all three models provide agreement within 5% of the opacity-versus-wet delay slope measurements at all WVR frequencies at both sites. One model provides agreement for all channels at both sites to the 2-3% level. This absorption model accuracy level represents a significant improvement over that attainable using radiosondes.« less

A systematic approach for the accurate and rapid measurement of water vapor transmission through ultra-high barrier films

NASA Astrophysics Data System (ADS)

Kiese, Sandra; Kücükpinar, Esra; Reinelt, Matthias; Miesbauer, Oliver; Ewender, Johann; Langowski, Horst-Christian

2017-02-01

Flexible organic electronic devices are often protected from degradation by encapsulation in multilayered films with very high barrier properties against moisture and oxygen. However, metrology must be improved to detect such low quantities of permeants. We therefore developed a modified ultra-low permeation measurement device based on a constant-flow carrier-gas system to measure both the transient and stationary water vapor permeation through high-performance barrier films. The accumulation of permeated water vapor before its transport to the detector allows the measurement of very low water vapor transmission rates (WVTRs) down to 2 × 10-5 g m-2 d-1. The measurement cells are stored in a temperature-controlled chamber, allowing WVTR measurements within the temperature range 23-80 °C. Differences in relative humidity can be controlled within the range 15%-90%. The WVTR values determined using the novel measurement device agree with those measured using a commercially available carrier-gas device from MOCON®. Depending on the structure and quality of the barrier film, it may take a long time for the WVTR to reach a steady-state value. However, by using a combination of the time-dependent measurement and the finite element method, we were able to estimate the steady-state WVTR accurately with significantly shorter measurement times.

Neutron-Induced Fission Cross Section Measurements for Full Suite of Uranium Isotopes

NASA Astrophysics Data System (ADS)

Laptev, Alexander; Tovesson, Fredrik; Hill, Tony

2010-11-01

A well established program of neutron-induced fission cross section measurement at Los Alamos Neutron Science Center (LANSCE) is supporting the Fuel Cycle Research program (FC R&D). The incident neutron energy range spans energies from sub-thermal energies up to 200 MeV by measuring both the Lujan Center and the Weapons Neutron Research center (WNR). Conventional parallel-plate fission ionization chambers with actinide deposited foils are used as a fission detector. The time-of-flight method is implemented to measure neutron energy. Counting rate ratio from investigated and standard U-235 foils is translated into fission cross section ratio. Different methods of normalization for measured ratio are employed, namely, using of actinide deposit thicknesses, normalization to evaluated data, etc. Finally, ratios are converted to cross sections based on the standard U-235 fission cross section data file. Preliminary data for newly investigated isotopes U-236 and U-234 will be reported. Those new data complete a full suite of Uranium isotopes, which were investigated with presented experimental approach. When analysis of the new measured data will is completed, data will be delivered to evaluators. Having data for full set of Uranium isotopes will increase theoretical modeling capabilities and make new data evaluations much more reliable.

On the calibration of continuous, high-precision delta18O and delta2H measurements using an off-axis integrated cavity output spectrometer.

PubMed

Wang, Lixin; Caylor, Kelly K; Dragoni, Danilo

2009-02-01

The (18)O and (2)H of water vapor serve as powerful tracers of hydrological processes. The typical method for determining water vapor delta(18)O and delta(2)H involves cryogenic trapping and isotope ratio mass spectrometry. Even with recent technical advances, these methods cannot resolve vapor composition at high temporal resolutions. In recent years, a few groups have developed continuous laser absorption spectroscopy (LAS) approaches for measuring delta(18)O and delta(2)H which achieve accuracy levels similar to those of lab-based mass spectrometry methods. Unfortunately, most LAS systems need cryogenic cooling and constant calibration to a reference gas, and have substantial power requirements, making them unsuitable for long-term field deployment at remote field sites. A new method called Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS) has been developed which requires extremely low-energy consumption and neither reference gas nor cryogenic cooling. In this report, we develop a relatively simple pumping system coupled to a dew point generator to calibrate an ICOS-based instrument (Los Gatos Research Water Vapor Isotope Analyzer (WVIA) DLT-100) under various pressures using liquid water with known isotopic signatures. Results show that the WVIA can be successfully calibrated using this customized system for different pressure settings, which ensure that this instrument can be combined with other gas-sampling systems. The precisions of this instrument and the associated calibration method can reach approximately 0.08 per thousand for delta(18)O and approximately 0.4 per thousand for delta(2)H. Compared with conventional mass spectrometry and other LAS-based methods, the OA-ICOS technique provides a promising alternative tool for continuous water vapor isotopic measurements in field deployments. Copyright 2009 John Wiley & Sons, Ltd.

Advances in Methane Isotope Measurements via Direct Absorption Spectroscopy with Applications to Oil and Gas Source Characterization

NASA Astrophysics Data System (ADS)

Yacovitch, T. I.; Herndon, S. C.; Roscioli, J. R.; Petron, G.; Shorter, J. H.; Jervis, D.; McManus, J. B.; Nelson, D. D.; Zahniser, M. S.; Kolb, C. E., Jr.

2015-12-01

Instrumental developments in the measurement of multiple isotopes of methane (12CH4, 13CH4 and 12CH3D) are presented. A first generation 8-micron instrument quantifies 12CH4 and 13CH4 at a 1-second rate via tunable infrared direct absorption spectroscopy (TILDAS). A second generation instrument uses two 3-micron intraband cascade lasers in an Aerodyne dual laser chassis for simultaneous measurement of 12CH4, 13CH4 and 12CH3D. Sensitivity and noise performance improvements are examined. The isotopic signature of methane provides valuable information for emission source identification of this greenhouse gas. A first generation spectrometer has been deployed in the field on a mobile laboratory along with a sophisticated 4-tank calibration system. Calibrations are done on an agressive schedule, allowing for the correction of measured isotope ratios to an absolute isotope scale. Distinct isotopic signatures are found for a number of emission sources in the Denver-Julesburg Basin: oil and gas gathering stations, compressor stations and processing plants; a municipal landfill, and dairy/cattle operations. The isotopic signatures are compared with measured ethane/methane ratios. These direct absorption measurements have larger uncertainties than samples measured via gas chromatography-mass spectrometry, but have several advantages over canister sampling methods: individual sources of short duration are easier to isolate; calibrated isotope ratio results are available immediately; replicate measurements on a single source are easily performed; and the number of sources sampled is not limited by canister availability and processing time.

Volatile particles measured by vapor-particle separator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Meng -Dawn; Corporan, Edwin

Vapor-Particle Separator (VPS) is a new technology developed for characterization of the volatile fraction of particulate matter in a combustion aerosol population. VPS incorporates a novel metallic membrane and operates in a cross-flow filtration mode for separation of vapor and solid (i.e. non-volatile) particles. Demonstration of the VPS technology on aircraft engine-emitted particles has led to the improvement of the technology and increased confidence on the robustness of its field performance. In this study, the performance of the VPS was evaluated against the Particle Measurement Programme (PMP) volatile particle remover (VPR), a standardized device used in heavy duty diesel enginesmore » for separation and characterization of non-volatile particulate matter. Using tetracontane particles in the laboratory reveals that the VPS performed reasonably well in removing the volatile species. In the field conditions, a single-mode particle size distribution was found for emitted particles from a T63 turboshaft engine at both idle and cruise engine power conditions. Removal of the volatile T63 engine particles by the VPS was consistent with that of PMP VPR. In tests on an F117 turbofan engine, the size distribution at the idle (4% rated) engine power condition was found to be bimodal, with the first mode consisting of particles smaller than 10nm, which are believed to be mostly semi-volatile particles, while the second mode of larger size was a mixture of semi-volatile and non-volatile particles. The distribution was single modal at the 33% rated engine power with no secondary mode observed. Altogether, for particles emitted by both engines, the removal efficiency of the VPS appears to surpass that of the PMP VPR by 8-10%.« less

Volatile particles measured by vapor-particle separator

DOE PAGES

Cheng, Meng -Dawn; Corporan, Edwin

2016-08-25

Vapor-Particle Separator (VPS) is a new technology developed for characterization of the volatile fraction of particulate matter in a combustion aerosol population. VPS incorporates a novel metallic membrane and operates in a cross-flow filtration mode for separation of vapor and solid (i.e. non-volatile) particles. Demonstration of the VPS technology on aircraft engine-emitted particles has led to the improvement of the technology and increased confidence on the robustness of its field performance. In this study, the performance of the VPS was evaluated against the Particle Measurement Programme (PMP) volatile particle remover (VPR), a standardized device used in heavy duty diesel enginesmore » for separation and characterization of non-volatile particulate matter. Using tetracontane particles in the laboratory reveals that the VPS performed reasonably well in removing the volatile species. In the field conditions, a single-mode particle size distribution was found for emitted particles from a T63 turboshaft engine at both idle and cruise engine power conditions. Removal of the volatile T63 engine particles by the VPS was consistent with that of PMP VPR. In tests on an F117 turbofan engine, the size distribution at the idle (4% rated) engine power condition was found to be bimodal, with the first mode consisting of particles smaller than 10nm, which are believed to be mostly semi-volatile particles, while the second mode of larger size was a mixture of semi-volatile and non-volatile particles. The distribution was single modal at the 33% rated engine power with no secondary mode observed. Altogether, for particles emitted by both engines, the removal efficiency of the VPS appears to surpass that of the PMP VPR by 8-10%.« less

Isotopic Ratios Measured in the Dust of Comet 67P/Churyumov-Gerasimenko Using Rosetta/COSIMA

NASA Astrophysics Data System (ADS)

Paquette, J. A.; Engrand, C.; Hilchenbach, M.; Fray, N.; Stenzel, O.; Merouane, S.

2017-12-01

The COSIMA instrument aboard the Rosetta orbiter captured dust from the coma of comet 67P/Churyumov-Gerasimenko on metal targets. The dust was then imaged, and some of it was subjected to Time of Flight Secondary Ion Mass Spectrometry, yielding information on the dust composition. Isotopic ratios for species such as oxygen and sulfur have been measured for a number of COSIMA dust particles and these measurements are presented in this talk. Isotopic ratios for several species have been measured for a number of comets, but with the exception of the Stardust results, these have been measurements in the gas phase. The measurements presented here are from the solid phase, most probably from silicate or carbonaceous material. The isotopic ratios measured in the dust are compared to the measurements in the gas, to values measured in the insoluble organic matter of meteorites, and to the values measured in interplanetary dust particles and Antarctic micrometeorites.

Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

NASA Astrophysics Data System (ADS)

Das, R.; Odom, A. L.

2007-12-01

Mercury is long known as a common environmental contaminant. In methylated form it is even more toxic and the methylation process is facilitated by microbial activities. Methyl mercury easily crosses cell membrane and accumulates in soft tissues of fishes and finally biomagnifies with increasing trophic levels. Natural variations in the isotopic composition of mercury have been reported and such variations have emphasized mass dependent fractionations, while theory and laboratory experiments indicate that mass-independent isotopic fractionation (MIF) effects are likely to be found as well. This study focuses on the MIF of mercury isotopes in the soft tissues of fishes. Samples include both fresh water and marine fish, from different continents and oceans. Approximately 1 gm of fish soft tissue was dissolved in 5 ml of conc. aqua regia for 24 hrs and filtered through a ¬¬¬100 μm filter paper and diluted with DI water. Hg is measured as a gaseous phase generated by reduction of the sample with SnCl2 in a continuous- flow cold-vapor generator connected to a Thermo-Finnigan Neptune MC-ICPMS. To minimize instrumental fractionation isotope ratios were measured by sample standard bracketing and reported as δ‰ relative to NIST SRM 3133 Hg standard where δAHg = [(A Hg/202Hg)sample/(A Hg/202Hg)NIST313] -1 ×1000‰. In this study we have measured the isotope ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg and 204Hg/202Hg. In all the fish samples δ198Hg, δ200Hg, δ202Hg, δ204Hg define a mass- dependent fractionation sequence, where as the δ199Hg and δ201Hg depart from the mass- dependent fractionation line and indicate an excess of the odd-N isotopes. The magnitude of the deviation (ΔAHg where A=199 or 201) as obtained by difference between the measured δ199Hg and δ201Hg of the samples and the value obtained by linear scaling defined by the even-N isotopes ranges from approximately 0.2 ‰ to 3‰. The ratios of Δ199Hg /Δ201Hg range from 0.8 to 1

New approaches to the Moon's isotopic crisis.

PubMed

Melosh, H J

2014-09-13

Recent comparisons of the isotopic compositions of the Earth and the Moon show that, unlike nearly every other body known in the Solar System, our satellite's isotopic ratios are nearly identical to the Earth's for nearly every isotopic system. The Moon's chemical make-up, however, differs from the Earth's in its low volatile content and perhaps in the elevated abundance of oxidized iron. This surprising situation is not readily explained by current impact models of the Moon's origin and offers a major clue to the Moon's formation, if we only could understand it properly. Current ideas to explain this similarity range from assuming an impactor with the same isotopic composition as the Earth to postulating a pure ice impactor that completely vaporized upon impact. Several recent proposals follow from the suggestion that the Earth-Moon system may have lost a great deal of angular momentum during early resonant interactions. The isotopic constraint may be the most stringent test yet for theories of the Moon's origin. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

Steps toward identifying a biogeochemical signal in non-equilibrium methane clumped isotope measurements

NASA Astrophysics Data System (ADS)

Douglas, P. M.; Eiler, J. M.; Sessions, A. L.; Dawson, K.; Walter Anthony, K. M.; Smith, D. A.; Lloyd, M. K.; Yanay, E.

2016-12-01

Microbially produced methane is a globally important greenhouse gas, energy source, and biological substrate. Methane clumped isotope measurements have recently been developed as a new analytical tool for understanding the source of methane in different environments. When methane forms in isotopic equilibrium clumped isotope values are determined by formation temperature, but in many cases microbial methane clumped isotope values deviate strongly from expected equilibrium values. Indeed, we observe a very wide range of clumped isotope values in microbial methane, which are likely strongly influenced by kinetic isotope effects, but thus far the biological and environmental parameters controlling this variability are not understood. We will present data from both culture experiments and natural environments to explore patterns of variability in non-equilibrium clumped isotope values on temporal and spatial scales. In methanogen batch cultures sampled at different time points along a growth curve we observe significant variability in clumped isotope values, with values decreasing from early to late exponential growth. Clumped isotope values then increase during stationary growth. This result is consistent with previous work suggesting that differences in the reversibility of methanogenesis related to metabolic rates control non-equilibrium clumped isotope values. Within single lakes in Alaska and Sweden we observe substantial variability in clumped isotope values on the order of 5‰. Lower clumped isotope values are associated with larger 2H isotopic fractionation between water and methane, which is also consistent with a kinetic isotope effect determined by the reversibility of methanogenesis. Finally, we analyzed a time-series clumped isotope compositions of methane emitted from two seeps in an Alaskan lake over several months. Temporal variability in these seeps is on the order of 2‰, which is much less than the observed spatial variability within the lake

Seasonality of Oxygen isotope composition in cow (Bos taurus) hair and its model interpretation

NASA Astrophysics Data System (ADS)

Chen, Guo; Schnyder, Hans; Auerswald, Karl

2017-04-01

Oxygen isotopes in animal and human tissues are expected to be good recorders of geographical origin and migration histories based on the isotopic relationship between hair oxygen and annual precipitation and the well-known spatial pattern of oxygen isotope composition in meteoric water. However, seasonal variation of oxygen isotope composition may diminish the origin information in the tissues. Here the seasonality of oxygen isotope composition in tail hair was investigated in a domestic suckler cow (Bos taurus) that underwent different ambient conditions, physiological states, and keeping and feeding strategies during five years. A detailed mechanistic model involving in ambient conditions, soil properties and animal physiology was built to explain this variation. The measured oxygen isotope composition in hair was significantly related (p<0.05) to the isotope composition in meteoric water in a regression analysis. Modelling suggested that this relation was only partly derived from the direct influence of feed moisture. Ambient conditions (temperature, moisture) did not only influence the isotopic signal of precipitation but also affected the animal itself (drinking water demand, transcutaneous vapor etc.). The clear temporal variation thus resulted from complex interactions with multiple influences. The twofold influence of ambient conditions via the feed and via the animal itself is advantageous for tracing the geographic origin because the oxygen isotope composition is then less influenced by variations in moisture uptake; however, it is unfavorable for indicating the production system, e.g. to distinguish between milk produced from fresh grass or from silage.

Application of neodymium isotope ratio measurements for the origin assessment of uranium ore concentrates.

PubMed

Krajkó, Judit; Varga, Zsolt; Yalcintas, Ezgi; Wallenius, Maria; Mayer, Klaus

2014-11-01

A novel procedure has been developed for the measurement of (143)Nd/(144)Nd isotope ratio in various uranium-bearing materials, such as uranium ores and ore concentrates (UOC) in order to evaluate the usefulness and applicability of variations of (143)Nd/(144)Nd isotope ratio for provenance assessment in nuclear forensics. Neodymium was separated and pre-concentrated by extraction chromatography and then the isotope ratios were measured by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method was validated by the measurement of standard reference materials (La Jolla, JB-2 and BCR-2) and the applicability of the procedure was demonstrated by the analysis of uranium samples of world-wide origin. The investigated samples show distinct (143)Nd/(144)Nd ratio depending on the ore type, deposit age and Sm/Nd ratio. Together with other characteristics of the material in question, the Nd isotope ratio is a promising signature for nuclear forensics and suggests being indicative of the source material, the uranium ore. Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.